JP5682928B2 - Phenolic resin, epoxy resin and cured product thereof - Google Patents
Phenolic resin, epoxy resin and cured product thereof Download PDFInfo
- Publication number
- JP5682928B2 JP5682928B2 JP2011222528A JP2011222528A JP5682928B2 JP 5682928 B2 JP5682928 B2 JP 5682928B2 JP 2011222528 A JP2011222528 A JP 2011222528A JP 2011222528 A JP2011222528 A JP 2011222528A JP 5682928 B2 JP5682928 B2 JP 5682928B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- present
- parts
- reaction
- epoxy
- 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.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 93
- 229920000647 polyepoxide Polymers 0.000 title claims description 93
- 239000005011 phenolic resin Substances 0.000 title claims description 38
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title description 7
- 229920001568 phenolic resin Polymers 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims description 42
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 26
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 25
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 25
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 25
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 25
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 150000001299 aldehydes Chemical class 0.000 claims description 15
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 13
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 12
- 235000012141 vanillin Nutrition 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- -1 octylphenol Chemical compound 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 150000002989 phenols Chemical class 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 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 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- 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
- 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
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 4
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-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
- 239000004593 Epoxy Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 230000002378 acidificating effect Effects 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
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 4
- KVVSCMOUFCNCGX-UHFFFAOYSA-N cardol Chemical compound CCCCCCCCCCCCCCCC1=CC(O)=CC(O)=C1 KVVSCMOUFCNCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- 239000011810 insulating 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
- 229930014626 natural product Natural products 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 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
- 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
- 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
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 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
- 239000002131 composite material Substances 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
- 239000010410 layer Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000035484 reaction time Effects 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
- 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
- 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
- 244000226021 Anacardium occidentale Species 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- UFMJCOLGRWKUKO-UHFFFAOYSA-N cardol diene Natural products CCCC=CCC=CCCCCCCCC1=CC(O)=CC(O)=C1 UFMJCOLGRWKUKO-UHFFFAOYSA-N 0.000 description 2
- 235000020226 cashew nut Nutrition 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
- 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
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920003986 novolac Polymers 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
- 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
- 238000006116 polymerization reaction Methods 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
- 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
- ZMQAAUBTXCXRIC-UHFFFAOYSA-N safrole Chemical compound C=CCC1=CC=C2OCOC2=C1 ZMQAAUBTXCXRIC-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 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
- 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000008096 xylene 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
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical compound CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- FCUBUGPGVCEURB-UHFFFAOYSA-N 3-methyl-2-propylphenol Chemical compound CCCC1=C(C)C=CC=C1O FCUBUGPGVCEURB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000005770 Eugenol Substances 0.000 description 1
- BKJLNJYDEMKREK-UHFFFAOYSA-N FNB(F)F Chemical class FNB(F)F BKJLNJYDEMKREK-UHFFFAOYSA-N 0.000 description 1
- 240000008620 Fagopyrum esculentum Species 0.000 description 1
- 235000009419 Fagopyrum esculentum Nutrition 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 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
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris 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
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000007513 acids Chemical class 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- KAOMOVYHGLSFHQ-UTOQUPLUSA-N anacardic acid Chemical compound CCC\C=C/C\C=C/CCCCCCCC1=CC=CC(O)=C1C(O)=O KAOMOVYHGLSFHQ-UTOQUPLUSA-N 0.000 description 1
- 235000014398 anacardic acid Nutrition 0.000 description 1
- ADFWQBGTDJIESE-UHFFFAOYSA-N anacardic acid 15:0 Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1C(O)=O ADFWQBGTDJIESE-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 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
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 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
- 239000004210 ether based solvent Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 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
- 238000001879 gelation Methods 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-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
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical compound C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- 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
- 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
- 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
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Description
本発明は、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）および積層板（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および該組成物の硬化物に関する。 The present invention relates to a composition containing a phenol resin and an epoxy resin having a plant-derived skeleton as a main skeleton, and a molded article thereof. The present invention particularly relates to an insulating material for electrical and electronic parts (such as a highly reliable semiconductor sealing material). ) And laminated boards (printed wiring boards, build-up boards, etc.), epoxy resins that give curable resin compositions useful for various composite materials including CFRP, adhesives, paints, etc., and cured products of the compositions .
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、石油を始めとする化学資源の枯渇化等が環境問題となっている。そこで、石油や石油由来のような化石資源ではなく、天然物由来の資源（いわゆる非石油資源）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 chemical 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 by using natural product-derived resources (so-called non-petroleum resources) instead of fossil resources such as petroleum and petroleum.
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.
一方、エポキシ樹脂組成物は作業性およ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１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、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、作業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得る高度な信頼性を付与することは難しい。 On the other hand, epoxy resin compositions are used in the fields of electrical / electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. Widely used. In such fields, epoxy resins using plant-derived compounds have been studied. Specifically, Patent Document 1 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 problems in workability. In addition, it has few functional groups, and it is difficult to impart a high degree of reliability that can withstand the use of electrical and electronic materials.
カシューナッツ殻を原料としたカルダノールを主骨格とするエポキシ樹脂として特許文献２、３に記載の樹脂が知られている。これらの樹脂は粘性が低く、作業性や耐水性に優れた樹脂特性を有する。しかしながらモノマーやダイマーなど低分子量成分に限られており、十分な耐熱性が得られないことから電気・電子部品への応用は限られている。 Resins described in Patent Documents 2 and 3 are known as epoxy resins having cardanol as a main skeleton using cashew nut shell as a raw material. These resins have a low viscosity and resin properties with excellent workability and water resistance. However, it is limited to low molecular weight components such as monomers and dimers, and since sufficient heat resistance cannot be obtained, application to electric and electronic parts is limited.
本発明は、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、室温で液状であり作業性に優れるため、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。また、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を目的とする。 The present invention provides a phenol resin, an epoxy resin, and an epoxy resin composition containing them, which have a plant-derived skeleton as a main skeleton, and are liquid at room temperature and excellent in workability. It is useful for insulating materials (such as highly reliable semiconductor sealing materials) and laminates (printed wiring boards, build-up substrates, etc.), various composite materials including CFRP, adhesives, paints, and the like. Another object of the present invention is to provide a phenol resin, an epoxy resin, and an epoxy resin composition thereof that contribute to a reduction in the amount of fossil energy used because they are compounds derived from natural products.
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）カルダノールとアルデヒド類を反応させることにより得られるフェノール樹脂、
（２）（１）に記載のアルデヒド類がホルムアルデヒド、フルフラール、バニリンのうち少なくとも１つであるフェノール樹脂、
（３）（１）または（２）に記載のフェノール樹脂に、エピハロヒドリンを反応させることにより得られるエポキシ樹脂、
（４）（ａ）エポキシ樹脂および（ｂ）（１）または（２）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、
（５）（ａ）（３）に記載のエポキシ樹脂および（ｂ）硬化剤を含有するエポキシ樹脂組成物、
（６）（ａ）（３）に記載のエポキシ樹脂および（ｂ）（１）または（２）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、
（７）（４）〜（６）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 phenolic resin obtained by reacting cardanol with aldehydes,
(2) A phenol resin in which the aldehyde according to (1) is at least one of formaldehyde, furfural, and vanillin,
(3) An epoxy resin obtained by reacting an epihalohydrin with the phenol resin according to (1) or (2),
(4) An epoxy resin composition containing (a) an epoxy resin and (b) the phenol resin according to (1) or (2),
(5) (a) an epoxy resin composition containing the epoxy resin according to (3) and (b) a curing agent,
(6) An epoxy resin composition containing the epoxy resin according to (a) (3) and the phenol resin according to (b) (1) or (2),
(7) A cured product obtained by curing the epoxy resin composition according to any one of (4) to (6),
About.
本発明のフェノール樹脂、エポキシ樹脂は、室温で液状であり作業性に優れるため、電気電子部品用絶縁材料（高信頼性半導体封止材料など）および積層板（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。 Since the phenol resin and epoxy resin of the present invention are liquid at room temperature and have excellent workability, insulating materials for electrical and electronic parts (high reliability semiconductor encapsulating materials, etc.) and laminated boards (printed wiring boards, build-up boards, 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、カルダノールとアルデヒド類を反応させることで得られる。本発明のエポキシ樹脂は骨格中に非極性な直鎖アルキルが存在するため、低吸水、低誘電などの高度な特性を与える。尚、使用するアルデヒド類にはホルムアルデヒド、フルフラール、バニリンのうち少なくとも１つを用いている。以下、カルダノール、フルフラール、バニリンについて説明する。
＜カルダノール（cardanol）＞
カルダノールはカシューナッツ殻液を分別蒸留にかけることにより得られる。カルダノールは不飽和基の数や位置が異なる４種の混合物であり、不純物としてカルドール、アナカルド酸、およびアルキルカルドールを含有している。
ここで、カルダノールは下記式（１）で表される。尚、置換基が４種類あるが、下記４種の置換基を有する化合物の混合物をカルダノールと称する。
トウモロコシの穂軸、燕麦などの籾殻、サトウキビの絞りかす、ふすまなどの農産物の
副産物やおがくずなどを原料にして製造される。
＜バニリン(vanilline)＞
バニリンはバニラビーンズより得られるものもあるが、一般には合成により製造されている。その製造法により、サフロールバニリン、オイゲノールバニリン、リグニンバニリン、グアヤコールバニリン等に分けられる。ただし、いずれも天然物由来の化合物からの誘導体である。
本発明において、ホルムアルデヒドは、パラホルムアルデヒド、ホルマリン等といったホルムアルデヒドの合成等価体も含む概念である。
ここで、本発明に用いるカルダノールは純度が８０％以上のものが好ましく、純度が９０％以上のものが特に好ましい。純度が低いと目的とするエポキシ樹脂が得られにくく、安定した樹脂物性が得られない恐れがある。具体的には重合反応による粘度上昇および作業性の低下・不純物カルドールの酸化による貯蔵中の色安定性低下等である。
The phenol resin of the present invention can be obtained by reacting cardanol with aldehydes. Since the non-polar linear alkyl exists in the skeleton of the epoxy resin of the present invention, it gives high properties such as low water absorption and low dielectric constant. The aldehyde used is at least one of formaldehyde, furfural, and vanillin. Hereinafter, cardanol, furfural and vanillin will be described.
<Cardanol>
Cardanol is obtained by subjecting cashew nut shell liquid to fractional distillation. Cardanol is a mixture of four types having different numbers and positions of unsaturated groups, and contains cardol, anacardic acid, and alkylcardol as impurities.
Here, cardanol is represented by the following formula (1). Although there are four types of substituents, a mixture of compounds having the following four types of substituents is referred to as cardanol.
Manufactured from raw materials such as corn cobs, rice husks such as buckwheat, sugarcane pomace, and by-products of agricultural products such as bran and sawdust.
<Vanilline>
Although some vanillin is obtained from vanilla beans, it is generally produced synthetically. Depending on the production method, it can be divided into safrole vanillin, eugenol vanillin, lignin vanillin, guaiacol vanillin and the like. However, all are derivatives from compounds derived from natural products.
In the present invention, formaldehyde is a concept including synthetic equivalents of formaldehyde such as paraformaldehyde and formalin.
Here, the cardanol used in the present invention preferably has a purity of 80% or more, and particularly preferably has a purity of 90% or more. If the purity is low, it is difficult to obtain the target epoxy resin, and stable resin physical properties may not be obtained. Specifically, there are an increase in viscosity due to a polymerization reaction and a decrease in workability, and a decrease in color stability during storage due to oxidation of the impurity cardol.
本発明においてカルダノール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、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。
カルダノールと共にフェノールを併用する場合、カルダノールの含有割合はカルダノール及び使用するフェノール類の総量に対して３０重量％以上が好ましい。
In the present invention, phenols that can be used in combination with cardanol 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, Phenols such as methylbutylphenol are exemplified, but not limited thereto as long as it has a phenolic hydroxyl group. Moreover, these phenols can be used individually or in mixture of 2 or more types.
When phenol is used together with cardanol, the content of cardanol is preferably 30% by weight or more based on the total amount of cardanol and phenols used.
本発明のフェノール樹脂は、カルダノール並びに必要によりこれをフェノール類の混合物にアルデヒド類を加え、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、カルダノール並びに必要によりこれをフェノール類およ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アルデヒド類を徐々に添加してもよい。アルデヒド類の使用量は、カルダノールおよびフェノール類の総量に対し、好ましくは０．３〜１．０倍モル、より好ましくは０．３〜０．７倍モルである。０．３倍モル以下では重合反応の進行が悪く、十分な耐熱性が得られない可能性があり、１．０倍モル以上ではゲル化してしまう恐れがある。反応時間は２〜１５０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、晶析あるいは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 phenol resin of the present invention can be obtained by adding cardanol and, if necessary, aldehydes to a mixture of phenols, and if necessary, adding a catalyst and heating in the presence of a solvent. Alternatively, cardanol and, if necessary, aldehydes may be gradually added to the mixture of phenols and solvent and catalyst mixture. The amount of aldehydes to be used is preferably 0.3 to 1.0 times mol, more preferably 0.3 to 0.7 times mol, based on the total amount of cardanol and phenols. If it is 0.3 times mol or less, the progress of the polymerization reaction is poor and there is a possibility that sufficient heat resistance may not be obtained, and if it is 1.0 times mol or more, gelation may occur. The reaction time is 2 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 after neutralization of the reaction mixture after completion of the reaction, the unreacted raw materials and solvents are usually crystallized or heated under reduced pressure. It is refined by removing 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およびアルデヒド類の総量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 in the range of 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total amount of phenols and aldehydes.
触媒としては酸性、塩基性いずれの触媒でも使用できるが、フルフラールを用いた場合、塩基性の物が好ましい。酸性触媒を使用した場合、フルフラール同士の反応も起こり、構造の特定できない化合物が多くなる。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、カルダノール並びに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、カルダノール並びに必要により使用するフェノール類の総量に対し、１０〜２００質量％程度添加することが好ましい。 As the catalyst, either an acidic or basic catalyst can be used, but when furfural is used, a basic substance is preferable. When an acidic catalyst is used, the reaction between furfural also occurs, and the number of compounds whose structures cannot be specified increases. 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 cardanol 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 10-200 mass% with respect to the total amount of cardanol and the phenols used as needed.
カルダノールとホルムアルデヒド、フルフラール、バニリンのうち少なくとも１つとの反応は、その条件により生成物が、分子量分布を有する樹脂状フェノール樹脂（本発明のフェノール樹脂）になる。 The reaction of cardanol with at least one of formaldehyde, furfural, and vanillin results in a resinous phenolic resin having the molecular weight distribution (the phenolic resin of the present invention).
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、a−メチルエピクロルヒドリン、g−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, a-methylepichlorohydrin, g-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, and 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, 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およびエピハロヒドリンを留出させ、さら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０．００〜１．１５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 alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are distilled off continuously under reduced pressure or normal pressure, followed by liquid separation to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.00 to 1 mol per mol of the hydroxyl group of the raw material 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質量％、好ましくは４〜３０質量％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質量％、好ましくは１０〜８０質量％である。 When using alcohol, the usage-amount is 2-50 mass% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-30 mass%. Moreover, when using an aprotic polar solvent, it is 5-100 mass% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 mass%.
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。 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.
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。
また、得られたエポキシ樹脂を含有するエポキシ樹脂組成物の硬化物は耐水性、低吸水、低誘電等の硬度な特性を有する。
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.
Moreover, the cured | curing material of the epoxy resin composition containing the obtained epoxy resin has hardness characteristics, such as water resistance, a low water absorption, and a low dielectric constant.
このようにして得られるエポキシ樹脂のエポキシ当量は３５０ｇ／ｅｑ．〜６００ｇ／ｅｑ．が好ましく、より好ましくは５００ｇ／ｅｑ．〜５５０ｇ／ｅｑ．であることが好ましい。 The epoxy equivalent of the epoxy resin thus obtained is 350 g / eq. ~ 600 g / eq. Is more preferable, and more preferably 500 g / eq. -550 g / eq. It is preferable that
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.
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質量％以上が好ましく、特に４０質量％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質量％を占める割合で添加する。 In the epoxy resin composition of the present invention, 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 mass or more, particularly preferably 40% by mass 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 mass% 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。
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, phenol aralkyl type epoxy resins and the like. 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-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, Polycondensates with 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, and the like, and modified products thereof Solid or liquid epoxy resins such as halogenated bisphenols such as tetrabromobisphenol A, glycidyl etherified products derived from alcohols, alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, etc. However, it is not limited to these. These 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、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の全硬化剤中に占める割合は３０質量％以上が好ましく、特に４０質量％以上が好ましい。ただし、本発明のフェノール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質量％の割合となるよう添加する。 In the epoxy resin composition of the present invention, 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 of the present invention in the total curing agent is preferably 30% by mass or more, particularly preferably 40% by mass or more. However, when using the phenol resin of this invention as a modifier of an epoxy resin composition, it adds so that it may become a ratio of 1-30 mass% 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.
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, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin. 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.
さら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質量％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質量％以上であり、４０〜９５質量％を占める割合で使用するのがより好ましい。 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 surface, it is preferable to use it in a proportion of 20% by mass or more in the epoxy resin composition, more preferably 30% by mass or more, and more preferably 40% to 95% by mass.
さら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、カーボン繊維、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質量％、好ましくは１５〜７０質量％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 obtained by hot press molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and drying by heating. The cured product of the epoxy resin composition of the present invention can be used. The solvent content of this epoxy resin varnish is usually about 10 to 70% by mass, preferably about 15 to 70% by mass, on an internal basis. 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 can be combined alone or 2
The above mixed solvent may be used.
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.
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), anisotropic conductive paste (ACP)
) And the like.
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さらに具体的に説明するが、以下において部は特に断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ＪＩＳＫ−７２３６に準じた方法で測定した。 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. In the examples, the epoxy equivalent was measured by a method according to JISK-7236.
実施例１
攪拌機、還流冷却管、攪拌装置を備えたフラスコに、窒素パージを施しながらカルダノール１５０部、ｐ−トルエンスルホン酸１部、トルエン２２５部を加え、８０℃で加熱しながら、３５％ホルマリン水溶液３０部を３０分かけて添加し、そのままの温度を保ち２時間反応を行った。続けて１００℃で１時間、１３０℃で１時間反応を行った。反応終了後、１０％トリポリリン酸ナトリウムを２０部加え、攪拌した後、水層が中性になるまで水洗を行った。得られた有機層をロータリーエバポレーターで１８０℃で減圧下、トルエン等の溶剤を留去することで本発明のフェノール樹脂１４８部を得た。得られたフェノール樹脂は液状茶褐色であり、水酸基当量は３２６ｇ／ｅｑ．、２５℃における粘度は３７．１３Ｐａ・ｓであった。
攪拌機、還流冷却管、攪拌装置を備えたフラスコに、窒素パージを施しながら得られた液状フェノール樹脂８４部、エピクロロヒドリン１０５部、メタノール７部、水２部を加え、７５℃にまで昇温した。次いでフレーク状の水酸化ナトリウム１１部を９０分かけて分割添加した後、さらに７５℃で７５分間反応を行った。反応終了後水洗を行い、有機層からロータリーエバポレーターを用いて１４０℃で減圧下、過剰のエピクロロ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１８４部を加え溶解し、７５℃にまで昇温した。攪拌下でメタノール２部、３０％水酸化ナトリウム水溶液３部を加え、１時間反応を行った後、メタノール２０部を加え、洗浄水が中性になるまで有機層を水洗し得られた有機層からロータリーエバポレーターを用いて１８０℃で減圧下にメチルイソブチルケトン等の溶剤を留去することで本発明のエポキシ樹脂を９３部得た。得られたエポキシ樹脂は液状茶褐色であり、エポキシ当量は５４５ｇ／ｅｑ．、２５℃における粘度は８．９８Ｐａ・ｓであった。
Example 1
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 150 parts of cardanol, 1 part of p-toluenesulfonic acid and 225 parts of toluene are added while purging with nitrogen, and 30 parts of 35% formalin aqueous solution while heating at 80 ° C. Was added over 30 minutes, and the reaction was carried out for 2 hours while maintaining the temperature as it was. Subsequently, the reaction was performed at 100 ° C. for 1 hour and at 130 ° C. for 1 hour. After completion of the reaction, 20 parts of 10% sodium tripolyphosphate was added and stirred, and then washed with water until the aqueous layer became neutral. The obtained organic layer was distilled off a solvent such as toluene under reduced pressure at 180 ° C. with a rotary evaporator to obtain 148 parts of the phenol resin of the present invention. The obtained phenol resin is liquid brown and has a hydroxyl group equivalent of 326 g / eq. The viscosity at 25 ° C. was 37.13 Pa · s.
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 84 parts of a liquid phenol resin obtained while purging with nitrogen, 105 parts of epichlorohydrin, 7 parts of methanol, and 2 parts of water were added, and the temperature was raised to 75 ° C. Warm up. Next, 11 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140 ° C. using a rotary evaporator. 184 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 75 ° C. Under stirring, 2 parts of methanol and 3 parts of 30% aqueous sodium hydroxide solution were added and reacted for 1 hour, then 20 parts of methanol was added, and the organic layer was washed with water until the washing water became neutral. Then, 93 parts of the epoxy resin of the present invention was obtained by distilling off a solvent such as methyl isobutyl ketone under reduced pressure at 180 ° C. using a rotary evaporator. The obtained epoxy resin was liquid brown and the epoxy equivalent was 545 g / eq. The viscosity at 25 ° C. was 8.98 Pa · s.
実施例２
攪拌機、還流冷却管、攪拌装置を備えたフラスコに、窒素パージを施しながらカルダノール９０部、３０％水酸化ナトリウム水溶液１０部を加え、８０℃で加熱しながら、フルフラール１０部を３０分かけて添加し、１１０℃にまで昇温し、４時間反応を行った。続けて１４０℃で４時間反応を行った。反応終了後、２０％リン酸ニ水素ナトリウム１１部、濃塩酸７部を加え、７０℃で３０分反応を行った。反応終了後、１０％トリポリリン酸ナトリウム２０部、メチルイソブチルケトン２００部を加え、水層が中性になるまで水洗を行った。得られた有機層をロータリーエバポレーターで１３０℃で減圧下、メチルイソブチルケトン等の溶剤を留去することで本発明のフェノール樹脂９５部を得た。得られたフェノール樹脂は液状茶褐色であり、水酸基当量は３５７ｇ／ｅｑ．、２５℃における粘度は４８４ｍＰａ・ｓであった。
攪拌機、還流冷却管、攪拌装置を備えたフラスコに、窒素パージを施しながら得られた液状フェノール樹脂４３部、エピクロロヒドリン４６部、メタノール３部、水１部を加え、７５℃にまで昇温した。次いでフレーク状の水酸化ナトリウム５部を９０分かけて分割添加した後、さらに７５℃で７５分間反応を行った。反応終了後水洗を行い、有機層からロータリーエバポレーターを用いて１４０℃で減圧下、過剰のエピクロロ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９２部を加え溶解し、７５℃にまで昇温した。攪拌下でメタノール１部、３０％水酸化ナトリウム水溶液１部を加え、１時間反応を行った後、メタノール２０部を加え、洗浄水が中性になるまで有機層を水洗し得られた有機層からロータリーエバポレーターを用いて１８０℃で減圧下にメチルイソブチルケトン等の溶剤を留去することで本発明のエポキシ樹脂を４７部得た。得られたエポキシ樹脂は液状茶褐色であり、エポキシ当量は５４５ｇ／ｅｑ．、２５℃における粘度は５４２ｍＰａ・ｓであった。
Example 2
To a flask equipped with a stirrer, reflux condenser and stirrer, add 90 parts of cardanol and 10 parts of 30% aqueous sodium hydroxide while purging with nitrogen, and add 10 parts of furfural over 30 minutes while heating at 80 ° C. The temperature was raised to 110 ° C. and the reaction was carried out for 4 hours. Subsequently, the reaction was carried out at 140 ° C. for 4 hours. After completion of the reaction, 11 parts of 20% sodium dihydrogen phosphate and 7 parts of concentrated hydrochloric acid were added and reacted at 70 ° C. for 30 minutes. After completion of the reaction, 20 parts of 10% sodium tripolyphosphate and 200 parts of methyl isobutyl ketone were added and washed with water until the aqueous layer became neutral. 95 parts of the phenol resin of the present invention was obtained by distilling off the solvent such as methyl isobutyl ketone under reduced pressure at 130 ° C. using a rotary evaporator. The obtained phenol resin was liquid brown and the hydroxyl group equivalent was 357 g / eq. The viscosity at 25 ° C. was 484 mPa · s.
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 43 parts of a liquid phenolic resin obtained while purging with nitrogen, 46 parts of epichlorohydrin, 3 parts of methanol, and 1 part of water, and rise to 75 ° C. Warm up. Next, 5 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140 ° C. using a rotary evaporator. 92 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 75 ° C. Under stirring, 1 part of methanol and 1 part of 30% sodium hydroxide aqueous solution were added and reacted for 1 hour, then 20 parts of methanol was added, and the organic layer was washed with water until the washing water became neutral. Then, 47 parts of the epoxy resin of the present invention was obtained by distilling off a solvent such as methyl isobutyl ketone under reduced pressure at 180 ° C. using a rotary evaporator. The obtained epoxy resin was liquid brown and the epoxy equivalent was 545 g / eq. The viscosity at 25 ° C. was 542 mPa · s.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011222528A JP5682928B2 (en) | 2011-10-07 | 2011-10-07 | Phenolic resin, epoxy resin and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011222528A JP5682928B2 (en) | 2011-10-07 | 2011-10-07 | Phenolic resin, epoxy resin and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013082785A JP2013082785A (en) | 2013-05-09 |
| JP5682928B2 true JP5682928B2 (en) | 2015-03-11 |
Family
ID=48528308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011222528A Active JP5682928B2 (en) | 2011-10-07 | 2011-10-07 | Phenolic resin, epoxy resin and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5682928B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6091295B2 (en) * | 2013-04-03 | 2017-03-08 | 日本化薬株式会社 | Epoxy resin composition and cured product thereof |
| JP6390581B2 (en) * | 2015-10-21 | 2018-09-19 | 住友ベークライト株式会社 | Method for producing liquid resol type phenolic resin, and method for producing wet paper friction material |
| JP6476527B2 (en) * | 2015-12-10 | 2019-03-06 | 群栄化学工業株式会社 | Liquid polyvalent hydroxy resin, production method thereof, curing agent for epoxy resin, epoxy resin composition, cured product thereof and epoxy resin |
| CN110546184B (en) * | 2017-04-28 | 2022-08-26 | 昭和电工材料株式会社 | Sealing film, sealing structure, and method for producing sealing structure |
| CN107488260B (en) * | 2017-07-10 | 2020-11-17 | 中国林业科学研究院林业新技术研究所 | Epoxy resin curing agent based on cardanol and furfural and preparation method thereof |
| JP7484081B2 (en) * | 2018-10-18 | 2024-05-16 | 株式会社レゾナック | Curable resin composition and electronic component device |
| CN109867760B (en) * | 2019-01-31 | 2021-03-16 | 泉州师范学院 | Cardanol-based photosensitive resin for 3D printing and preparation method thereof |
| WO2023048164A1 (en) * | 2021-09-24 | 2023-03-30 | リンテック株式会社 | Multifunctional phenolic compound and production method therefor |
| WO2023048163A1 (en) * | 2021-09-24 | 2023-03-30 | リンテック株式会社 | Multifunctional phenolic compound and production method therefor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5466362B2 (en) * | 2007-11-29 | 2014-04-09 | 昭和電工株式会社 | Cashew novolac resin, method for producing the same, and curing agent for epoxy resin |
| JP5435641B2 (en) * | 2010-01-19 | 2014-03-05 | 日本化薬株式会社 | Phenol resin, epoxy resin, epoxy resin composition, and cured product thereof |
| JP5771088B2 (en) * | 2011-07-25 | 2015-08-26 | 群栄化学工業株式会社 | Solid resol type biomass phenol resin and rubber composition |
-
2011
- 2011-10-07 JP JP2011222528A patent/JP5682928B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013082785A (en) | 2013-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5682928B2 (en) | Phenolic resin, epoxy resin and cured product thereof | |
| JP6091295B2 (en) | Epoxy resin composition and cured product thereof | |
| JP2010001427A (en) | Epoxy resin, epoxy resin composition, and its cured product | |
| JP5273762B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| TWI425019B (en) | Liquid epoxy resin, epoxy resin composition and hardened product | |
| KR101408535B1 (en) | Modified liquid epoxy resin, epoxy resin composition using the same, and cured product thereof | |
| TWI648317B (en) | Phenolic resin, phenol resin mixture, epoxy resin, epoxy resin composition and hardened materials | |
| JP5366263B2 (en) | Phenol aralkyl resin, epoxy resin composition and cured product thereof | |
| JP6513372B2 (en) | Phenolic resin, epoxy resin, epoxy resin composition and cured product thereof | |
| JP2008195843A (en) | Phenolic resin, epoxy resin, epoxy resin composition, and cured product of the same | |
| JP5322143B2 (en) | Phenol resin, epoxy resin, epoxy resin composition, and cured product thereof | |
| TWI522385B (en) | An epoxy resin, an epoxy resin composition, and a cured product thereof | |
| JP5435641B2 (en) | Phenol resin, epoxy resin, epoxy resin composition, and cured product thereof | |
| JP7240989B2 (en) | Curable resin composition and its cured product | |
| JP4628621B2 (en) | Method for producing phenol aralkyl resin | |
| JP6302280B2 (en) | Epoxy resin, curable resin composition and cured product | |
| JP5881202B2 (en) | Phenol resin, epoxy resin, epoxy resin composition, and cured product thereof | |
| JP2014141688A (en) | Phenol resin, epoxy resin, epoxy resin composition and cured product thereof | |
| KR101799365B1 (en) | Epoxy resin, method for manufacturing the same, intermediate, epoxy resin composition and cured product | |
| WO2015060307A1 (en) | Phenolic resin, epoxy resin, epoxy resin composition, prepreg, and cured product thereof | |
| JP4086630B2 (en) | Polyhydric phenol compound, epoxy resin composition and cured product thereof | |
| JP3886060B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| TWI432478B (en) | Phenol resin, epoxy resin, curable resin composition, cured product the reof and production process of phenol resin | |
| JP4776446B2 (en) | Epoxy resin, epoxy resin composition, and cured product thereof | |
| KR20230107539A (en) | Epoxy resin, curable resin composition, and cured product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140513 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140728 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140730 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140919 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141016 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141201 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150107 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150107 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5682928 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |