JP2014141688A - Phenol resin, epoxy resin, epoxy resin composition and cured product thereof - Google Patents
Phenol resin, epoxy resin, epoxy resin composition and cured product thereof Download PDFInfo
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- JP2014141688A JP2014141688A JP2014101091A JP2014101091A JP2014141688A JP 2014141688 A JP2014141688 A JP 2014141688A JP 2014101091 A JP2014101091 A JP 2014101091A JP 2014101091 A JP2014101091 A JP 2014101091A JP 2014141688 A JP2014141688 A JP 2014141688A
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- Prior art keywords
- epoxy resin
- phenol
- resin composition
- phenol resin
- present
- 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.)
- Pending
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 99
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 39
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical class COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000002989 phenols Chemical class 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 abstract description 15
- 230000001070 adhesive effect Effects 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000004918 carbon fiber reinforced polymer Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000003566 sealing material Substances 0.000 abstract description 3
- 239000008199 coating composition Substances 0.000 abstract 1
- 239000012774 insulation material Substances 0.000 abstract 1
- -1 etc. Substances 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- 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 13
- 239000000047 product Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000005770 Eugenol Substances 0.000 description 8
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 8
- 229960002217 eugenol Drugs 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 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
- 238000010438 heat treatment Methods 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000019256 formaldehyde Nutrition 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000007789 sealing 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
- 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 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid 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
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 229920005610 lignin Polymers 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
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000005844 Thymol Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229960000790 thymol Drugs 0.000 description 3
- 239000002966 varnish Substances 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
- 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 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
- 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-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
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 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
- 238000009835 boiling Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 2
- 239000010634 clove oil Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 229930014626 natural product Natural products 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
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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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- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 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
- 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
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、地球上の二酸化炭素を積極的に固定化して得られ、地球温暖化防止に期待がもたれる植物由来の骨格を主骨格とするフェノール樹脂、エポキシ樹脂を含む組成物とその成形体に関するものであり、本発明は特に電気電子部品用絶縁材料（高信頼性半導体封止材料など）及び積層板（プリント配線板、ビルドアップ基板など）やＣＦＲＰを始めとする各種複合材料、接着剤、塗料等に有用である硬化性樹脂組成物を与えるエポキシ樹脂及び該組成物の硬化物に関する。 The present invention relates to a composition containing a phenolic resin, an epoxy resin, and a molded article thereof, obtained by positively fixing carbon dioxide on the earth and having a plant-derived skeleton that is expected to prevent global warming as a main skeleton. In particular, the present invention particularly relates to insulating materials for electrical and electronic parts (such as highly reliable semiconductor sealing materials) and various composite materials including laminated boards (printed wiring boards, build-up boards, etc.) and CFRP, adhesives, The present invention relates to an epoxy resin that provides a curable resin composition useful for paints and the like, and a cured product of the composition.
現在、植物を原料とする化学品や高分子材料が脚光を浴びている。
２０世紀において石油資源は、プラスチックの原料やエネルギーとして採掘され限りなく使用されてきた。しかし、近年、石油を初めとする化石資源の枯渇化等が環境問題となっている。そこで、石油や石炭由来のような化石資源ではなく、天然物由来の資源（いわゆる非化石資源）を利用した環境破壊の恐れの少ないプラスチック材料の開発が盛んに進められている。
例えば、植物は太陽の光をエネルギーとして、水分と大気中の炭酸ガスを吸収することによって成長する。植物（もしくはそこから抽出される成分）を原料とする材料の場合、太陽エネルギーを原料の製造エネルギーとして有効に利用していることから、化石エネルギーの使用量が少なくてすむことになる。これにより、化石資源の使用を節約できることになる。
At present, chemicals and polymer materials made from plants are in the spotlight.
In the 20th century, petroleum resources have been mined and used as plastic raw materials and energy. However, in recent years, depletion of fossil resources such as oil has become an environmental problem. Therefore, development of plastic materials that are less likely to cause environmental destruction is being actively promoted using natural product-derived resources (so-called non-fossil resources) instead of fossil resources such as those derived from petroleum and coal.
For example, plants grow by absorbing moisture and carbon dioxide in the atmosphere using sunlight as energy. In the case of materials using plants (or components extracted therefrom) as raw materials, the amount of fossil energy used can be reduced because solar energy is effectively used as raw material production energy. This saves the use of fossil resources.
エポキシ樹脂組成物は作業性及びその硬化物の優れた電気特性、耐熱性、接着性、耐湿性（耐水性）等により電気・電子部品、構造用材料、接着剤、塗料等の分野で幅広く用いられている。このような分野においても植物由来の化合物を使用したエポキシ樹脂が検討されている。具体的には特許文献２においてはリグニンのエポキシ化物およびその硬化物が報告されている。しかしながら、植物より抽出されたリグニンをそのまま使用していることから、非常に高い分子量の化合物であり、成形性に問題が生じる場合がある。また、官能基も少なく、電気・電子材料の用途に耐えうる高度な信頼性を持たせることが難しい。 Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been. In such fields, epoxy resins using plant-derived compounds have been studied. Specifically, Patent Document 2 reports a lignin epoxidized product and a cured product thereof. However, since lignin extracted from a plant is used as it is, it is a very high molecular weight compound, which may cause a problem in moldability. In addition, since it has few functional groups, it is difficult to provide a high degree of reliability that can withstand the use of electrical and electronic materials.
また、オイゲノールやチモールを使用したエポキシ樹脂としては特許文献３に記載されているが、その立体的な要因から多官能化が難しく、高い耐熱性が要求される基板材料等の分野においては使いづらいという問題があった。 Moreover, although it describes in patent document 3 as an epoxy resin using eugenol or thymol, it is difficult to use in the field | area of a substrate material etc. in which polyfunctionalization is difficult from the three-dimensional factor, and high heat resistance is requested | required. There was a problem.
本発明の目的は植物由来の骨格を主骨格とするフェノール樹脂、エポキシ樹脂、およびそれらを含有するエポキシ樹脂組成物の提供であって、特に電気電子部品用絶縁材料（高信頼性半導体封止材料など）及び積層板（プリント配線板、ビルドアップ基板など）やＣＦＲＰを始めとする各種複合材料、接着剤、塗料等に有用である、作業性、耐熱性、機械特性を有するフェノール樹脂、エポキシ樹脂、およびそのエポキシ樹脂組成物を提供すること。 An object of the present invention is to provide a phenol resin, an epoxy resin, and an epoxy resin composition containing them, which have a plant-derived skeleton as a main skeleton, and particularly an insulating material for electrical and electronic parts (highly reliable semiconductor sealing material) Etc.) and laminated boards (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, etc., phenolic resins and epoxy resins with workability, heat resistance and mechanical properties And an epoxy resin composition thereof.
本発明者らは前記課題を解決するため鋭意研究の結果、本発明を完成した。即ち、本発明は、
（１）オイゲノール誘導体を３０重量％以上含有するフェノール類（少なくとも1つのフェノール性水酸基を有する化合物）とホルムアルデヒド（もしくはその合成等価体）との反応により得られるフェノール樹脂、
（２）上記（１）に記載のフェノール樹脂をエピハロヒドリンと反応させることにより得られるエポキシ樹脂、
（３）（ａ）エポキシ樹脂および（ｂ）上記（１）に記載のフェノール樹脂を含有するエポキシ樹脂組成物、
（４）（ｃ）上記（２）に記載のエポキシ樹脂及び（ｄ）硬化剤を含有するエポキシ樹脂組成物、
（５）（ｃ）上記（２）に記載のエポキシ樹脂及び（ｂ）上記（１）に記載のフェノール樹脂を含有するエポキシ樹脂組成物、
（６）上記（３）〜（５）のいずれか１項に記載のエポキシ樹脂組成物を硬化してなる硬化物、
に関する。
The present inventors have completed the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention
(1) a phenol resin obtained by a reaction of phenols (compounds having at least one phenolic hydroxyl group) containing eugenol derivatives of 30% by weight or more with formaldehyde (or a synthetic equivalent thereof),
(2) An epoxy resin obtained by reacting the phenol resin described in (1) above with epihalohydrin,
(3) (a) an epoxy resin and (b) an epoxy resin composition containing the phenol resin according to (1) above,
(4) (c) an epoxy resin composition containing the epoxy resin according to (2) and (d) a curing agent,
(5) (c) an epoxy resin composition comprising the epoxy resin according to (2) and (b) the phenol resin according to (1) above,
(6) Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of said (3)-(5),
About.
本発明のフェノール樹脂、エポキシ樹脂は、高度な硬化物性を有する硬化物を与え、電気電子部品用絶縁材料（高信頼性半導体封止材料など）及び積層板（プリント配線板、ビルドアップ基板など）やＣＦＲＰを始めとする各種複合材料、接着剤、塗料等に有用であり、天然物由来の化合物であるため化石エネルギーの使用量の低減に寄与する。 The phenolic resin and epoxy resin of the present invention give a cured product having a high degree of cured material, and insulating materials for electrical and electronic parts (such as highly reliable semiconductor encapsulating materials) and laminates (printed wiring boards, build-up substrates, etc.) It is useful for various composite materials including CFRP, CFRP, adhesives, paints, etc., and contributes to the reduction of the amount of fossil energy used because it is a compound derived from natural products.
本発明のフェノール樹脂は、オイゲノール誘導体を３０重量％以上、好ましくは５０重量％以上、特に好ましくは７０〜１００重量％含有するフェノール類（少なくとも1つのフェノール性水酸基を有する化合物）をノボラック化することで得られる。以下、オイゲノールについて説明する。
＜オイゲノール(eugenol)＞
チョウジ油、ウイキョウ油、ケイヒ油の主成分の1つであり、シキミ酸経路で生合成されるフェニルプロパノイド系物質である。オイゲノールは医薬品として口腔内殺菌薬、虫歯の鎮痛などに用いるほか、バニリンの製造原料となる。例えば、チョウジ油からであれば、アルカリ水溶液を適量加え、浸透して他の油を除いてから希硫酸を加えてオイゲノールを析出させ、洗浄、乾燥後減圧蒸留によって精留するという手法が一般に知られている。
本発明においてオイゲノール誘導体とは、オイゲノールから派生される化合物を示し、具体的にはオイゲノールの転移反応により製造されるイソオイゲノールが挙げられる。
The phenol resin of the present invention is a novolak form of phenols (compounds having at least one phenolic hydroxyl group) containing 30% by weight or more, preferably 50% by weight or more, particularly preferably 70 to 100% by weight of an eugenol derivative. It is obtained by. Hereinafter, eugenol will be described.
<Eugenol>
It is one of the main components of clove oil, fennel oil, and cinnamon oil, and is a phenylpropanoid substance biosynthesized through the shikimic acid pathway. Eugenol is used as a pharmaceutical product for oral bactericides and caries analgesia, and as a raw material for producing vanillin. For example, from clove oil, it is generally known to add an appropriate amount of alkaline aqueous solution, permeate and remove other oils, add dilute sulfuric acid to precipitate eugenol, wash, dry and then rectify by vacuum distillation. It has been.
In the present invention, the eugenol derivative refers to a compound derived from eugenol, and specific examples include isoeugenol produced by a transfer reaction of eugenol.
本発明においてオイゲノール誘導体と併用できるフェノール類について説明する。
フェノール類は、芳香環に少なくとも１個のフェノール性水酸基を有する化合物であれば使用できる。具体的には、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、エチルフェノール、ｎ−プロピルフェノール、イソプロピルフェノール、ｔ−ブチルフェノール、オクチルフェノール、ノニルフェノール、フェニルフェノール、シクロヘキシルフェノール、キシレノール、メチルプロピルフェノール、メチルブチルフェノール、チモール等のフェノール類が挙げられるがフェノール性水酸基を有する限りこれらに限定されるものではない。また、これらフェノール類は単独でまたは２種以上を混合して使用することができる。
The phenols that can be used in combination with the eugenol derivative in the present invention will be described.
The phenol can be used as long as it has at least one phenolic hydroxyl group in the aromatic ring. Specifically, phenol, o-cresol, m-cresol, p-cresol, ethylphenol, n-propylphenol, isopropylphenol, t-butylphenol, octylphenol, nonylphenol, phenylphenol, cyclohexylphenol, xylenol, methylpropylphenol, Although phenols, such as methylbutylphenol and thymol, are mentioned, it is not limited to these as long as it has a phenolic hydroxyl group. Moreover, these phenols can be used individually or in mixture of 2 or more types.
本発明のフェノール樹脂は、オイゲノール誘導体、ホルムアルデヒド（およびその合成等価体、例えば、ホルマリン、パラホルムアルデヒド等が挙げられる。以下ホルムアルデヒド類と称する）、必要により溶媒の存在下、触媒を加えて加熱することにより得られる。また、オイゲノール誘導体及び／またはチモール並びに必要によりフェノール類及び溶媒の混合物と触媒の混合物を加熱しているところにホルムアルデヒド類を徐々に添加してもよい。反応時間は５〜１５０時間、反応温度は４０〜１５０℃である。このようにして得られたフェノール樹脂は用途によって、精製せずに用いることもできるが、通常、反応終了後に反応混合物を中和してから、加熱減圧下において未反応原料及び溶媒類を除去する事で精製して各種用途に使用する。なお、この中和工程は、燐酸二水素ナトリウムを添加してもよいし、水洗などでも可能であるが、両者を併用するとより簡便で効果的である。 The phenolic resin of the present invention is heated by adding a catalyst in the presence of a eugenol derivative, formaldehyde (and synthetic equivalents thereof such as formalin, paraformaldehyde, etc., hereinafter referred to as formaldehyde), and if necessary, a solvent. Is obtained. In addition, formaldehydes may be gradually added to a heated mixture of eugenol derivative and / or thymol and, if necessary, a mixture of phenols and solvent and a catalyst. The reaction time is 5 to 150 hours, and the reaction temperature is 40 to 150 ° C. The phenolic resin thus obtained can be used without purification depending on the use, but usually the reaction mixture is neutralized after completion of the reaction, and then unreacted raw materials and solvents are removed under heating and reduced pressure. It can be refined and used for various purposes. This neutralization step may be performed by adding sodium dihydrogen phosphate or washing with water, but it is more convenient and effective to use both in combination.
本発明のフェノール樹脂の合成において使用できる溶媒としては、メタノール、エタノール、プロパノール、イソプロパノール、トルエン、キシレンなどが挙げられるがこれらに限定されるものではなく、単独でも２種以上併用してもよい。溶媒を使用する場合、その使用量はフェノール類１００重量部に対し、通常５〜５００重量部、好ましくは１０〜３００重量部の範囲である。 Examples of the solvent that can be used in the synthesis of the phenol resin of the present invention include methanol, ethanol, propanol, isopropanol, toluene, xylene, and the like. However, the solvent is not limited to these, and may be used alone or in combination of two or more. When a solvent is used, the amount used is usually 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of phenols.
触媒としては酸性、塩基性いずれの触媒でも使用できる。用いうる酸性触媒の具体例としては塩酸、硫酸、リン酸等の鉱酸類；シュウ酸、トルエンスルホン酸、酢酸等の有機酸類；タングステン酸等のヘテロポリ酸、活性白土、無機酸、塩化第二錫、塩化亜鉛、塩化第二鉄等、その他酸性を示す有機、無機酸塩類、等のノボラック樹脂製造用に通常使用される酸性触媒などが挙げられる。用いうる塩基性触媒の具体例としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属水酸化物、ナトリウムメトキシド、ナトリウムエトキシド、カリウムメトキシド、カリウムエトキシド、カリウム−ｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシド、マグネシウムメトキシド、マグネシウムエトキシド等のアルカリ土類金属アルコキシド等が挙げられる。またアミン系の触媒を使用することもでき、トリエチルアミン、エタノールアミン、ピリジン、ピペリジン、モルホリン等が挙げられる。特にアミン系の触媒を使用する場合は溶媒として兼用することもできる。これら触媒は、前述に挙げた物に限定されるものではなく、単独でも２種以上を併用してもよい。触媒の使用量は、オイゲノール誘導体、必要により使用するフェノール類の総量に対し、通常０．００５〜２．０倍モル、好ましくは０．０１〜１．１倍モルの範囲である。なお、触媒を溶媒として使用する場合は、オイゲノール誘導体、必要により使用するフェノール類の総量に対し、３０〜２００重量％程度添加することが好ましい。 As the catalyst, either acidic or basic catalysts can be used. Specific examples of acidic catalysts that can be used include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropolyacids such as tungstic acid, activated clays, inorganic acids, stannic chloride , Zinc chloride, ferric chloride, and other acidic catalysts such as organic and inorganic acid salts that are usually used for producing novolak resins. Specific examples of basic catalysts that can be used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, sodium methoxide. Alkali metal alkoxides such as sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, and alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide. An amine-based catalyst can also be used, and examples thereof include triethylamine, ethanolamine, pyridine, piperidine, morpholine and the like. In particular, when an amine-based catalyst is used, it can also be used as a solvent. These catalysts are not limited to those mentioned above, and may be used alone or in combination of two or more. The usage-amount of a catalyst is 0.005-2.0 times mole normally with respect to the total amount of eugenol derivative and the phenols used as needed, Preferably it is the range of 0.01-1.1 times mole. In addition, when using a catalyst as a solvent, it is preferable to add about 30-200 weight% with respect to the total amount of eugenol derivatives and the phenols used as needed.
オイゲノール誘導体のノボラック化反応は、単純なホルムアルデヒド類との反応によるメチレン結合の生成だけでなく、オイゲノール誘導体に含まれるアリル基もしくはプロペニル基とフェノール核との結合、あるいはそれらの重合による結合が生成している可能性もあるが、同定が困難である。得られた樹脂は分子量分布を有する無定形の樹脂となる。 The novolak reaction of eugenol derivatives not only generates methylene bonds by reaction with simple formaldehydes, but also bonds between allyl or propenyl groups contained in eugenol derivatives and phenol nuclei, or bonds due to their polymerization. May be difficult to identify. The obtained resin becomes an amorphous resin having a molecular weight distribution.
本発明のフェノール樹脂は、そのままで熱可塑性プラスチック（もしくはその原料）として使用したり、下記するようなエポキシ樹脂の原料やその硬化剤として使用したりすることもできる。 The phenol resin of the present invention can be used as it is as a thermoplastic (or a raw material thereof), or as a raw material for an epoxy resin and a curing agent thereof as described below.
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、本発明のフェノール樹脂とエピハロヒドリンとを反応させることで得ることができる。
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 can be obtained by reacting the phenol resin of the present invention with epihalohydrin.
本発明のエポキシ樹脂を得る反応において、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使用でき、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フェノール樹脂またはビスフェノール化合物の水酸基１モルに対し通常３〜２０モル、好ましくは４〜１０モルである。 In the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin. In the present invention, epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 3-20 mol normally with respect to 1 mol of hydroxyl groups of a phenol resin or a bisphenol compound, Preferably it is 4-10 mol.
上記反応において使用しうる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、固形物を利用してもよく、その水溶液を使用してもよい。水溶液を使用する場合は該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、または常圧下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でもよい。アルカリ金属水酸化物の使用量は原料フェノール樹脂の水酸基１モルに対して通常０．９０〜１．５モルであり、好ましくは０．９５〜１．２５モル、より好ましくは０．９９〜１．１５モルである。 Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The amount of alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99 to 1 mol per mol of hydroxyl group of the starting phenol resin. .15 moles.
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は好ましい。４級アンモニウム塩の使用量としては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 order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol resin.
この際、メタノール、エタノール、イソプロピルアルコール、ｔ−ブタノールなどのアルコール類、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。 At this time, it is preferable for the reaction to proceed by adding an alcohol such as methanol, ethanol, isopropyl alcohol, or t-butanol, an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, or dioxane.
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重量％、好ましくは４〜３０重量％である。また非プロトン性極性溶媒を用いる場合はエピハロヒドリンの使用量に対し通常５〜１００重量％、好ましくは１０〜８０重量％である。 When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-30 weight%. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.
反応温度は通常３０〜９０℃であり、好ましくは３５〜８０℃である。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を水洗後、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。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、回収したエポキシ樹脂をトルエン、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反応を行い、閉環を確実なものにすることも出来る。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原料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、好ましくは０．０５〜０．２モルである。反応温度は通常５０〜１２０℃、反応時間は通常０．５〜２時間である。 The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin 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 added. The reaction can be carried out to ensure the ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the starting phenol resin used for epoxidation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
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が得られる。
ここで、本発明のフェノール樹脂又はエポキシ樹脂は多官能であれば、硬化が３次元的に進み易く、高耐熱性、機械的特性において高い特性が期待できるため、好ましい。具体的には、本発明のフェノール樹脂又はエポキシ樹脂において分子量分布を有する多量体に繋がった構造、すなわち数平均分子量が４００以上であることが好ましい。
After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.
Here, if the phenol resin or epoxy resin of the present invention is polyfunctional, curing is likely to proceed three-dimensionally, and high characteristics in high heat resistance and mechanical characteristics can be expected. Specifically, it is preferable that the structure connected to the multimer having a molecular weight distribution in the phenol resin or epoxy resin of the present invention, that is, the number average molecular weight is 400 or more.
このようにして得られるエポキシ樹脂はその骨格に非化石燃料由来の骨格を有するばかりでなく、従来のたとえばリグニン由来の化合物等に比べ、取り扱い、および硬化性等にも優れ、電気電子材料に有用なエポキシ樹脂となる。また、本発明のエポキシ樹脂は、アクリル酸との反応により光硬化性を有するエポキシアクリレート、およびその誘導体とすることも可能である他、カーボネート化合物、オキサゾリドン樹脂等、多様な骨格への変換も可能であり、種々の用途に適用できる。 The epoxy resin thus obtained not only has a non-fossil fuel-derived skeleton in its skeleton, but also has excellent handling and curability compared to conventional compounds derived from lignin, for example, and is useful for electrical and electronic materials. Epoxy resin. In addition, the epoxy resin of the present invention can be converted into various skeletons such as an epoxy acrylate having photo-curability and a derivative thereof by reaction with acrylic acid, and a carbonate compound, an oxazolidone resin, and the like. It can be applied to various uses.
以下に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エポキシ樹脂と硬化剤を含有し、少なくともエポキシ樹脂として本発明のエポキシ樹脂を含有するか、硬化剤として本発明のフェノール樹脂を含有する。なお、本発明のエポキシ樹脂組成物において、エポキシ樹脂または硬化剤として、他の成分を使用する場合、非石油原料由来のものが好ましい。
また、特に、本発明のエポキシ樹脂、フェノール樹脂は作業性が非常に改善されていることから、従来知られているリグニン由来の化合物と併用することで、エポキシ樹脂組成物の改質剤の役割に使用することも可能である。
The epoxy resin composition of the present invention is described below.
The epoxy resin composition of the present invention contains an epoxy resin and a curing agent, and at least contains the epoxy resin of the present invention as an epoxy resin, or contains the phenol resin of the present invention as a curing agent. In addition, when using another component as an epoxy resin or a hardening | curing agent in the epoxy resin composition of this invention, the thing derived from a non-petroleum raw material is preferable.
In particular, since the workability of the epoxy resin and phenol resin of the present invention is greatly improved, the role of a modifier of the epoxy resin composition can be obtained by using it together with a conventionally known lignin-derived compound. It can also be used.
上記（４）及び（５）記載の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は単独でまたは他のエポキシ樹脂と併用して使用することが出来る。併用する場合、本発明のエポキシ樹脂の全エポキシ樹脂中に占める割合は３０重量％以上が好ましく、特に４０重量％以上が好ましい。ただし、本発明のエポキシ樹脂をエポキシ樹脂組成物の改質剤として使用する場合は、エポキシ樹脂組成物中で１〜３０重量％を占める割合で添加する。 In the epoxy resin composition of the present invention described in the above (4) and (5), the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when using the epoxy resin of this invention as a modifier of an epoxy resin composition, it adds in the ratio which occupies 1-30 weight% in an epoxy resin composition.
本発明のエポキシ樹脂と併用し得る他のエポキシ樹脂のとしては、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 may be used alone or in combination of two or more.
上記（３）及び（５）記載の本発明のエポキシ樹脂組成物において、本発明のフェノール樹脂は、単独でまたは他の硬化剤と併用して使用することが出来る。併用する場合、本発明のフェノール樹脂またはビスフェノール化合物の全硬化剤中に占める割合は３０重量％以上が好ましく、特に４０重量％以上が好ましい。ただし、本発明のフェノール樹脂またはビスフェノール化合物をエポキシ樹脂組成物の改質剤として使用する場合は、エポキシ樹脂組成物中で１〜３０重量％の割合となるよう添加する。 In the epoxy resin composition of the present invention described in the above (3) and (5), the phenol resin of the present invention can be used alone or in combination with other curing agents. When used in combination, the proportion of the phenol resin or bisphenol compound of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when using the phenol resin or bisphenol compound of this invention as a modifier of an epoxy resin composition, it adds so that it may become a 1-30 weight% ratio in an epoxy resin composition.
本発明のフェノール樹脂と併用し得る他の硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノール系化合物、カルボン酸系化合物などが挙げられる。用いう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、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、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、本発明のフェノール樹脂、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、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、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、これらに限定されるものではない。これらは単独で用いてもよく、２種以上を用いてもよい。 Examples of other curing agents that can be used in combination with the phenol resin of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenolic resin of the present invention, bisphenol A, bisphenol F Bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-bi Enyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 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, furfural, 4 , 4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chlorome E) polycondensates with benzene, 1,4′-bis (methoxymethyl) benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, Although the condensate of a terpene and phenols is mentioned, it is not limited to these. These may be used alone or in combination of two or more.
上記（３）記載の本発明のエポキシ樹脂組成物において、（ａ）成分であるエポキシ樹脂としては、上記他のエポキシ樹脂等が挙げられる。
上記（４）記載の本発明のエポキシ樹脂組成物において、（ｄ）成分である硬化剤としては、上記他の硬化剤等が挙げられる。
In the epoxy resin composition of the present invention described in (3) above, examples of the epoxy resin as the component (a) include the other epoxy resins described above.
In the epoxy resin composition of the present invention described in (4) above, examples of the curing agent as component (d) include the other curing agents described above.
上記（３）〜（４）記載の本発明のエポキシ樹脂組成物において硬化剤の使用量は、エポキシ樹脂のエポキシ基１当量に対して０．５〜１．５当量が好ましく、０．６〜１．２当量が特に好ましい。エポキシ基１当量に対して、０．５当量に満たない場合、あるいは１．５当量を超える場合、いずれも硬化が不完全になり良好な硬化物性が得られない恐れがある。 In the epoxy resin composition of the present invention described in the above (3) to (4), the amount of the curing agent used is preferably 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin, and is preferably 0.6 to 1.2 equivalents are particularly preferred. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.
また上記硬化剤を用いる際に硬化促進剤を併用しても差し支えない。用いうる硬化促進剤としては、例えば、２−メチルイミダゾール、２−エチルイミダゾール、２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、２−（ジメチルアミノメチル）フェノール、トリエチレンジアミン、トリエタノールアミン、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、ジフェニルホスフィン、トリブチルホスフィン等の有機ホスフィン類、オクチル酸スズなどの金属化合物、テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・エチルトリフェニルボレート等のテトラ置換ホスホニウム・テトラ置換ボレート、２−エチル−４−メチルイミダゾール・テトラフェニルボレート、Ｎ−メチルモルホリン・テトラフェニルボレート等のテトラフェニルボロン塩などが挙げられる。硬化促進剤を使用する場合の使用量はエポキシ樹脂１００重量部に対して０．０１〜１５重量部が必要に応じ用いられる。 Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, Triethanolamine, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, Tetraphenylphosphonium / tetraphenylborate, tetrasubstituted phosphonium / tetrasubstituted borate such as tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmol Such as tetraphenyl boron salts such as phosphorus-tetraphenylborate and the like. When the curing accelerator is used, the amount used is 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.
更に、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やシランカップリング材、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。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。これらは単独で用いてもよく、２種以上を用いてもよい。これら無機充填剤は、用途によりその使用量は異なるが、例えば半導体の封止剤用途に使用する場合はエポキシ樹脂組成物の硬化物の耐熱性、耐湿性、力学的性質、難燃性などの面からエポキシ樹脂組成物中で２０重量％以上占める割合で使用するのが好ましく、より好ましくは３０重量％以上であり、４０〜９５重量％を占める割合で使用するのがさらに好ましい。 Furthermore, an inorganic filler, a silane coupling material, a release agent, various compounding agents such as a pigment, and various thermosetting resins 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 may be used alone or in combination of two or more. These inorganic fillers may be used in different amounts depending on the application. For example, when used for semiconductor encapsulants, the heat resistance, moisture resistance, mechanical properties, flame retardancy, etc. of the cured epoxy resin composition From the aspect, it is preferably used in a proportion of 20% by weight or more in the epoxy resin composition, more preferably 30% by weight or more, and further preferably in a proportion of 40 to 95% by weight.
更に本発明のエポキシ樹脂組成物には、必要に応じて公知の添加剤を配合することが出来る。用いうる添加剤の具体例としては、ポリブタジエン及びこの変性物、アクリロニトリル共重合体の変性物、ポリフェニレンエーテル、ポリスチレン、ポリエチレン、ポリイミド、フッ素樹脂、マレイミド系化合物、シアネート樹脂（もしくはそのプレポリマー）、シリコーンゲル、シリコーンオイル、並びにシリカ、アルミナ、炭酸カルシウム、石英粉、アルミニウム粉末、グラファイト、タルク、クレー、酸化鉄、酸化チタン、窒化アルミニウム、アスベスト、マイカ、ガラス粉末、ガラス繊維、ガラス不織布または、カーボン繊維等の無機充填材、シランカップリング剤のような充填材の表面処理剤、離型剤、カーボンブラック、フタロシアニンブルー、フタロシアニングリーン等の着色剤が挙げられる。 Furthermore, a known additive can be blended in the epoxy resin composition of the present invention as necessary. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluorine resin, maleimide compound, cyanate resin (or its prepolymer), silicone Gel, silicone oil, silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, glass fiber, glass nonwoven fabric or carbon fiber Inorganic fillers such as, surface treatment agents for fillers such as silane coupling agents, release agents, colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
本発明のエポキシ樹脂組成物は、上記各成分を均一に混合することにより得られる。そして、本発明のエポキシ樹脂組成物は従来知られている方法と同様の方法で容易にその硬化物とすることができる。例えば、エポキシ樹脂と硬化剤、並びに必要により硬化促進剤及び無機充填剤、配合剤、各種熱硬化性樹脂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することより本発明のエポキシ樹脂組成物を得て、そのエポキシ樹脂組成物を溶融注型法あるいはトランスファー成型法やインジェクション成型法、圧縮成型法などによって成型し、更に８０〜２００℃で２〜１０時間に加熱することにより硬化物を得ることができる。 The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. And the epoxy resin composition of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. For example, an epoxy resin and a curing agent and, if necessary, a curing accelerator and an inorganic filler, a compounding agent, and various thermosetting resins are mixed thoroughly using an extruder, kneader, roll, etc. as necessary until uniform. Thus, the epoxy resin composition of the present invention is obtained, and the epoxy resin composition is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and further, 2 to 10 at 80 to 200 ° C. A cured product can be obtained by heating for hours.
また本発明のエポキシ樹脂組成物は場合により溶剤を含んでいてもよい。溶剤を含むエポキシ樹脂組成物（エポキシ樹脂ワニス）はガラス繊維、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、本発明のエポキシ樹脂組成物の硬化物とすることができる。このエポキシ樹脂ワニスの溶剤含量は、内割りで通常１０〜７０重量％、好ましくは１５〜７０重量％程度である。該溶剤としては例えばγ−ブチロラクトン類、Ｎ−メチルピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルイミダゾリジノン等のアミド系溶剤、テトラメチレンスルフォン等のスルフォン類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルモノアセテート、プロピレングリコールモノブチルエーテル等のエーテル系溶剤、好ましくは低級アルキレングリコールモノ又はジ低級アルキルエーテル、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、好ましくは２つのアルキル基が同一でも異なってもよいジ低級アルキルケトン、トルエン、キシレンなどの芳香族系溶剤が挙げられる。これらは単独で合っても、また２以上の混合溶媒であってもよい。 Moreover, the epoxy resin composition of the present invention may optionally contain a solvent. An epoxy resin composition (epoxy resin varnish) containing a solvent is formed by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. By this, it can be set as the hardened | cured material of the epoxy resin composition of this invention. The solvent content of the epoxy resin varnish is usually about 10 to 70% by weight, and preferably about 15 to 70% by weight. Examples of the solvent include amide solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone, tetra Sulfones such as methylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, preferably lower alkylene glycol mono or di-lower alkyl ether, methyl ethyl ketone, Ketone-based solvents such as methyl isobutyl ketone, preferably di-lower alkyl ketones in which two alkyl groups may be the same or different; Emissions, and aromatic solvents such as xylene. These may be used alone or in combination of two or more.
また、剥離フィルム上に前記ワニスを塗布し加熱下で溶剤を除去、Ｂステージ化を行うことによりシート状の接着剤を得ることが出来る。このシート状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出来る。 Moreover, a sheet-like adhesive can be obtained by applying the varnish on a release film, removing the solvent under heating, and performing B-stage. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
作業性、成形性の観点から本発明で得られる硬化物の軟化点は２０〜１７０℃であることが好ましく、４０〜１２０℃であることがより好ましい。この範囲より軟化点が低いとタック性、べた付きがあり、取り扱いが困難となる。また、この範囲より軟化点が高いと流動性が悪く、成形性が悪くなる。 From the viewpoint of workability and moldability, the softened point of the cured product obtained in the present invention is preferably 20 to 170 ° C, and more preferably 40 to 120 ° C. If the softening point is lower than this range, tackiness and stickiness occur, and handling becomes difficult. On the other hand, if the softening point is higher than this range, the fluidity is poor and the moldability is poor.
本発明で得られる硬化物は各種用途に使用できる。具体的にはエポキシ樹脂等の熱硬化性樹脂が使用される一般の用途が挙げられ、例えば、接着剤、塗料、コーティング剤、成形材料（シート、フィルム、ＦＲＰ等を含む）、絶縁材料（プリント基板、電線被覆等を含む）、封止剤の他、他樹脂等への添加剤等が挙げられる。 The cured product obtained in the present invention can be used for various applications. Specific examples include general uses in which thermosetting resins such as epoxy resins are used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (prints) In addition to a sealing agent, an additive to other resins and the like are included.
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。これらのうち電子材料用の接着剤としては、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。 Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
封止剤としては、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など用のポッティング、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など用のといったポッティング封止、フリップチップなどの用のアンダーフィル、ＱＦＰ、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を含む）などを挙げることができる。 As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.
次に本発明を実施例により更に具体的に説明するが、以下において部は特に断わりのない限り重量部である。尚、本発明はこれら実施例に限定されるものではない。また実施例において、エポキシ当量はＪＩＳ Ｋ−７２３６、軟化点はＪＩＳ Ｋ−７２３４に準じた方法で測定した。また、ゲルパーミエーションクロマトグラフィー（以下、「ＧＰＣ」という）の測定においては以下の通りである。
カラムは、Ｓｈｏｄｅｘ ＳＹＳＴＥＭ−２１カラム（ＫＦ−８０３Ｌ、ＫＦ−８０２．５（×２本）、ＫＦ−８０２）、連結溶離液はテトラヒドロフラン、流速は１ｍｌ／ｍｉｎ．カラム温度は４０℃、また検出はＵＶ（２５４ｎｍ）で行い、検量線はＳｈｏｄｅｘ製標準ポリスチレンを使用した。
EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. Moreover, in the Example, the epoxy equivalent was measured by the method according to JIS K-7236, and the softening point according to JIS K-7234. Further, the measurement in gel permeation chromatography (hereinafter referred to as “GPC”) is as follows.
The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., detection was performed at UV (254 nm), and a standard polystyrene manufactured by Shodex was used for the calibration curve.
実施例１
撹拌機、還流冷却管、撹拌装置、ディーンスターク管を備えたフラスコに、窒素パージを施しながら、イソオイゲノール１６４部、キシレン１００部、トルエン１００部、ｐ−トルエンスルホン酸３部を加え、７０℃でホルマリン１０５部を１時間かけて滴下し、そのまま１時間撹拌した。その後、水を抜きながら３０時間反応を行った。
反応終了後、９０℃まで冷却し、無水燐酸水素２ナトリウム１５部を加え、そのまま３０分撹拌し、系中の酸をクエンチした。ここに水２００部を加え、水洗後、さらに水１００部／回で廃水が中性になるまで水洗を繰り返し、得られた有機層をロータリーエバポレータで加熱減圧下、トルエン、キシレン等の低沸分を留去することで、本発明のフェノール樹脂（ＰＡ１）１６２部が得られた。得られた樹脂は赤褐色であり、軟化点８３．２℃、１５０℃における溶融粘度（ＩＣＩ コーン＃３）は０．０８Ｐａ・ｓであった。また重量平均分子量は７２４、数平均分子量は５８７であった。
Example 1
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube, 164 parts of isoeugenol, 100 parts of xylene, 100 parts of toluene and 3 parts of p-toluenesulfonic acid were added while purging with nitrogen. The formalin 105 parts was dripped over 1 hour, and it stirred as it was for 1 hour. Thereafter, the reaction was carried out for 30 hours while draining water.
After completion of the reaction, the mixture was cooled to 90 ° C., 15 parts of anhydrous sodium hydrogenphosphate was added, and the mixture was stirred as it was for 30 minutes to quench the acid in the system. 200 parts of water was added thereto, and after washing with water, washing with water was repeated at 100 parts / time until the wastewater became neutral, and the resulting organic layer was heated with a rotary evaporator under reduced pressure to lower the boiling point of toluene, xylene, etc. To obtain 162 parts of phenol resin (PA1) of the present invention. The obtained resin was reddish brown, and its melt viscosity (ICI cone # 3) at a softening point of 83.2 ° C. and 150 ° C. was 0.08 Pa · s. The weight average molecular weight was 724, and the number average molecular weight was 587.
実施例２
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実施例１で得られたフェノール樹脂（ＰＡ１）８０部、エピクロロヒドリン２８０部、メタノール５０部を加え、７０℃にまで昇温した。次いでフレーク状の水酸化ナトリウム２１部を９０分かけて分割添加した後、更に７０℃で１時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて１４０℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン２００部を加え溶解し、７０℃にまで昇温した。撹拌下で３０重量％の水酸化ナトリウム水溶液５部を加え、１時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂（ＥＰ１）を９７部得た。得られたエポキシ樹脂のエポキシ当量は２２３ｇ／ｅｑ．、軟化点が５９．５℃、１５０℃における溶融粘度（ＩＣＩ コーン＃３）は０．０５Ｐａ・ｓであった。また重量平均分子量は１０２２、数平均分子量は６６７であった。
Example 2
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 80 parts of the phenol resin (PA1) obtained in Example 1, 280 parts of epichlorohydrin and 50 parts of methanol were added while purging with nitrogen, and 70 ° C. The temperature was raised to. Next, 21 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 200 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 5 parts of a 30% by weight sodium hydroxide aqueous solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was obtained at 180 ° C. using a rotary evaporator. 97 parts of epoxy resin (EP1) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 223 g / eq. The melt viscosity (ICI cone # 3) at a softening point of 59.5 ° C. and 150 ° C. was 0.05 Pa · s. The weight average molecular weight was 1022, and the number average molecular weight was 667.
実施例３
撹拌機、還流冷却管、撹拌装置、ディーンスターク管を備えたフラスコに、窒素パージを施しながら、オイゲノール１６４部、キシレン１００部、トルエン１００部、ｐ−トルエンスルホン酸３部を加え、７０℃でホルマリン１０５部を１時間かけて滴下し、そのまま１時間撹拌した。その後、水を抜きながら３０時間反応を行った。
反応終了後、９０℃まで冷却し、無水燐酸水素２ナトリウム１５部を加え、そのまま３０分撹拌し、系中の酸をクエンチした。ここに水２００部を加え、水洗後、さらに水１００部／回で廃水が中性になるまで水洗を繰り返し、得られた有機層をロータリーエバポレータで加熱減圧下、トルエン、キシレン等の低沸分を留去することで、本発明のフェノール樹脂（ＰＡ１）１６２部が得られた。得られた樹脂は赤褐色であり、軟化点４８℃、１５０℃における溶融粘度（ＩＣＩ コーン＃１）は０．２０Ｐａ・ｓであった。また重量平均分子量は１０２４、数平均分子量は７３３であった。
Example 3
Add 164 parts eugenol, 100 parts xylene, 100 parts toluene, 3 parts p-toluenesulfonic acid to a flask equipped with a stirrer, reflux condenser, stirrer, and Dean-Stark tube while purging with nitrogen. Formalin 105 parts was dripped over 1 hour, and it stirred as it was for 1 hour. Thereafter, the reaction was carried out for 30 hours while draining water.
After completion of the reaction, the mixture was cooled to 90 ° C., 15 parts of anhydrous sodium hydrogenphosphate was added, and the mixture was stirred as it was for 30 minutes to quench the acid in the system. 200 parts of water was added thereto, and after washing with water, washing with water was repeated at 100 parts / time until the wastewater became neutral, and the resulting organic layer was heated with a rotary evaporator under reduced pressure to lower the boiling point of toluene, xylene, etc. To obtain 162 parts of phenol resin (PA1) of the present invention. The obtained resin was reddish brown, and the melt viscosity (ICI cone # 1) at a softening point of 48 ° C. and 150 ° C. was 0.20 Pa · s. The weight average molecular weight was 1024, and the number average molecular weight was 733.
Claims (6)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023162975A1 (en) * | 2022-02-28 | 2023-08-31 | 住友ベークライト株式会社 | Sealing resin composition and semiconductor device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04225012A (en) * | 1990-12-27 | 1992-08-14 | Nippon Kayaku Co Ltd | Tetra-nuclear phenolic novolak and its production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04225012A (en) * | 1990-12-27 | 1992-08-14 | Nippon Kayaku Co Ltd | Tetra-nuclear phenolic novolak and its production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023162975A1 (en) * | 2022-02-28 | 2023-08-31 | 住友ベークライト株式会社 | Sealing resin composition and semiconductor device |
| JPWO2023162975A1 (en) * | 2022-02-28 | 2023-08-31 | ||
| JP7477055B2 (en) | 2022-02-28 | 2024-05-01 | 住友ベークライト株式会社 | Encapsulating resin composition and semiconductor device |
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