JP7437253B2 - Phenol resin, epoxy resin, epoxy resin composition and cured product thereof - Google Patents
Phenol resin, epoxy resin, epoxy resin composition and cured product thereof Download PDFInfo
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- JP7437253B2 JP7437253B2 JP2020120659A JP2020120659A JP7437253B2 JP 7437253 B2 JP7437253 B2 JP 7437253B2 JP 2020120659 A JP2020120659 A JP 2020120659A JP 2020120659 A JP2020120659 A JP 2020120659A JP 7437253 B2 JP7437253 B2 JP 7437253B2
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- JP
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- Prior art keywords
- epoxy resin
- phenol
- resin
- mass
- 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.)
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- 229920000647 polyepoxide Polymers 0.000 title claims description 74
- 239000003822 epoxy resin Substances 0.000 title claims description 73
- 239000000203 mixture Substances 0.000 title claims description 32
- 239000005011 phenolic resin Substances 0.000 title claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 30
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- -1 especially laminates Substances 0.000 description 19
- 150000002989 phenols Chemical class 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 15
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 13
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 13
- 238000005406 washing Methods 0.000 description 12
- 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 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 9
- 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 8
- 239000000243 solution Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000011151 fibre-reinforced plastic Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical class CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 3
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 3
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 3
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 150000004074 biphenyls Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000007517 lewis acids Chemical group 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical class CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical class CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 239000002966 varnish 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
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical class O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- MBNMVPPPCZKPIJ-UHFFFAOYSA-N 1-[3-[3-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=C(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)C=CC=2)=C1 MBNMVPPPCZKPIJ-UHFFFAOYSA-N 0.000 description 1
- UGJHILWNNSROJV-UHFFFAOYSA-N 1-[4-[3-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=CC(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)=C1 UGJHILWNNSROJV-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
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-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
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Images
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- Epoxy Resins (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
本発明は電気電子部品用絶縁材料（高信頼性半導体封止材料など）、積層板（プリント配線板、ビルドアップ基板など）及びＦＲＰ（繊維強化プラスチック）を始めとする各種複合材料、接着剤、塗料等、中でも特に積層板等の用途に有用であり、金属箔張り積層板、ビルドアップ基板用絶縁材料、フレキシブル基板材料などに有用である硬化性樹脂組成物を与えるエポキシ樹脂及びエポキシ樹脂組成物に関する。 The present invention relates to insulating materials for electrical and electronic components (highly reliable semiconductor encapsulation materials, etc.), laminates (printed wiring boards, build-up boards, etc.), various composite materials including FRP (fiber reinforced plastics), adhesives, Epoxy resins and epoxy resin compositions that provide curable resin compositions that are particularly useful for applications such as paints, especially laminates, metal foil-clad laminates, insulating materials for build-up boards, flexible board materials, etc. Regarding.
エポキシ樹脂組成物は作業性、及びその硬化物の優れた電気特性、耐熱性、接着性、耐吸水性等により電気・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。 Epoxy resin compositions are widely used in fields such as electrical and electronic parts, structural materials, adhesives, and paints due to their workability and the excellent electrical properties, heat resistance, adhesiveness, and water absorption resistance of their cured products. There is.
近年、電気・電子分野においては、樹脂組成物の高純度化、密着性向上、フィラーを高充填させるための低粘度化、成型サイクルを短くするための反応性向上等の諸特性のさらなる向上が求められている。特に半導体関連材料の分野においては、非常に高い特性が求められ、電気特性、耐吸水性等の特性が重要視されている。 In recent years, in the electrical and electronic fields, further improvements have been made in various properties such as higher purity of resin compositions, improved adhesion, lower viscosity for higher filler loading, and improved reactivity for shorter molding cycles. It has been demanded. Particularly in the field of semiconductor-related materials, extremely high properties are required, and properties such as electrical properties and water absorption resistance are emphasized.
近年の電子デバイスの高性能化及び軽薄短小化に伴い、伝送信号の高周波化が進み、パッケージ材料や基板材料に使用する材料に対して、高周波領域での低誘電率、低誘電正接化が強く求められている。しかしながら、エポキシ樹脂は、エポキシ基と活性水素との反応により極性の高いヒドロキシ基が発生することにより誘電率、誘電正接が高くなるため、未だ充分な電気特性が得られていない。 In recent years, as electronic devices have improved in performance and become lighter, thinner, and smaller, the frequency of transmission signals has increased, and the materials used for packaging and substrate materials are strongly required to have a low dielectric constant and a low dielectric loss tangent in the high frequency range. It has been demanded. However, epoxy resins do not yet have sufficient electrical properties because highly polar hydroxy groups are generated by the reaction between epoxy groups and active hydrogen, resulting in high dielectric constants and dielectric loss tangents.
また、吸水性が高い材料は、はんだリフロー時にクラックや剥離不良の原因となるおそれもある。 Furthermore, materials with high water absorption may cause cracks or poor peeling during solder reflow.
特許文献１では（メタ）アリルエーテル樹脂を酸化してエポキシ樹脂を得ている。また、特許文献２では４,４'－ブチリデンビス（６－ｔ－ブチル－３－メチルフェノール）のジグリシジルエーテルを得ている。しかし、これらの特許文献に記載されているエポキシ樹脂の硬化物の耐吸水性、電気特性は未だ不十分であり、さらなる改善が求められる。 In Patent Document 1, an epoxy resin is obtained by oxidizing a (meth)allyl ether resin. Further, in Patent Document 2, diglycidyl ether of 4,4'-butylidene bis(6-t-butyl-3-methylphenol) is obtained. However, the water absorption resistance and electrical properties of the cured epoxy resins described in these patent documents are still insufficient, and further improvements are required.
本発明は、このような状況を鑑みてなされたものであり、優れた耐吸水性、電気特性を示すエポキシ樹脂、エポキシ樹脂組成物およびその硬化物、その前駆体のフェノール樹脂を提供することを目的とする。 The present invention has been made in view of these circumstances, and aims to provide an epoxy resin, an epoxy resin composition, a cured product thereof, and a phenolic resin precursor thereof, which exhibit excellent water absorption resistance and electrical properties. purpose.
本発明者らは、鋭意研究した結果、特定の構造を有するジシクロペンタジエン型エポキシ樹脂の硬化物が耐吸水性、電気特性に優れることを見出し、本発明を完成するに至った。 As a result of extensive research, the present inventors have discovered that a cured product of a dicyclopentadiene type epoxy resin having a specific structure has excellent water absorption resistance and electrical properties, and has completed the present invention.
すなわち本発明は、以下の［１］～［７］に示すものである。
［１］
下記式（１）で表されるエポキシ樹脂。
That is, the present invention is as shown in [1] to [7] below.
[1]
An epoxy resin represented by the following formula (1).
（式（１）中、Ｒ１、Ｒ２はそれぞれ独立して炭素数１～１０のアルキル基またはアリル基、Ｒ３、Ｒ４はそれぞれ独立して水素原子、グリシジルエーテル基、炭素数１～１０のアルキル基またはアリル基を表す。ａ、ｂは０～２の実数を表し、ａ＋ｂ≧１である。ｃ、ｄは１～３の実数を表す。ｎは繰り返し数であり１～２０の実数を表す。）
［２］
前記式（１）中、Ｒ１、Ｒ２がともに炭素数１～１０のアルキル基であり、Ｒ３、Ｒ４が水素原子である前項［１］に記載のエポキシ樹脂。
［３］
前記式（１）中、Ｒ１、Ｒ２がともにメチル基であり、Ｒ３、Ｒ４が水素原子である前項［１］に記載のエポキシ樹脂。
［４］
下記式（２）で表されるフェノール樹脂にエピクロロヒドリンを反応させて得られる前項［１］乃至［３］のいずれか一項に記載のエポキシ樹脂。
(In formula (1), R 1 and R 2 are each independently an alkyl group or allyl group having 1 to 10 carbon atoms; R 3 and R 4 are each independently a hydrogen atom, a glycidyl ether group, and Represents an alkyl group or an allyl group of 10. a, b represent a real number of 0 to 2, and a+b≧1. c, d represent a real number of 1 to 3. n is a repeating number of 1 to 20. (Represents a real number.)
[2]
The epoxy resin according to the above item [1], wherein in the formula (1), R 1 and R 2 are both alkyl groups having 1 to 10 carbon atoms, and R 3 and R 4 are hydrogen atoms.
[3]
The epoxy resin according to the above item [1], wherein in the formula (1), R 1 and R 2 are both methyl groups, and R 3 and R 4 are hydrogen atoms.
[4]
The epoxy resin according to any one of the above items [1] to [3], which is obtained by reacting a phenol resin represented by the following formula (2) with epichlorohydrin.
（式（２）中、Ｒ１、Ｒ２はそれぞれ独立して炭素数１～１０のアルキル基またはアリル基、Ｒ３、Ｒ４はそれぞれ独立して水素原子、水酸基、炭素数１～１０のアルキル基またはアリル基を表す。ａ、ｂは０～２の実数を表し、ａ＋ｂ≧１である。ｃ、ｄは１～３の実数を表す。ｎは繰り返し数であり１～２０の実数を表す。）
［５］
前項［１］乃至［４］のいずれか一項に記載のエポキシ樹脂と硬化剤とを含有してなるエポキシ樹脂組成物。
［６］
前項［５］に記載のエポキシ樹脂組成物を硬化して得られる硬化物。
［７］
下記式（２）で表されるフェノール樹脂。
(In formula (2), R 1 and R 2 are each independently an alkyl group or allyl group having 1 to 10 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom, a hydroxyl group, or an allyl group having 1 to 10 carbon atoms. Represents an alkyl group or an allyl group.a and b represent a real number from 0 to 2, and a+b≧1.c and d represent a real number from 1 to 3.n is the repeating number and represents a real number from 1 to 20. represent.)
[5]
An epoxy resin composition comprising the epoxy resin according to any one of items [1] to [4] above and a curing agent.
[6]
A cured product obtained by curing the epoxy resin composition described in the preceding item [5].
[7]
A phenol resin represented by the following formula (2).
（式（２）中、Ｒ１、Ｒ２はそれぞれ独立して炭素数１～１０のアルキル基またはアリル基、Ｒ３、Ｒ４はそれぞれ独立して水素原子、水酸基、炭素数１～１０のアルキル基またはアリル基を表す。ａ、ｂは０～２の実数を表し、ａ＋ｂ≧１である。ｃ、ｄは１～３の実数を表す。ｎは繰り返し数であり１～２０の実数を表す。） (In formula (2), R 1 and R 2 are each independently an alkyl group or allyl group having 1 to 10 carbon atoms, and R 3 and R 4 are each independently a hydrogen atom, a hydroxyl group, or an allyl group having 1 to 10 carbon atoms. Represents an alkyl group or an allyl group.a and b represent a real number from 0 to 2, and a+b≧1.c and d represent a real number from 1 to 3.n is the repeating number and represents a real number from 1 to 20. represent.)
本発明によれば、その硬化物が優れた耐吸水性、電気特性を有するエポキシ樹脂、エポキシ樹脂組成物、それを用いた硬化物を提供することができる。そのため、電気電子部品の封止や回路基板、ＦＲＰなどに有用である。 According to the present invention, it is possible to provide an epoxy resin, an epoxy resin composition, and a cured product using the same, the cured product of which has excellent water absorption resistance and electrical properties. Therefore, it is useful for sealing electrical and electronic components, circuit boards, FRP, etc.
本発明のエポキシ樹脂は下記式（１）で表される。 The epoxy resin of the present invention is represented by the following formula (1).
式（１）中、Ｒ１、Ｒ２は炭素数１～１０のアルキル基またはアリル基、Ｒ３、Ｒ４は水素原子、グリシジルエーテル基、炭素数１～１０のアルキル基またはアリル基をそれぞれ表す。ａ、ｂは０～２の実数を表し、ａ＋ｂ≧１である。ｃ、ｄは１～３の実数を表す。ｎは繰り返し数であり１～２０の実数を示す。 In formula (1), R 1 and R 2 are an alkyl group or an allyl group having 1 to 10 carbon atoms, and R 3 and R 4 are a hydrogen atom, a glycidyl ether group, an alkyl group having 1 to 10 carbon atoms, or an allyl group, respectively. represent. a and b represent real numbers from 0 to 2, and a+b≧1. c and d represent real numbers from 1 to 3. n is the number of repetitions and is a real number from 1 to 20.
前記式（１）中、Ｒ１、Ｒ２は炭素数１～１０のアルキル基またはアリル基から選択されるが、好ましくは炭素数１～１０のアルキル基であり、さらに好ましくは１～３のアルキル基であり、特に好ましくはメチル基である。上記置換基を有することにより耐吸水性、誘電特性が向上するからである。前記式（１）中、ａ、ｂは０～２の実数を表し、ａ＋ｂ≧１であるが、ａ、ｂがともに１である場合が好ましい。 In the formula (1), R 1 and R 2 are selected from an alkyl group having 1 to 10 carbon atoms or an allyl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. It is an alkyl group, particularly preferably a methyl group. This is because water absorption resistance and dielectric properties are improved by having the above substituent. In the formula (1), a and b represent real numbers from 0 to 2, and a+b≧1, but it is preferable that a and b are both 1.
前記式（１）中、Ｒ３、Ｒ４は水素原子、グリシジルエーテル基、炭素数１～１０のアルキル基またはアリル基から選択されるが、線膨張率を小さくしたい場合は、Ｒ３、Ｒ４が水素原子であることが好ましい。Ｒ３、Ｒ４が水素原子である場合、分子運動をするような嵩高い置換基が存在しないため自由体積が小さくなり線膨張率は小さくなる。弾性率を向上させたい場合は、Ｒ３、Ｒ４が炭素数１～１０のアルキル基またはアリル基であることが好ましく、耐熱性を向上させたい場合は、Ｒ３、Ｒ４がグリシジルエーテル基であることが好ましい。Ｒ３、Ｒ４の置換基の配向性は、グリシジルエーテル基に対して、オルソ位、メタ位、パラ位のいずれでも良いが、グリシジルエーテル基であればメタ位、炭素数１～１０のアルキル基またはアリル基であればパラ位であることが好ましい。 In the formula (1), R 3 and R 4 are selected from a hydrogen atom, a glycidyl ether group, an alkyl group having 1 to 10 carbon atoms, or an allyl group. It is preferred that 4 is a hydrogen atom. When R 3 and R 4 are hydrogen atoms, there is no bulky substituent that causes molecular movement, so the free volume becomes small and the coefficient of linear expansion becomes small. If you want to improve the elastic modulus, R 3 and R 4 are preferably an alkyl group or an allyl group having 1 to 10 carbon atoms, and if you want to improve heat resistance, R 3 and R 4 are preferably glycidyl ether groups. It is preferable that The orientation of the substituents for R 3 and R 4 may be in the ortho, meta, or para position with respect to the glycidyl ether group, but in the case of a glycidyl ether group, the orientation may be in the meta position or in the alkyl having 1 to 10 carbon atoms. or allyl group, the para position is preferred.
前記式（１）中、ｎの値はゲルパーミエーションクロマトグラフィー（ＧＰＣ、検出器：ＲＩ）の測定により求めることが出来る。ｎは通常１～２０の実数であるが、１～１０であることが好ましく、１～５であることがより好ましい。ｎが２０よりも大きくなると分子量が増大して高粘度になるため加工性が劣る。
また、ｎの平均値はゲルパーミエーションクロマトグラフィー（ＧＰＣ、検出器：ＲＩ）の測定により求められた数平均分子量、あるいは分離したピークの各々の面積比から算出することが出来る。ｎの平均値は１～１０であることが好ましく、１．１～１０であることがより好ましく、１．１～５であることが特に好ましい。
In the formula (1), the value of n can be determined by gel permeation chromatography (GPC, detector: RI). n is usually a real number from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5. When n is larger than 20, the molecular weight increases and the viscosity becomes high, resulting in poor processability.
Further, the average value of n can be calculated from the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) or the area ratio of each separated peak. The average value of n is preferably 1 to 10, more preferably 1.1 to 10, particularly preferably 1.1 to 5.
前記式（１）で表されるエポキシ樹脂のエポキシ当量の好ましい範囲は３００ｇ／ｅｑ．以上６００ｇ／ｅｑ．未満であり、更に好ましくは３１０ｇ／ｅｑ．以上５５０ｇ／ｅｑ．未満である。前記式（１）で表されるエポキシ当量が３００ｇ／ｅｑ．未満の場合、架橋密度が増加し耐熱性は向上するが、固くもろくなり機械強度の低下を招くことから好ましくない。また前記式（１）で表されるエポキシ当量が６００ｇ／ｅｑ．以上の場合、架橋密度が減少し硬化物の脆さが改善されるが、耐熱性の低下を招くため好ましくない。エポキシ当量が適正な場合、機械強度の低下を引き起こすことなく硬化物の耐熱性を向上させることができる。 A preferable range of the epoxy equivalent of the epoxy resin represented by the above formula (1) is 300 g/eq. More than 600g/eq. less than 310 g/eq., more preferably 310 g/eq. More than 550g/eq. less than The epoxy equivalent represented by the above formula (1) is 300 g/eq. If it is less than that, the crosslinking density increases and the heat resistance improves, but it becomes hard and brittle and causes a decrease in mechanical strength, which is not preferable. Further, the epoxy equivalent represented by the above formula (1) is 600 g/eq. In the above case, the crosslinking density decreases and the brittleness of the cured product is improved, but this is not preferable because it causes a decrease in heat resistance. When the epoxy equivalent is appropriate, the heat resistance of the cured product can be improved without causing a decrease in mechanical strength.
本発明において、エポキシ当量は下記条件で測定する。
［エポキシ当量の各種条件］
ＪＩＳ Ｋ－７２３６に記載された方法で測定し、単位はｇ／ｅｑ．である。
In the present invention, the epoxy equivalent is measured under the following conditions.
[Various conditions for epoxy equivalent]
Measured by the method described in JIS K-7236, and the unit is g/eq. It is.
前記式（１）で表されるエポキシ樹脂の軟化点の好ましい範囲は５０～１２０℃であり、更に好ましくは５５～１１０℃である。軟化点が上記の範囲であると樹脂同士が室温においてブロッキングしないため、ハンドリング性に優れる。 The softening point of the epoxy resin represented by formula (1) is preferably from 50 to 120°C, more preferably from 55 to 110°C. When the softening point is within the above range, the resins do not block each other at room temperature, resulting in excellent handling properties.
本発明のエポキシ樹脂は、耐吸水性、電気特性に優れる。１００℃の水中で２４時間煮沸した後の吸水率は１．４以下であることが好ましく、さらに好ましくは１．２以下であり、特に好ましくは１．０以下である。吸水率が高すぎると前述したようにクラックや剥離の原因となることに加え、硬化物が水分を吸着することで材料が著しく軟化し、機械的強度が低く影響を及ぼすため好ましくない。電気特性は１ＧＨｚでの誘電正接が０．０３０以下であることが好ましい。誘電正接が高いと、通信に用いられる電気信号の一部を熱へと変換してしまい、信号の損失が生じてしまう。高周波になるにつれて、誘電正接の影響が顕著に表れてくる。 The epoxy resin of the present invention has excellent water absorption resistance and electrical properties. The water absorption coefficient after boiling in water at 100° C. for 24 hours is preferably 1.4 or less, more preferably 1.2 or less, particularly preferably 1.0 or less. If the water absorption rate is too high, in addition to causing cracks and peeling as described above, the cured product absorbs water, causing the material to become significantly softer and lowering its mechanical strength, which is undesirable. As for the electrical properties, it is preferable that the dielectric loss tangent at 1 GHz is 0.030 or less. If the dielectric loss tangent is high, part of the electrical signal used for communication will be converted into heat, resulting in signal loss. As the frequency increases, the influence of the dielectric loss tangent becomes more apparent.
本発明のエポキシ樹脂は、下記式（２）で表されるフェノール樹脂とエピクロロヒドリンとの反応により得ることができる。 The epoxy resin of the present invention can be obtained by reacting a phenol resin represented by the following formula (2) with epichlorohydrin.
式（２）中のＲ１～Ｒ４、ａ～ｄ、ｎの値、および好ましい範囲は前記式（１）と同様である。 The values and preferred ranges of R 1 to R 4 , a to d, and n in formula (2) are the same as in formula (1) above.
前記式（２）で表されるフェノール樹脂の合成法としては、ジシクロペンタジエン類とフェノール類との縮合反応が挙げられ、この場合のフェノール類の使用量はジシクロペンタジエン類１モルに対して好ましくは２～２０モルである。 A method for synthesizing the phenolic resin represented by the above formula (2) includes a condensation reaction between dicyclopentadiene and phenol, and in this case, the amount of phenol used is 1 mole of dicyclopentadiene. Preferably it is 2 to 20 moles.
フェノール類としては、２置換フェノールとしてカテコール、レゾルシノール、ハイドロキノン、１置換フェノールとしてフェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾールが挙げられ、単独でも２種類以上を併用しても良い。 Examples of phenols include catechol, resorcinol, and hydroquinone as disubstituted phenols, and phenol, o-cresol, m-cresol, and p-cresol as monosubstituted phenols, and these may be used alone or in combination of two or more.
ジシクロペンタジエン類としては、メチルジシクロペンタジエン、エチルジシクロペンタジエン、アリルジシクロペンタジエンなどが挙げられるが、好ましくはメチルジシクロペンタジエン、エチルジシクロペンタジエンであり、さらに好ましくは、メチルジシクロペンタジエンである。無置換のジシクロペンタジエンと比較して、ジシクロペンタジエン類のように、アルキル基やアリル基が導入されることにより疎水性が増し相対的に低吸水、低分極になり、硬化物が優れた耐吸水性と電気特性を示すようになる。また長鎖のアルキル鎖を持ったジシクロペンタジエン類を原料に用いた場合、エポキシ樹脂の溶融粘度が高くなってしまいプリプレグ作製の際の樹脂の含侵性が悪くなってしまい、強度低下を引き起こす可能性がある。そのため、炭素数１～２の短鎖のアルキル鎖が結合したジシクロペンタジエン類を用いることが好ましい。 Examples of dicyclopentadiene include methyldicyclopentadiene, ethyldicyclopentadiene, allyldicyclopentadiene, etc., but methyldicyclopentadiene and ethyldicyclopentadiene are preferable, and methyldicyclopentadiene is more preferable. be. Compared to unsubstituted dicyclopentadiene, the introduction of alkyl or allyl groups, such as dicyclopentadiene, increases hydrophobicity, resulting in relatively low water absorption and low polarization, resulting in excellent cured products. It exhibits water absorption resistance and electrical properties. In addition, when dicyclopentadienes with long alkyl chains are used as raw materials, the melt viscosity of the epoxy resin increases, which impairs the impregnability of the resin during prepreg production, resulting in a decrease in strength. there is a possibility. Therefore, it is preferable to use dicyclopentadienes to which a short alkyl chain having 1 to 2 carbon atoms is bonded.
上記縮合反応においては酸触媒を用いるのが好ましく、酸触媒としては三フッ化ホウ素、無水塩化アルミニウム、塩化亜鉛、硫酸、塩化チタンなどのルイス酸が好ましく、特に上記のルイス酸のエーテル錯体、フェノール錯体か好ましい。これらの酸触媒は単独でも２種類以上を併用しても良い。 In the above condensation reaction, it is preferable to use an acid catalyst, and the acid catalyst is preferably a Lewis acid such as boron trifluoride, anhydrous aluminum chloride, zinc chloride, sulfuric acid, titanium chloride, etc. In particular, an ether complex of the above Lewis acid, phenol Complexes are preferred. These acid catalysts may be used alone or in combination of two or more.
これら酸触媒の使用量は特に限定されるものではないが、使用するジシクロペンタジエンの使用量に対して０．００１～０．１モルの範囲で選定することができる。また、これらの酸触媒を反応系内に添加する場合は予めフェノール類の加熱溶融物に添加しておいたり適当な溶剤に希釈したりして徐々に添加することも可能である。 The amount of these acid catalysts used is not particularly limited, but can be selected within the range of 0.001 to 0.1 mol relative to the amount of dicyclopentadiene used. Furthermore, when adding these acid catalysts into the reaction system, it is also possible to add them in advance to a heated melt of phenols, or to dilute them with a suitable solvent and then gradually add them.
これら酸触媒存在下の縮合反応は４０～１８０℃で行われるのが好ましく、反応時間は通常０．５～１２時間である。また、これらの反応はニトロベンゼン、ジフェニルエーテル、ジクロロベンゼン、二硫化炭素など反応に不活性な溶媒の存在下で行うこともできる。さらにこうして得られた反応物は系内が中性になるように中和を行ったり溶媒の存在下に水洗を繰り返したりした後、水を分離排水後、水蒸気蒸留により、溶媒及び未反応物を除去することにより前記式（２）で表されるフェノール樹脂が得られる。 These condensation reactions in the presence of an acid catalyst are preferably carried out at 40 to 180°C, and the reaction time is usually 0.5 to 12 hours. Further, these reactions can also be carried out in the presence of a solvent inert to the reaction, such as nitrobenzene, diphenyl ether, dichlorobenzene, carbon disulfide, or the like. Furthermore, the reaction product thus obtained is neutralized to make the system neutral, and after repeated washing with water in the presence of a solvent, the water is separated and drained, and the solvent and unreacted materials are removed by steam distillation. By removing it, a phenol resin represented by the above formula (2) is obtained.
前記式（２）で表されるフェノール樹脂の水酸基当量の好ましい範囲は２１０ｇ／ｅｑ．以上３５０ｇ／ｅｑ．未満であり、更に好ましくは２３０ｇ／ｅｑ．以上～３３０ｇ／ｅｑ．未満である。前記式（２）で表されるフェノール樹脂中の水酸基濃度が高い場合、架橋密度が増加するため固くもろくなり機械強度の低下を招くことから好ましくない。水酸基当量が適正な場合、機械強度の低下を引き起こすことなく硬化物の耐熱性を向上させることができる。 The preferred range of the hydroxyl equivalent of the phenol resin represented by the above formula (2) is 210 g/eq. More than 350g/eq. less than 230g/eq., more preferably 230g/eq. Above ~330g/eq. less than A high concentration of hydroxyl groups in the phenol resin represented by the above formula (2) is not preferable because the crosslinking density increases, making it hard and brittle, leading to a decrease in mechanical strength. When the hydroxyl equivalent is appropriate, the heat resistance of the cured product can be improved without causing a decrease in mechanical strength.
本発明において、水酸基当量は下記条件で測定する。
［水酸基当量の各種条件］
ＪＩＳ Ｋ－７２３６に記載された方法で測定し、単位はｇ／ｅｑ．である。
In the present invention, the hydroxyl equivalent is measured under the following conditions.
[Various conditions for hydroxyl group equivalent]
Measured by the method described in JIS K-7236, and the unit is g/eq. It is.
前記式（２）で表されるフェノール樹脂の軟化点の好ましい範囲は５０～１２０℃であり、更に好ましくは５５～１１０℃である。軟化点が上記の範囲であると樹脂同士が室温においてブロッキングしないため、ハンドリング性に優れる。 The softening point of the phenolic resin represented by formula (2) is preferably 50 to 120°C, more preferably 55 to 110°C. When the softening point is within the above range, the resins do not block each other at room temperature, resulting in excellent handling properties.
つづいて、本発明のエポキシ樹脂を得る反応について説明する。
本発明のエポキシ樹脂は、前記式（２）で表されるフェノール樹脂とエピクロロヒドリンとを反応させて得られる。
Next, the reaction for obtaining the epoxy resin of the present invention will be explained.
The epoxy resin of the present invention is obtained by reacting the phenol resin represented by the formula (2) with epichlorohydrin.
前記エピクロロヒドリンは市場から容易に入手できる。エピクロロヒドリンの使用量は原料フェノール混合物の水酸基１モルに対し通常３．０～１０モル、好ましくは３．５～８．０モル、より好ましくは４．０～７．０モルである。 The epichlorohydrin is easily available on the market. The amount of epichlorohydrin used is usually 3.0 to 10 mol, preferably 3.5 to 8.0 mol, more preferably 4.0 to 7.0 mol, per 1 mol of hydroxyl groups in the raw material phenol mixture.
上記反応において、エポキシ化工程を促進する触媒としてアルカリ金属水酸化物を使用することができる。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が、本発明においては特に、溶解性、ハンドリングの面からフレーク状に成型された固形物の使用が好ましい。
アルカリ金属水酸化物の使用量は原料フェノール混合物の水酸基１モルに対して通常０．９０～１．５０モルである。
In the above reaction, an alkali metal hydroxide can be used as a catalyst to accelerate the epoxidation process. Examples of alkali metal hydroxides that can be used include sodium hydroxide, potassium hydroxide, etc., and solid forms or aqueous solutions thereof may be used; however, in the present invention, in particular, solubility, From the viewpoint of handling, it is preferable to use a solid material shaped into flakes.
The amount of alkali metal hydroxide used is usually 0.90 to 1.50 mol per 1 mol of hydroxyl groups in the raw phenol mixture.
また、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してもかまわない。４級アンモニウム塩の使用量としては原料フェノール混合物の水酸基１モルに対し通常０．０００９～０．１５モルである。 Further, in order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, etc. may be added as a catalyst. The amount of quaternary ammonium salt used is usually 0.0009 to 0.15 mol per 1 mol of hydroxyl groups in the raw phenol mixture.
反応温度は通常３０～９０℃であり、好ましくは３５～８０℃である。特に本発明においては、より高純度なエポキシ化のために５０℃以上が好ましい。反応時間は通常０．５～１０時間であり、好ましくは１～８時間、特に好ましくは１～３時間である。反応時間が短いと反応が進みきらず、反応時間が長くなると副生成物ができることから好ましくない。
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クロ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炭素数４～７のケトン化合物（たとえば、メチルイソブチルケトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン等が挙げられる。）を溶剤として溶解し、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混合物の水酸基１モルに対して通常０．０１～０．３モル、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. Particularly in the present invention, the temperature is preferably 50° C. or higher for higher purity epoxidation. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is too short, the reaction will not proceed to completion, and if the reaction time is too long, by-products will be produced, which is not preferable.
After washing the reactants of these epoxidation reactions with water, or without washing with water, epichlorohydrin, solvent, etc. are removed under heating and reduced pressure. Furthermore, in order to obtain an epoxy resin with even less hydrolyzable halogen, the recovered epoxy resin is treated with a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent. It is also possible to ensure ring closure by dissolving the compound as a reaction mixture and adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to carry out the reaction. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol per 1 mol of hydroxyl groups in the raw material phenol mixture 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 the reaction is completed, 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.
本発明のエポキシ樹脂組成物は硬化剤を含有する。用い得る硬化剤としては、例えばアミン系硬化剤、酸無水物系硬化剤、アミド系硬化剤、及びフェノール系硬化剤等が挙げられる。 The epoxy resin composition of the present invention contains a curing agent. Examples of the curing agent that can be used include amine curing agents, acid anhydride curing agents, amide curing agents, and phenolic curing agents.
本発明のエポキシ樹脂組成物においては特に、エポキシ樹脂組成物の低線膨張と樹脂硬化物の耐熱性をバランス良く両立できるためアミン硬化剤が好ましい。アミン系硬化剤としては、３，３’－ジアミノジフェニルスルホン（３，３’－ＤＤＳ）、４，４’－ジアミノジフェニルスルホン（４，４’－ＤＤＳ）、ジアミノジフェニルメタン（ＤＤＭ）、３，３’－ジイソプロピル－４，４’－ジアミノジフェニルメタン、３，３’－ジ－ｔ－ブチル－４，４’－ジアミノジフェニルメタン、３，３’－ジエチル－５，５’－ジメチル－４，４’－ジアミノジフェニルメタン、３，３’－ジイソプロピル－５，５’－ジメチル－４，４’－ジアミノジフェニルメタン、３，３’－ジ－ｔ－ブチル－５，５’－ジメチル－４，４’－ジアミノジフェニルメタン、３，３’,５，５’－テトラエチル－４，４’－ジアミノジフェニルメタン、３，３’－ジイソプロピル－５，５’－ジエチル－４，４’－ジアミノジフェニルメタン、３，３’－ジ－ｔ－ブチル－５，５’－ジエチル－４，４’－ジアミノジフェニルメタン、３，３’，５，５’－テトライソプロピル－４，４’－ジアミノジフェニルメタン、３，３’－ジ－ｔ－ブチル－５，５’－ジイソプロピル－４，４’－ジアミノジフェニルメタン、３，３’，５，５’－テトラ－ｔ－ブチル－４，４’－ジアミノジフェニルメタン、ジアミノジフェニルエーテル（ＤＡＤＰＥ）、ビスアニリン、ベンジルジメチルアニリン、２－（ジメチルアミノメチル）フェノール（ＤＭＰ－１０）、２，４，６－トリス（ジメチルアミノメチル）フェノール（ＤＭＰ－３０）、２，４，６－トリス（ジメチルアミノメチル）フェノールの２－エチルヘキサン酸エステル等を使用することができる。また、アニリンノボラック、オルソエチルアニリンノボラック、アニリンとキシリレンクロライドとの反応により得られるアニリン樹脂、アニリンと置換ビフェニル類（４，４’－ビス（クロルメチル）－１，１’－ビフェニル及び４，４’－ビス（メトキシメチル）－１，１’－ビフェニル等）、若しくは置換フェニル類（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）ベンゼン及び１，４－ビス（ヒドロキシメチル）ベンゼン等）等との重縮合により得られるアニリン樹脂等が挙げられる。 In the epoxy resin composition of the present invention, an amine curing agent is particularly preferred because it can achieve both low linear expansion of the epoxy resin composition and heat resistance of the cured resin in a well-balanced manner. Examples of the amine curing agent include 3,3'-diaminodiphenylsulfone (3,3'-DDS), 4,4'-diaminodiphenylsulfone (4,4'-DDS), diaminodiphenylmethane (DDM), 3,3 '-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'- Diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane , 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-di- t-Butyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl -5,5'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetra-t-butyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether (DADPE), bisaniline, benzyl dimethyl Aniline, 2-(dimethylaminomethyl)phenol (DMP-10), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), 2,4,6-tris(dimethylaminomethyl)phenol - Ethylhexanoic acid ester etc. can be used. In addition, aniline novolak, orthoethylaniline novolac, aniline resin obtained by the reaction of aniline and xylylene chloride, aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4 '-bis(methoxymethyl)-1,1'-biphenyl) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis( Examples include aniline resins obtained by polycondensation with hydroxymethyl)benzene, etc.).
酸無水物系硬化剤としては無水フタル酸、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及びメチルヘキサヒドロ無水フタル酸等が挙げられる。 Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydro. Examples include phthalic anhydride.
アミド系硬化剤としては、ジシアンジアミド、若しくはリノレン酸の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等が挙げられる。 Examples of the amide curing agent include polyamide resins synthesized from dicyandiamide or a dimer of linolenic acid and ethylenediamine.
フェノール系硬化剤としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂;多価フェノール類（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’－ジヒドロキシビフェニル、２，２’－ジヒドロキシビフェニル、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）メタン及び１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン等）；フェノール類（例えば、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及びジヒドロキシナフタレン等）と、アルデヒド類（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及びフルフラール等）、ケトン類（ｐ－ヒドロキシアセトフェノン及びｏ－ヒドロキシアセトフェノン等）、若しくはジエン類（ジシクロペンタジエン及びトリシクロペンタジエン等）との縮合により得られるフェノール樹脂；前記フェノール類と、置換ビフェニル類（４，４’－ビス（クロルメチル）－１，１’－ビフェニル及び４，４’－ビス（メトキシメチル）－１，１’－ビフェニル等）、若しくは置換フェニル類（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）ベンゼン及び１，４－ビス（ヒドロキシメチル）ベンゼン等）等との重縮合により得られるフェノール樹脂；前記フェノール類及び／又は前記フェノール樹脂の変性物；テトラブロモビスフェノールＡ及び臭素化フェノール樹脂等のハロゲン化フェノール類が挙げられる。 Examples of phenolic curing agents include phenol novolak resin, cresol novolac resin, phenol aralkyl resin; polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-dihydroxybiphenyl, 2, 2'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-(1,1'-biphenyl)-4,4'-diol, hydroquinone, resorcinol, naphthalene diol, tris-(4-hydroxyphenyl) methane and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, etc.); phenols (e.g., phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.); aldehydes (e.g., Formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, furfural, etc.), ketones (p-hydroxyacetophenone, o-hydroxyacetophenone, etc.), or dienes (dicyclopentadiene, tricyclopentadiene, etc.) Phenol resin obtained by condensation; the above phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), etc.) obtained by polycondensation with Phenol resin; the above-mentioned phenols and/or modified products of the above-mentioned phenol resins; halogenated phenols such as tetrabromobisphenol A and brominated phenol resins.
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０．７～１．２当量が好ましい。エポキシ基１当量に対して０．７当量に満たない場合、或いは１．２当量を越える場合、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 curing agent used is preferably 0.7 to 1.2 equivalents per equivalent of epoxy groups in the epoxy resin. If the amount is less than 0.7 equivalents or more than 1.2 equivalents per equivalent of epoxy group, curing may be incomplete and good cured physical properties may not be obtained.
また本発明のエポキシ樹脂組成物においては必要に応じて、硬化促進剤を配合しても良い。硬化促進剤を使用することによりゲル化時間を調整することも出来る。使用できる硬化促進剤の例としては２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾールなどのイミダゾール類、２－（ジメチルアミノメチル）フェノール、１，８－ジアザ－ビシクロ（５，４，０）ウンデセン－７等の第３級アミン類、トリフェニルホスフィンなどのホスフィン類、オクチル酸スズ等の金属化合物が挙げられる。硬化促進剤はエポキシ樹脂１００重量部に対して０．０１～５．０重量部が必要に応じ用いられる。 Furthermore, the epoxy resin composition of the present invention may contain a curing accelerator, if necessary. The gelation time can also be adjusted by using a curing accelerator. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, and 1,8-diaza-bicyclo(5 , 4,0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.
本発明のエポキシ樹脂組成物においては、他のエポキシ樹脂を配合しても良く、具体例としては、フェノール類（フェノール、アルキル置換フェノール、芳香族置換フェノール、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、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等）と各種アルデヒド（ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等）との重縮合物、フェノール類と各種ジエン化合物（ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等）との重合物、フェノール類とケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等）との重縮合物、フェノール類と置換ビフェニル類（４，４’－ビス（クロルメチル）－１，１’－ビフェニル及び４，４’－ビス（メトキシメチル）－１，１’－ビフェニル等）、若しくは置換フェニル類（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）ベンゼン及び１，４－ビス（ヒドロキシメチル）ベンゼン等）等との重縮合により得られるフェノール樹脂、ビスフェノール類と各種アルデヒドの重縮合物、アルコール類等をグリシジル化したグリシジルエーテル系エポキシ樹脂、４－ビニル－１－シクロヘキセンジエポキシドや３，４－エポキシシクロヘキシルメチル－３，４’－エポキシシクロヘキサンカルボキシラートなどを代表とする脂環式エポキシ樹脂、テトラグリシジルジアミノジフェニルメタン（ＴＧＤＤＭ）やトリグリシジル－ｐ－アミノフェノールなどを代表とする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が挙げられるが、通常用いられるエポキシ樹脂であればこれらに限定されるものではない。 In the epoxy resin composition of the present invention, other epoxy resins may be blended, and specific examples include phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted phenol, polycondensates of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); Polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'- bis(methoxymethyl)-1,1'-biphenyl, etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1,4-bis(hydroxymethyl) ), benzene, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, etc., 4-vinyl-1-cyclohexene diepoxide, 3, Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate; glycidylamine-based epoxies such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol; Examples include resins, glycidyl ester epoxy resins, etc., but the epoxy resin is not limited to these as long as it is a commonly used epoxy resin.
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、シアネートエステル系化合物、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。 Known additives can be added to the epoxy resin composition of the present invention, if necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesins, maleimide compounds, cyanate ester compounds, silicone gels, and silicone oils. , as well as inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, and fillers such as silane coupling agents. Examples include surface treatment agents for materials, mold release agents, and coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green.
本発明のエポキシ樹脂組成物には、必要に応じて公知のマレイミド系化合物を配合することができる。用いうるマレイミド化合物の具体例としては、４，４’－ジフェニルメタンビスマレイミド、ポリフェニルメタンマレイミド、ｍ－フェニレンビスマレイミド、２，２’－ビス〔４－（４－マレイミドフェノキシ）フェニル〕プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、４，４’－ジフェニルエーテルビスマレイミド、４，４’－ジフェニルスルフォンビスマレイミド、１，３－ビス（３－マレイミドフェノキシ）ベンゼン、１，３－ビス（４－マレイミドフェノキシ）ベンゼン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種以上併用してもよい。マレイミド系化合物を配合する際は、必要により硬化促進剤を配合するが、前記硬化促進剤や、有機過酸化物、アゾ化合物などのラジカル重合開始剤など使用できる。 The epoxy resin composition of the present invention may contain a known maleimide compound, if necessary. Specific examples of maleimide compounds that can be used include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, , 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone Examples include, but are not limited to, bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and 1,3-bis(4-maleimidophenoxy)benzene. These may be used alone or in combination of two or more. When blending the maleimide compound, a curing accelerator is blended if necessary, and the above curing accelerators and radical polymerization initiators such as organic peroxides and azo compounds can be used.
本発明のエポキシ樹脂組成物は、有機溶剤を添加しワニス状の組成物（以下、単にワニスという。）とすることができる。用いられる溶剤としては、例えばγ－ブチロラクトン類、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、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、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、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン等のケトン系溶剤、トルエン、キシレンなどの芳香族系溶剤が挙げられる。溶剤は、得られたワニス中の溶剤を除く固形分濃度が通常１０～８０重量％、好ましくは２０～７０重量％となる範囲で使用する。 The epoxy resin composition of the present invention can be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. Examples of the solvents used include amide solvents such as γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone, and tetramethylene sulfone. Ether solvents such as sulfones, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Solvents include aromatic solvents such as toluene and xylene. The solvent is used in such a range that the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight.
つづいて、本発明の硬化物、樹脂シート、プリプレグ、ＦＲＰを説明する。
本発明のエポキシ樹脂組成物を支持基材の片面または両面に塗布し、樹脂シートとして用いてもよい。塗布方法としては、例えば、注型法、ポンプや押し出し機等により樹脂をノズルやダイスから押し出し、ブレードで厚さを調整する方法、ロールによりカレンダー加工して厚さを表製する方法、スプレー等を用いて噴霧する方法等が挙げられる。なお、層を形成する工程においては、エポキシ樹脂組成物の熱分解を回避可能な温度範囲で加熱しながら行ってもよい。また、必要に応じて圧延処理、研削処理等を施してもよい。支持基材としては、例えば紙、布、不織布等からなる多孔質基材、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルムなどのプラスチックフィルムあるいはシート、ネット、発泡体、金属箔、およびこれらのラミネート体などの適宜な薄葉体等が挙げられるが、これらに限定されるものではない。支持基材に厚さは特に制限されず、用途に応じて適宜に決定される。
Next, the cured product, resin sheet, prepreg, and FRP of the present invention will be explained.
The epoxy resin composition of the present invention may be applied to one or both sides of a supporting base material and used as a resin sheet. Application methods include, for example, casting, extruding the resin through a nozzle or die using a pump or extruder, adjusting the thickness with a blade, calendering with a roll to measure the thickness, spraying, etc. Examples include a method of spraying using a. In addition, in the step of forming the layer, the epoxy resin composition may be heated while being heated within a temperature range that can avoid thermal decomposition. Further, rolling treatment, grinding treatment, etc. may be performed as necessary. Examples of supporting substrates include porous substrates made of paper, cloth, nonwoven fabric, etc., plastic films or sheets such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, nets, foams, metal foils, and laminates thereof. Examples include, but are not limited to, appropriate thin film bodies. The thickness of the supporting base material is not particularly limited and is appropriately determined depending on the application.
本発明のエポキシ樹脂組成物および／または樹脂シートを加熱溶融して低粘度化して繊維基材に含浸させることにより本発明のプリプレグを得ることができる。 The prepreg of the present invention can be obtained by heating and melting the epoxy resin composition and/or resin sheet of the present invention to lower the viscosity and impregnating it into a fiber base material.
また、ワニス状のエポキシ樹脂組成物を、繊維基材に含浸させて加熱乾燥させることにより本発明のプリプレグを得ることもできる。上記のプリプレグを所望の形に裁断、積層後、積層物にプレス成形法やオートクレーブ成形法、シートワインディング成形法などで圧力をかけながらエポキシ樹脂組成物を加熱硬化させることにより本発明のＦＲＰを得ることができる。また、プリプレグの積層時に銅箔や有機フィルムを積層することもできる。 Further, the prepreg of the present invention can also be obtained by impregnating a fiber base material with a varnish-like epoxy resin composition and heating and drying the impregnated fiber base material. After cutting and laminating the above prepreg into a desired shape, the FRP of the present invention is obtained by heating and curing the epoxy resin composition while applying pressure to the laminate using a press molding method, an autoclave molding method, a sheet winding molding method, etc. be able to. Moreover, copper foil or an organic film can also be laminated at the time of laminating the prepreg.
さらに、本発明のＦＲＰの成形方法は、上記の方法のほかに、公知の方法にて成形して得ることもできる。例えば、炭素繊維基材（通常、炭素繊維織物を使用）を裁断、積層、賦形してプリフォーム（樹脂を含浸する前の予備成形体）を作製、プリフォームを成形型内に配置して型を閉じ、樹脂を注入してプリフォームに含浸、硬化させた後、型を開いて成形品を取り出すレジントランスファー成形技術（ＲＴＭ法）を用いることもできる。
また、ＲＴＭ法の一種である、例えば、ＶａＲＴＭ法、ＳＣＲＩＭＰ（Ｓｅｅｍａｎ’ｓ Ｃｏｍｐｏｓｉｔｅ Ｒｅｓｉｎ Ｉｎｆｕｓｉｏｎ Ｍｏｌｄｉｎｇ Ｐｒｏｃｅｓｓ）法、特表２００５－５２７４１０記載の樹脂供給タンクを大気圧よりも低い圧力まで排気し、循環圧縮を用い、かつ正味の成形圧力を制御することにとよって、樹脂注入プロセス、特にＶａＲＴＭ法をより適切に制御するＣＡＰＲＩ（Ｃｏｎｔｒｏｌｌｅｄ Ａｔｍｏｓｐｈｅｒｉｃ Ｐｒｅｓｓｕｒｅ Ｒｅｓｉｎ Ｉｎｆｕｓｉｏｎ）法なども用いることができる。
Furthermore, in addition to the above-mentioned method, the FRP of the present invention can be molded by a known method. For example, a carbon fiber base material (usually carbon fiber fabric is used) is cut, laminated, and shaped to create a preform (a preform before being impregnated with resin), and the preform is placed in a mold. It is also possible to use a resin transfer molding technique (RTM method) in which the mold is closed, a resin is injected to impregnate the preform and cured, and then the mold is opened to take out the molded product.
In addition, a type of RTM method, for example, the VaRTM method, the SCRIMP (Seeman's Composite Resin Infusion Molding Process) method, the resin supply tank described in Special Table 2005-527410 is evacuated to a pressure lower than atmospheric pressure, and the cyclic compression is performed. The CAPRI (Controlled Atmospheric Pressure Resin Infusion) method, which more appropriately controls the resin injection process, especially the VaRTM method, can also be used by using and controlling the net molding pressure.
さらに、繊維基材を樹脂シート（フィルム）で挟み込むフィルムスタッキング法や、含浸向上のため強化繊維基材にパウダー状の樹脂を付着させる方法、繊維基材に樹脂を混ぜる過程において流動層あるいは流体スラリー法を用いる成形方法（Ｐｏｗｄｅｒ Ｉｍｐｒｅｇｎａｔｅｄ Ｙａｒｎ）、繊維基材に樹脂繊維を混繊させる方法も用いることができる。 In addition, we have developed a film stacking method in which the fiber base material is sandwiched between resin sheets (films), a method in which powdered resin is attached to the reinforcing fiber base material to improve impregnation, and a fluidized bed or fluid slurry method in the process of mixing resin with the fiber base material. A molding method using a powder impregnated yarn method and a method of mixing resin fibers into a fiber base material can also be used.
炭素繊維としては、アクリル系、ピッチ系、レーヨン系などの炭素繊維が挙げられ、なかでも引張強度の高いアクリル系の炭素繊維が好ましく用いられる。炭素繊維の形態としては、有撚糸、解撚糸および無撚糸等を使用することができるが、繊維強化複合材料の成形性と強度特性のバランスが良いため、解撚糸または無撚糸が好ましく用いられる。 Examples of the carbon fibers include acrylic, pitch, and rayon carbon fibers, and among them, acrylic carbon fibers with high tensile strength are preferably used. As the form of the carbon fiber, twisted yarn, untwisted yarn, untwisted yarn, etc. can be used, but untwisted yarn or untwisted yarn is preferably used because it provides a good balance between the formability and strength characteristics of the fiber reinforced composite material.
以下に実施例を挙げて本発明をさらに具体的に説明する。以下に示す材料、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。
以下に実施例で用いた各種分析方法について記載する。
The present invention will be explained in more detail with reference to Examples below. The materials, processing details, processing procedures, etc. shown below can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below.
Various analytical methods used in the examples are described below.
各種分析方法について以下の条件で行った。
・水酸基当量、エポキシ当量
ＪＩＳ Ｋ－７２３６に記載された方法で測定し、単位はｇ／ｅｑ．である。
・軟化点
ＪＩＳ Ｋ－７２３４に準拠した方法で測定し、単位は℃である。
・溶融粘度
ＩＣＩ溶融粘度（１５０℃）コーンプレート法で測定し、単位はＰａ・ｓである。
Various analytical methods were conducted under the following conditions.
- Hydroxyl group equivalent, epoxy equivalent Measured by the method described in JIS K-7236, and the unit is g/eq. It is.
- Softening point Measured according to JIS K-7234, and the unit is °C.
- Melt viscosity ICI melt viscosity (150° C.) Measured by cone plate method, unit is Pa·s.
・ＧＰＣ（ゲルパーエミッションクロマトグラフィー）分析
メーカー：Ｗａｔｅｒｓ
カラム：ガードカラム ＳＨＯＤＥＸ ＧＰＣ ＫＦ－６０１（２本）、ＫＦ－６０２ ＫＦ－６０２．５、ＫＦ－６０３
流速：１．２３ｍｌ／ｍｉｎ．
カラム温度：２５℃
使用溶剤：ＴＨＦ（テトラヒドロフラン）
検出器：ＲＩ（示差屈折検出器）
・GPC (gel per emission chromatography) analysis Manufacturer: Waters
Column: Guard column SHODEX GPC KF-601 (2 pieces), KF-602 KF-602.5, KF-603
Flow rate: 1.23ml/min.
Column temperature: 25℃
Solvent used: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
［実施例１］
温度計、攪拌機、滴下ロート、冷却器を備え付けた４つ口フラスコにフェノール１６９．１質量部、三フッ化ホウ素ジエチルエーテル錯体３．８質量部を仕込み５０℃で溶解させた。メチルジシクロペンタジエン１４４．０質量部を１時間かけて滴下して仕込み、そのまま３時間反応させた後、７５℃で２時間、１３５℃で２時間、１６０℃で３時間段階的に昇温させながら反応させた。反応終了後トリポリりん酸ソーダ１９．８質量部、メチルイソブチルケトン４６９．６質量部加え撹拌し、温水を加え水洗を繰り返し、系内を中性にした。その後得られた溶液を、ロータリーエバポレータを用いて１８０℃減圧下でメチルイソブチルケトン等を留去することでフェノール樹脂（Ｐ－１）を１８８質量部得た。得られた樹脂の水酸基当量は２８４ｇ／ｅｑ．であった。繰り返し数ｎの平均値は４．１３であった。図１にＧＰＣチャートを示す。
[Example 1]
In a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser, 169.1 parts by mass of phenol and 3.8 parts by mass of boron trifluoride diethyl ether complex were charged and dissolved at 50°C. 144.0 parts by mass of methyldicyclopentadiene was added dropwise over 1 hour and reacted for 3 hours, then heated stepwise at 75°C for 2 hours, 135°C for 2 hours, and 160°C for 3 hours. I reacted while doing so. After the reaction was completed, 19.8 parts by mass of sodium tripolyphosphate and 469.6 parts by mass of methyl isobutyl ketone were added and stirred. Warm water was added and water washing was repeated to neutralize the system. Thereafter, methyl isobutyl ketone and the like were distilled off from the resulting solution at 180° C. under reduced pressure using a rotary evaporator to obtain 188 parts by mass of phenol resin (P-1). The hydroxyl equivalent of the obtained resin was 284 g/eq. Met. The average value of the number of repetitions n was 4.13. Figure 1 shows a GPC chart.
［実施例２］
撹拌機、還流冷却管を備えた四つ口フラスコに窒素パージを施しながら実施例１で得られるフェノール樹脂Ｐ－１を３２０質量部、エピクロロヒドリン４３８．２９質量部、ジメチルスルホキシド１０７．１９質量部を加え、水浴を４３℃にまで昇温した。内温が４３℃で安定したところでフレーク状の水酸化ナトリウム４７．１３質量部を１２０分かけて分割添加した後、更に４３℃で２時間、７０℃で３０分反応を行った。反応終了後、ロータリーエバポレータを用いて１２５℃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７０１．０７質量部を加え溶解し、７５℃にまで昇温した。撹拌下で３０重量％の水酸化ナトリウム水溶液１３．５２質量部加え、１時間反応を行った後、水洗を行い、ｐＨ試験紙で洗浄水が中性になったことを確認した。得られた溶液を、ロータリーエバポレータを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂（ＥＰ１）を３４４．７９質量部得た。得られたエポキシ樹脂のエポキシ当量は３７７ｇ／ｅｑ．、軟化点が８５．８℃、ＩＣＩ溶融粘度０．８２Ｐａ・ｓ（１５０℃）であった。繰り返し数ｎの平均値は３．８２であった。図２にＧＰＣチャートを示す。
[Example 2]
While purging with nitrogen into a four-necked flask equipped with a stirrer and a reflux condenser, 320 parts by mass of the phenolic resin P-1 obtained in Example 1, 438.29 parts by mass of epichlorohydrin, and 107.19 parts by mass of dimethyl sulfoxide were added. parts by mass were added and the water bath was heated to 43°C. When the internal temperature became stable at 43°C, 47.13 parts by mass of flaky sodium hydroxide was added in portions over 120 minutes, and the reaction was further carried out at 43°C for 2 hours and at 70°C for 30 minutes. After the reaction was completed, excess epichlorohydrin and other solvents were distilled off under reduced pressure at 125° C. using a rotary evaporator. 701.07 parts by mass of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 75°C. 13.52 parts by mass of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the mixture was reacted for 1 hour, followed by washing with water, and it was confirmed with pH test paper that the washing water had become neutral. Methyl isobutyl ketone and the like were distilled off from the obtained solution under reduced pressure at 180° C. using a rotary evaporator to obtain 344.79 parts by mass of epoxy resin (EP1). The epoxy equivalent of the obtained epoxy resin was 377 g/eq. , the softening point was 85.8°C, and the ICI melt viscosity was 0.82 Pa·s (150°C). The average value of the number of repetitions n was 3.82. Figure 2 shows a GPC chart.
[実施例３]
フェノールの使用量を６００質量部に変更した以外は実施例１と同様の方法で合成し、フェノール樹脂（Ｐ－２）を１６７質量部得た。得られた樹脂の水酸基当量は２３６ｇ／ｅｑ．、軟化点は８８．２℃であった。ＩＣＩ溶融粘度０．２２Ｐａ・ｓ（１５０℃）であった。繰り返し数ｎの平均値は２．４２であった。図３にＧＰＣチャートを示す。
[Example 3]
Synthesis was carried out in the same manner as in Example 1, except that the amount of phenol used was changed to 600 parts by mass, and 167 parts by mass of phenol resin (P-2) was obtained. The hydroxyl equivalent of the obtained resin was 236 g/eq. , the softening point was 88.2°C. The ICI melt viscosity was 0.22 Pa·s (150°C). The average value of the number of repetitions n was 2.42. Figure 3 shows a GPC chart.
[実施例４]
撹拌機、還流冷却管を備えた四つ口フラスコに窒素パージを施しながら実施例３で得られるフェノール樹脂Ｐ－２を１３０質量部、エピクロロヒドリン２１７．７４質量部、ジメチルスルホキシド５２．４０質量部を加え、水浴を４３℃にまで昇温した。内温が４３℃で安定したところでフレーク状の水酸化ナトリウム２３．０４質量部を１２０分かけて分割添加した後、更に４３℃で２時間、７０℃で３０分反応を行った。反応終了後、ロータリーエバポレータを用いて１２５℃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２９４．２６質量部を加え溶解し、７５℃にまで昇温した。撹拌下で３０重量％の水酸化ナトリウム水溶液６．６１質量部加え、１時間反応を行った後、水洗を行い、ｐＨ試験紙で洗浄水が中性になったことを確認した。得られた溶液を、ロータリーエバポレータを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂（ＥＰ２）を１４５質量部得た。得られたエポキシ樹脂のエポキシ当量は３１１ｇ／ｅｑ．、軟化点が５８℃、ＩＣＩ溶融粘度０．０５Ｐａ・ｓ（１５０℃）であった。
[Example 4]
While purging with nitrogen into a four-neck flask equipped with a stirrer and a reflux condenser, 130 parts by mass of phenolic resin P-2 obtained in Example 3, 217.74 parts by mass of epichlorohydrin, and 52.40 parts by mass of dimethyl sulfoxide were added. parts by mass were added and the water bath was heated to 43°C. When the internal temperature became stable at 43°C, 23.04 parts by mass of flaky sodium hydroxide was added in portions over 120 minutes, and the reaction was further carried out at 43°C for 2 hours and at 70°C for 30 minutes. After the reaction was completed, excess epichlorohydrin and other solvents were distilled off under reduced pressure at 125° C. using a rotary evaporator. 294.26 parts by mass of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 75°C. 6.61 parts by mass of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the mixture was reacted for 1 hour, followed by washing with water, and it was confirmed with pH test paper that the washing water had become neutral. Methyl isobutyl ketone and the like were distilled off from the obtained solution under reduced pressure at 180° C. using a rotary evaporator to obtain 145 parts by mass of epoxy resin (EP2). The epoxy equivalent of the obtained epoxy resin was 311 g/eq. , the softening point was 58°C, and the ICI melt viscosity was 0.05 Pa·s (150°C).
［実施例５］
温度計、攪拌機、滴下ロート、冷却器を備え付けた４つ口フラスコにｐ－クレゾール３９０．０質量部、三フッ化ホウ素ジエチルエーテル錯体０．６質量部を仕込み５０℃で溶解させた。メチルジシクロペンタジエン７２．３質量部を１時間かけて滴下して仕込み、そのまま３時間反応させた後、７５℃で２時間、１０５℃で２時間、１３５℃で２時間、１６０℃で１時間段階的に昇温させながら反応させた。反応終了後トリポリりん酸ソーダ３．３質量部、メチルイソブチルケトン２３７．７質量部加え撹拌し、温水を加え水洗を繰り返し、系内を中性にした。その後得られた溶液を、ロータリーエバポレータを用いて１９０℃減圧下でメチルイソブチルケトン等を留去することでフェノール樹脂（Ｐ－３）を１０２質量部得た。得られた樹脂の水酸基当量は４２６ｇ／ｅｑ．、軟化点が５４．３℃、ＩＣＩ溶融粘度０．０２Ｐａ・ｓ（１５０℃）であった。繰り返し数ｎの平均値は１．９３であった。図４にＧＰＣチャートを示す。
[Example 5]
390.0 parts by mass of p-cresol and 0.6 parts by mass of boron trifluoride diethyl ether complex were charged into a four-necked flask equipped with a thermometer, stirrer, dropping funnel, and condenser, and dissolved at 50°C. 72.3 parts by mass of methyldicyclopentadiene was added dropwise over 1 hour and reacted for 3 hours, followed by 2 hours at 75°C, 2 hours at 105°C, 2 hours at 135°C, and 1 hour at 160°C. The reaction was carried out while raising the temperature stepwise. After the reaction was completed, 3.3 parts by mass of sodium tripolyphosphate and 237.7 parts by mass of methyl isobutyl ketone were added and stirred. Warm water was added and water washing was repeated to neutralize the system. Thereafter, methyl isobutyl ketone and the like were distilled off from the resulting solution using a rotary evaporator at 190° C. under reduced pressure to obtain 102 parts by mass of phenol resin (P-3). The hydroxyl equivalent of the obtained resin was 426 g/eq. , the softening point was 54.3°C, and the ICI melt viscosity was 0.02 Pa·s (150°C). The average value of the number of repetitions n was 1.93. FIG. 4 shows a GPC chart.
［実施例６］
撹拌機、還流冷却管を備えた四つ口フラスコに窒素パージを施しながら実施例５で得られるフェノール樹脂Ｐ－３を９０質量部、エピクロロヒドリン８２．１８質量部、ジメチルスルホキシド２０．１０質量部を加え、水浴を４５℃にまで昇温した。内温が４５℃で安定したところでフレーク状の水酸化ナトリウム８．８４質量部を９０分かけて分割添加した後、更に４５℃で２時間、７０℃３０分反応を行った。その後、５０℃以下になるように冷却を行った。反応終了後、ロータリーエバポレータを用いて１２４℃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１８６．２９質量部を加え溶解し、７５℃にまで昇温した。撹拌下で３０重量％の水酸化ナトリウム水溶液２．５４質量部加え、１時間反応を行った後、水洗を行い、ｐＨ試験紙で洗浄水が中性になったことを確認した。得られた溶液を、ロータリーエバポレータを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂（ＥＰ３）を９１．６２質量部得た。得られたエポキシ樹脂のエポキシ当量は５３１ｇ／ｅｑ．であった。
[Example 6]
While purging with nitrogen into a four-necked flask equipped with a stirrer and a reflux condenser, 90 parts by mass of phenolic resin P-3 obtained in Example 5, 82.18 parts by mass of epichlorohydrin, and 20.10 parts by mass of dimethyl sulfoxide were added. parts by weight were added and the water bath was heated to 45°C. When the internal temperature became stable at 45°C, 8.84 parts by mass of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 45°C for 2 hours and at 70°C for 30 minutes. Thereafter, it was cooled to 50° C. or lower. After the reaction was completed, excess epichlorohydrin and other solvents were distilled off under reduced pressure at 124° C. using a rotary evaporator. 186.29 parts by mass of methyl isobutyl ketone was added and dissolved in the residue, and the temperature was raised to 75°C. 2.54 parts by mass of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, followed by washing with water, and it was confirmed with pH test paper that the washing water had become neutral. Methyl isobutyl ketone and the like were distilled off from the obtained solution under reduced pressure at 180° C. using a rotary evaporator to obtain 91.62 parts by mass of epoxy resin (EP3). The epoxy equivalent of the obtained epoxy resin was 531 g/eq. Met.
［実施例７，８、比較例１,２］
実施例２，４で得られたエポキシ樹脂（ＥＰ１、２）、比較例１としてジシクロペンタジエン型エポキシ樹脂（ＸＤ－１０００－２Ｌ、日本化薬株式会社製）、比較例２としてｐ－クレゾールジシクロペンタジエン型エポキシ樹脂（ＥＰ３）をそれぞれ主剤とし、硬化剤としてフェノールノボラック（略称；ＰＮ、水酸基当量１０３ｇ／ｅｑ．）、硬化促進剤としてトリフェニルホスフィン（略称；ＴＰＰ）を用いて表１の配合組成に示す重量比で配合、二本ロールで混錬、タブレット化後、トランスファー成形で樹脂成形体を調製し、１６０℃２時間、更に１８０℃６時間の硬化条件で硬化させた。
[Examples 7 and 8, Comparative Examples 1 and 2]
Epoxy resins (EP1, 2) obtained in Examples 2 and 4, dicyclopentadiene type epoxy resin (XD-1000-2L, manufactured by Nippon Kayaku Co., Ltd.) as Comparative Example 1, p-cresol di as Comparative Example 2 Using cyclopentadiene type epoxy resin (EP3) as the main resin, phenol novolak (abbreviation: PN, hydroxyl equivalent: 103 g/eq.) as a curing agent, and triphenylphosphine (abbreviation: TPP) as a curing accelerator, the formulations shown in Table 1 were used. After blending in the weight ratio shown in the composition, kneading with two rolls, and tabletting, a resin molded body was prepared by transfer molding, and cured at 160°C for 2 hours and then at 180°C for 6 hours.
物性値の測定は以下の条件で測定した。
・吸水湿性
メーカー：エスペック株式会社
装置：ＳＨ－６４２（小型環境試験機）、ＥＨＳ－４１１Ｍ（高度加速寿命試験装置）
直径５ｃｍ×厚み４ｍｍの円盤状の試験片について下記試験をした後の重量増加率（％）を測定した。
１．１００℃の水中で２４時間煮沸
２．８５℃８５％の小型環境試験機内に２４時間放置
３．１２１℃１００％の高加速寿命試験装置に２４時間放置
・誘電率試験、誘電正接試験
メーカー：株式会社ＡＥＴ
装置：１ＧＨｚ空洞共振器
今回は空洞共振器摂動法にてテストを行った。
Physical property values were measured under the following conditions.
・Water absorption and humidity Manufacturer: ESPEC Co., Ltd. Equipment: SH-642 (small environmental tester), EHS-411M (highly accelerated life tester)
The weight increase rate (%) was measured after performing the following test on a disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm.
1. Boiled in water at 100°C for 24 hours 2. Left in a small environmental tester at 85°C 85% for 24 hours 3. Left in a highly accelerated life tester at 100% at 121°C for 24 hours / Dielectric constant test, dielectric loss tangent test Manufacturer :AET Co., Ltd.
Equipment: 1 GHz cavity resonator This time we tested using the cavity resonator perturbation method.
表１の結果より、本願実施例の硬化物は耐吸水性、電気特性に優れることが確認された。 From the results in Table 1, it was confirmed that the cured products of Examples of the present application were excellent in water absorption resistance and electrical properties.
本発明は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ＦＲＰを始めとする各種複合材料、接着剤、塗料等、中でも特に積層板等の用途に有用であり、金属箔張り積層板、ビルドアップ基板用絶縁材料、フレキシブル基板材料などに有用である。 The present invention is particularly applicable to insulating materials for electrical and electronic components (highly reliable semiconductor encapsulation materials, etc.), various composite materials including laminates (printed wiring boards, build-up boards, etc.) and FRP, adhesives, paints, etc. It is useful for applications such as laminates, metal foil-clad laminates, insulating materials for build-up boards, and flexible board materials.
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