CN116891564A - Epoxy resin composition and cured product - Google Patents
Epoxy resin composition and cured product Download PDFInfo
- Publication number
- CN116891564A CN116891564A CN202310298292.0A CN202310298292A CN116891564A CN 116891564 A CN116891564 A CN 116891564A CN 202310298292 A CN202310298292 A CN 202310298292A CN 116891564 A CN116891564 A CN 116891564A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin composition
- cured product
- hardener
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 109
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 33
- -1 phenol compound Chemical class 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- 230000004927 fusion Effects 0.000 claims description 7
- 238000004455 differential thermal analysis Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 238000000646 scanning calorimetry Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 239000011256 inorganic filler Substances 0.000 description 16
- 229910003475 inorganic filler Inorganic materials 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 229920003986 novolac Polymers 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 7
- 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 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 229940079877 pyrogallol Drugs 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds 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
- 238000012856 packing Methods 0.000 description 2
- 229960001553 phloroglucinol Drugs 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- WTMVBEPSTKDZQD-UHFFFAOYSA-N (4-phenylphenyl)methanediol Chemical group C1=CC(C(O)O)=CC=C1C1=CC=CC=C1 WTMVBEPSTKDZQD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RAZKIGBWDJNTKX-UHFFFAOYSA-N 1-(dichloromethyl)-4-phenylbenzene Chemical group C1=CC(C(Cl)Cl)=CC=C1C1=CC=CC=C1 RAZKIGBWDJNTKX-UHFFFAOYSA-N 0.000 description 1
- DOKYYRMYJFIMEB-UHFFFAOYSA-N 1-(dimethoxymethyl)-4-phenylbenzene Chemical group C1=CC(C(OC)OC)=CC=C1C1=CC=CC=C1 DOKYYRMYJFIMEB-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- WRGWSECFFPBWMV-UHFFFAOYSA-N 1-benzothiophene;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2SC=CC2=C1 WRGWSECFFPBWMV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GPCXMLFPENNRSI-UHFFFAOYSA-N 1h-indene;phenol;styrene Chemical compound OC1=CC=CC=C1.C=CC1=CC=CC=C1.C1=CC=C2CC=CC2=C1 GPCXMLFPENNRSI-UHFFFAOYSA-N 0.000 description 1
- PJEKFSKIOOHJNR-UHFFFAOYSA-N 1h-indene;styrene Chemical compound C=CC1=CC=CC=C1.C1=CC=C2CC=CC2=C1 PJEKFSKIOOHJNR-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- ZUSZPUNTECJHJZ-UHFFFAOYSA-N 2,3-dibromo-1,4-dimethylbenzene Chemical group CC1=CC=C(C)C(Br)=C1Br ZUSZPUNTECJHJZ-UHFFFAOYSA-N 0.000 description 1
- UGHIQYNKFXEQPU-UHFFFAOYSA-N 2,3-dichloro-1,4-dimethylbenzene Chemical group CC1=CC=C(C)C(Cl)=C1Cl UGHIQYNKFXEQPU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-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
- 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 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- DVNYTAVYBRSTGK-UHFFFAOYSA-N 5-aminoimidazole-4-carboxamide Chemical compound NC(=O)C=1N=CNC=1N DVNYTAVYBRSTGK-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- USBHQTSMWCBZJE-UHFFFAOYSA-N [O-][N+]([Fe])=O Chemical compound [O-][N+]([Fe])=O USBHQTSMWCBZJE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 210000005097 arteria cerebelosa anteroinferior Anatomy 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-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
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000004206 montan acid ester Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 1
- SWDYEOBSKYXKLZ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O SWDYEOBSKYXKLZ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides an epoxy resin composition which can obtain a cured product excellent in high temperature characteristics such as heat resistance, thermal conductivity, high temperature elastic modulus, and the like, and further provides a cured product using the epoxy resin composition. An epoxy resin composition comprising an epoxy resin and a hardener, wherein the epoxy resin composition comprises a polyfunctional epoxy resin represented by the following general formula (1) [ chemical formula 1]]As a hardener component, makeA difunctional phenol compound represented by the following general formula (2) [ formula 2]]
Description
Technical Field
The present invention relates to an epoxy resin composition which is effectively used as an insulating material for electric/electronic materials such as semiconductor sealing materials, laminated boards, heat dissipating substrates, and the like, a carbon fiber reinforced composite material, and a cured product using the epoxy resin composition.
Background
Conventionally, as a sealing method for an electric component, an electronic component, a semiconductor device, or the like, for example, a sealing method using an epoxy resin, a silicone resin, or the like, or an airtight sealing method using glass, metal, ceramic, or the like has been used, but in recent years, a resin sealing material using transfer molding has been mainly used which can be mass-produced while improving reliability and has a cost advantage.
In general, a resin composition for a resin seal by transfer molding is used as a sealing material comprising a resin composition containing an epoxy resin and a phenol resin as a main component.
In order to cope with a large amount of heat emitted from an element, an epoxy resin composition used for protecting the element such as a power device (power device) is required to further improve heat resistance, heat dissipation, and low thermal expansion.
In view of the above background, for example, patent document 1 proposes a rigid mesogenic liquid crystalline epoxy resin and an epoxy resin composition using the epoxy resin. However, although the liquid crystalline property of the cured product thus obtained was confirmed, the cured product did not have crystallinity with a clear melting point, and was insufficient in heat resistance, high thermal conductivity, low thermal expansion property, low hygroscopicity, and the like. Patent document 2 discloses an epoxy resin composition and a cured product using an epoxy resin having a bisphenol mesogenic structure and a curing agent containing a difunctional phenolic compound as a main component, and discloses a cured product that can be crystallized, but the reaction between difunctional components does not satisfy the characteristics required strictly at present.
[ Prior Art literature ]
[ patent literature ]
Patent document 1 Japanese patent laid-open No. 2004-331811
[ patent document 2] Japanese patent application laid-open No. 2012-2323206
Disclosure of Invention
[ problem to be solved by the invention ]
Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide an epoxy resin composition which is excellent in moldability and can give a cured product having excellent heat resistance, low hygroscopicity and high thermal conductivity, and further to provide a cured product using the epoxy resin composition.
[ means of solving the problems ]
The present inventors have found that when a specific difunctional hardener, in which the reaction as a hardener proceeds two-dimensionally, is combined with an epoxy resin having a specific structure, a crystalline hardened product having a crosslinked structure can be obtained, and that physical properties such as heat resistance, low hygroscopicity, high-temperature elastic modulus, thermal conductivity, flame retardancy and the like are specifically improved, leading to the present invention.
The present invention is an epoxy resin composition comprising an epoxy resin and a hardener, wherein 50wt% or more of the epoxy resin is a polyfunctional epoxy resin and 50wt% of the hardener comprises a difunctional phenol compound, and is a crystalline epoxy resin cured product obtained by curing the epoxy resin composition.
The multifunctional epoxy resin is represented by the following formula (1).
[ chemical 1]
(wherein X independently represents-CH 2 -、-CH(Me)-、-CH(φ)-、-CH 2 -φ-CH 2 -、-CH(Me)-φ-CH(Me)-、-C(Me) 2 -φ-C(Me) 2 -、-CH 2 -φ-φ-CH 2 -、-CH(Me)-φ-φ-CH(Me)-、-C(Me) 2 -φ-φ-C(Me) 2 -; where Me represents methyl, φ represents phenylene, and n represents a number from 0 to 10)
The difunctional phenol compound is represented by the following formula (2).
[ chemical 2]
(wherein Y represents a single bond, -CH 2 -, -O-, -CO-; -phi-; here, Φ represents a phenylene group; m represents a number of 0 to 2)
The present invention also provides a cured product, particularly a crystalline cured product, which is obtained by curing the epoxy resin composition.
The heat of fusion (heat of fusion in terms of resin component) of the crystals in the scanning differential thermal analysis or the hardened material is preferably 3J/g or more, and the endothermic peak (melting point) accompanying the melting of the crystals in the scanning differential thermal analysis is in the range of 170 ℃ to 350 ℃.
[ Effect of the invention ]
The epoxy resin composition of the present invention is excellent in moldability and reliability, and can give a molded article excellent in heat resistance, low water absorption, high thermal conductivity, low thermal expansion and the like, and is suitably used for insulating materials for electric/electronic materials such as semiconductor sealing materials, laminated boards, heat dissipating substrates and the like, and further suitably used for composite materials such as fiber reinforced composite materials, molded materials for machine parts and the like, and can exhibit excellent high heat dissipation, high heat resistance and high dimensional stability. The reason for this specific effect is that: the cured product can have high heat resistance, low water absorption, thermal conductivity, low thermal expansion, flame retardancy, and the like by reacting a specific polyfunctional epoxy resin with a specific difunctional phenolic hardener, mainly by reacting a difunctional component of n=0 in the polyfunctional epoxy resin represented by the general formula (1) with a difunctional phenol compound to form a unit of a two-dimensional molecular chain having a high melting point and crystallinity of high elastic modulus at high temperature, and introducing a crosslinked structure by using the polyfunctional epoxy resin component.
Detailed Description
The present invention will be described in detail below.
In the epoxy resin composition of the present invention, the epoxy resin contains an epoxy resin represented by the following general formula (1) as an essential component.
[ chemical 3]
In formula (1), X independently represents-CH 2 -、-CH(Me)-、-CH(φ)-、-CH 2 -φ-CH 2 -、-CH(Me)-φ-CH(Me)-、-C(Me) 2 -φ-C(Me) 2 -、-CH 2 -φ-φ-CH 2 -、-CH(Me)-φ-φ-CH(Me)-、-C(Me) 2 -φ-φ-C(Me) 2 -. From the viewpoints of compatibility with a hardener and heat resistance, it is preferably-CH 2 -、-CH 2 -φ-CH 2 -、-CH 2 -φ-φ-CH 2 -。
n is a repetition number and represents a number of 0 to 10. The epoxy resin used in the present invention is a mixture of various compounds, and the average value of n (Σn/Σ molecular number) is in the range of 0 to 10. In order to increase the filling rate of the inorganic filler, the epoxy resin composition desirably has a low viscosity, and n is preferably in the range of 0.1 to 3.0 (average value). In order to make the cured product exhibit crystallinity, the composition may contain 25% or more, preferably 30% or more, and more preferably 40% or more of n=0. If the n=0 component is less than 25%, the polyfunctional component increases, and the crosslinking density in the cured product increases, and the molecular orientation is hindered, so that the crystallinity decreases. The molecular weight distribution of the epoxy resin substantially reflects the molecular weight distribution of the polyhydric hydroxyl resin of the raw material, and is preferably 25 to 60% in terms of the area ratio of gel permeation chromatography (Gel Permeation Chromatography, GPC), 15 to 25% in terms of n=0, 5 to 15% in terms of n=1, and 10 to 50% in terms of n=3.
The multifunctional epoxy resin used in the present invention can be synthesized by reacting a polyhydric hydroxyl resin represented by the following general formula (3) with epichlorohydrin. Here, X and n have the same meaning as in formula (1).
[ chemical 4]
The hydroxyl (OH) equivalent of the polyhydric hydroxyl resin of the formula (3) is preferably in the range of 80g/eq. to 300g/eq., more preferably 90g/eq. to 200g/eq., still more preferably 100g/eq. to 150g/eq. The melting point is preferably in the range of 100℃to 300℃and more preferably in the range of 200℃to 250 ℃. The molecular weight distribution is preferably 30 to 50% in terms of GPC area ratio, 20 to 30% in terms of n=0, 10 to 20% in terms of n=1, and 10 to 35% in terms of n+.3.
The polyhydric resin of the formula (3) can be synthesized by reacting 4,4 '-dihydroxybiphenyl with a crosslinking agent such as formaldehyde, acetaldehyde, benzaldehyde, terephthalyl alcohol dimethyl ether, dichloro-p-xylene, dibromo-p-xylene, divinylbenzene, 4' -dihydroxymethylbiphenyl, 4 '-dimethoxymethylbiphenyl, 4' -dichloromethylbiphenyl, etc. The amount of the crosslinking agent used in this case is usually in the range of 0.1 to 0.9 mol, preferably 0.2 to 0.6 mol, based on 1 mol of 4,4' -dihydroxybiphenyl. If the amount is smaller than this, the amount of unreacted 4,4' -dihydroxybiphenyl increases, the melting point becomes high when an epoxy resin is produced, and the compatibility with a hardener decreases. If the viscosity is higher than this, the moldability is lowered.
The epoxy resin used in the present invention generally has an epoxy equivalent (g/eq.) in the range of 100 to 500, but may be a low-viscosity epoxy resin in terms of an improvement in the filling rate and fluidity of the inorganic filler, and the epoxy equivalent is preferably in the range of 120 to 400. More preferably 130 to 300, and still more preferably 140 to 200.
The epoxy resin used in the present invention is suitably an epoxy resin having crystallinity at ordinary temperature. The melting point is preferably in the range of 50 to 250 ℃, more preferably 70 to 200 ℃, and even more preferably 100 to 150 ℃. If it is lower than this, the workability is lowered due to blocking when the epoxy resin composition is produced, and if it is higher than this, the compatibility with a hardener, the solubility in a solvent, and the like are lowered.
The purity of the epoxy resin used in the present invention, particularly the amount of hydrolyzable chlorine, is preferably as small as possible from the viewpoint of improving the reliability of applicable electronic parts. Although not particularly limited, it is preferably 1000ppm or less, and more preferably 500ppm or less. In addition, whatThe amount of hydrolyzable chlorine referred to in the present invention is a value measured by the following method. Specifically, 0.5g of a sample was dissolved in 30ml of dioxane, 1N-KOH and 10ml of the solution were added, the mixture was boiled and refluxed for 30 minutes, and then cooled to room temperature, and 100ml of 80% acetone water was further added to use 0.002N-AgNO 3 The aqueous solution was subjected to potential difference titration to obtain a value.
The viscosity of the epoxy resin of the present invention at 150℃is preferably 1000 mPas or less, more preferably 500 mPas or less, and may be 50 mPas or less.
In the epoxy resin composition of the present invention, other epoxy resins having two or more epoxy groups in the molecule may be used as the epoxy resin component in addition to the epoxy resin of the formula (1) used as an essential component. If exemplified, there is: divalent phenols such as bisphenol A, 4 '-dihydroxydiphenyl sulfone, 4' -dihydroxydiphenyl sulfide, fluorene bisphenol, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, etc.; or trivalent or more phenols such as phenol novolak, bisphenol a novolak, orthocresol novolak, metacresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, tris- (4-hydroxyphenyl) methane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, phloroglucinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2, 4-phloroglucinol, 2,3, 4-trihydroxybenzophenone, phenol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene resins, and the like; or glycidyl etherate derived from halogenated bisphenols such as tetrabromobisphenol A. One or two or more of these epoxy resins may be used.
The proportion of the epoxy resin of formula (1) used in the epoxy resin composition of the present invention is 50wt% or more, preferably 60wt% or more, more preferably 70wt% or more, and still more preferably 80wt% or more of the total epoxy resin. If the amount of the organic compound is less than this, the effect of improving physical properties such as thermal conductivity is small when the cured product is produced.
In the epoxy resin composition of the present invention, the hardener contains a difunctional phenol compound represented by the following general formula (2) as an essential component.
[ chemical 5]
In the formula (2), Y represents a single bond, -CH 2 -, -O-, -CO-; -phi-. From the viewpoint of compatibility with epoxy resins, it is preferably-CH 2 -, -O-, -CO-, from the viewpoint of heat resistance when a cured product is produced, preferably a single bond, -phi-. M represents a number of 0 to 2, preferably 1 or 2.
If the preferred difunctional phenol compounds are specifically exemplified, there may be mentioned: 4,4 '-dihydroxybiphenyl, 4' -dihydroxydiphenylmethane, 4 '-dihydroxydiphenyl ether, 4' -dihydroxybenzophenone, 4 "-dihydroxym-terphenyl or mixtures of these.
The hydroxyl equivalent weight of the difunctional phenol compound is preferably 80g/eq to 200g/eq, more preferably 80g/eq to 150g/eq, and still more preferably 80g/eq to 110g/eq.
The amount of the difunctional phenol compound used as the hardener is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more of the total hardener. If the amount of the organic compound is less than this, the crystallinity of the cured product is insufficient, and the effect of improving physical properties such as heat resistance and thermal conductivity is small.
The hardener used in the epoxy resin composition of the present invention may be used in combination with other hardeners generally known as hardeners, in addition to the difunctional phenol compound of the formula (2). If for example, the following are listed: amine-based hardeners, acid anhydride-based hardeners, phenol-based hardeners, polythiol-based hardeners, polyaminoamide-based hardeners, isocyanate-based hardeners, blocked isocyanate-based hardeners, and the like. The amount of the other curing agent to be blended may be appropriately set in consideration of the type of curing agent to be blended and the physical properties of the thermally conductive epoxy resin molded article to be obtained. However, even when other hardeners are used, the amount of the hardening agents to be blended is less than 50wt%, preferably less than 40wt%, more preferably less than 30wt%, based on the total amount of the hardening agents.
In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin to the hardener is preferably in the range of 0.8 to 1.5 in terms of equivalent ratio of the epoxy group to the functional group in the hardener. The range is preferably set in order to prevent degradation of reliability of the insulating material for electronic parts, which is caused by the residual unreacted epoxy groups or functional groups in the curing agent after curing.
In the epoxy resin composition of the present invention, an inorganic filler is preferably formulated. The amount of the inorganic filler to be added is usually 50 to 96wt%, preferably 60 to 94wt%, and more preferably 70 to 92wt% based on the epoxy resin composition. If the amount of the heat-resistant polymer is less than this, the effects such as high thermal conductivity, low thermal expansion and high heat resistance cannot be sufficiently exhibited. The effect increases as the amount of the inorganic filler added increases, but the effect increases dramatically from the time when the amount reaches a specific addition amount or more, not by the volume fraction thereof. These physical properties are due to the effect of controlling the higher order structure in the high molecular state, which is mainly achieved on the surface of the inorganic filler, and therefore, it is considered that a specific amount of the inorganic filler is required. On the other hand, from the viewpoint of viscosity and moldability, the addition amount of the inorganic filler is preferably not more than the upper limit value.
As the inorganic filler, preferably: powder such as silica, alumina, boron nitride, aluminum nitride, carbon powder, carbon fiber powder, etc.; fibrous substrates such as glass fibers, carbon fibers, and aramid fibers may be used in an amount of 50wt% or more of the inorganic filler. The inorganic filler is preferably spherical, but is not particularly limited as long as it is spherical including a case where the cross section is elliptical, but is particularly preferably as close to a true sphere as possible from the viewpoint of improving fluidity. Thus, a closest packing structure such as a face-centered cubic structure or a close-packed hexagonal structure can be easily obtained, and a sufficient packing amount can be obtained. If the filler amount is not spherical, the friction between the fillers increases, and the fluidity decreases or the viscosity increases before the upper limit of the blending amount is reached, which may affect the moldability.
From the viewpoint of improving the thermal conductivity, 50wt% or more, preferably 80wt% or more of the inorganic filler may be set to have a thermal conductivity of 5W/m·k or more. As the inorganic filler, alumina, aluminum nitride, crystalline silica, and the like are suitable. Among these, spherical alumina is excellent. In addition, an amorphous inorganic filler such as fused silica, crystalline silica, or the like may be used in combination as needed regardless of the shape.
Known hardening accelerators can be used in the epoxy resin composition of the present invention. For example, amines, imidazoles, organic phosphines, lewis acids, and the like are present, specifically: tertiary amines such as 1, 8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, and tris (4-methoxyphenyl) phosphine; tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium tetra-phenylborates, tetraphenylphosphonium ethyl triphenylborates, tetrabutylphosphonium tetra-butylborates, and the like; tetraphenylboron salts such as 2-ethyl-4-methylimidazole-tetraphenylborate and N-methylmorpholine-tetraphenylborate. These may be used alone or in combination.
The amount of the hardening accelerator is preferably 0.1 to 10.0 parts by weight based on 100 parts by weight of the total of the epoxy resin and the hardening agent. If the amount is less than 0.1 parts by weight, the gelation time becomes slow, the workability is lowered due to the lowering of the rigidity during the heating reaction, whereas if it exceeds 10.0 parts by weight, the reaction proceeds during the molding, and the unfilling is likely to occur.
In addition to the above components, the epoxy resin composition of the present invention may be suitably formulated into a mold release agent, a coupling agent, a thermoplastic oligomer, or other substances which can be generally used in an epoxy resin composition. For example, phosphorus flame retardants, flame retardants such as bromine compounds and antimony trioxide, colorants such as carbon black and organic dyes, and the like can be used.
As the release agent, wax can be used. Examples of waxes that can be used include stearic acid, montanic acid (montanic acid), montanic acid esters, and phosphoric acid esters. In addition, as the coupling agent, for example, epoxy silane is used for improving the adhesion between the inorganic filler and the resin component. Examples of the thermoplastic oligomers include C5-and C9-series petroleum resins, styrene resins, indene-styrene copolymer resins, indene-styrene-phenol copolymer resins, indene-coumarone copolymer resins, and indene-benzothiophene copolymer resins, which are used for improving fluidity during molding of an epoxy resin composition and improving adhesion to a substrate such as a lead frame.
The epoxy resin composition of the present invention can be produced by uniformly mixing a blending component (excluding a coupling agent) containing an epoxy resin and a curing agent as essential components and optionally an inorganic filler, and then adding a coupling agent if necessary, and kneading the mixture with a heated roll, a kneader, or the like using a mixer or the like. The order of preparation of these components is not particularly limited, except for coupling agents. Further, the melt-kneaded product may be pulverized after kneading to be pulverized or tableted.
The epoxy resin composition of the present invention is suitable for use as an electronic material, particularly for use in sealing electronic parts and for use in heat dissipating substrates.
The epoxy resin composition of the present invention can be compounded with fibrous substrates such as glass fibers to produce a composite material. For example, an epoxy resin composition containing an epoxy resin and a curing agent as main components is dissolved in a commonly used organic solvent, the resultant is impregnated into a sheet-like fibrous base material, and the resultant is heat-dried to partially dry the epoxy resin, thereby producing a prepreg.
In order to obtain a cured product (molded product) using the epoxy resin composition of the present invention, for example, a heat molding method such as transfer molding, press molding, casting molding, injection molding, extrusion molding, etc. may be applied, but transfer molding is preferable from the viewpoint of mass productivity.
The cured product of the present invention has crystallinity, and in a scanning differential thermal analysis measured at a heating rate of 10 ℃/min, the endothermic peak temperature (melting point) accompanying melting of the crystal is 170 ℃ to 350 ℃, preferably 180 ℃ to 350 ℃, more preferably 200 ℃ to 350 ℃.
Here, the effect of the present invention in which crystallinity is exhibited will be briefly described. In general, the glass transition point is used as an index of heat resistance in an epoxy resin cured product. The reason for this is that: the epoxy resin cured product is usually an amorphous (glassy) molded product having no crystallinity, and the physical properties are greatly changed by taking the glass transition point as a boundary. Therefore, in order to improve the heat resistance of the cured epoxy resin, that is, to improve the glass transition point, it is necessary to increase the crosslinking density, but there is a disadvantage that the flexibility is lowered and the cured epoxy resin becomes brittle. In contrast, since the cured molded article of the present invention has developed crystallinity, the change in physical properties before the melting point is small, and the melting point can be used as an index of heat resistance. Since the melting point of the polymer is higher than the glass transition point, the cured product of the present invention can maintain high flexibility by a low crosslinking density while securing high heat resistance. In addition, the crystallization means a high intermolecular force, whereby the movement of molecules is suppressed, low thermal expansion is achieved, high thermal diffusivity is exhibited, and thermal conductivity is improved. Further, due to the high stacking property of the molecular chains, both the water vapor permeability and the saturated water absorption amount are reduced, and the water resistance is improved.
Therefore, the higher the crystallinity of the cured product of the present invention, the better. The degree of crystallization can be evaluated based on the heat of fusion (the amount of heat absorbed by melting accompanying crystallization) in the scanning differential thermal analysis. The heat of fusion is preferably 3J/g or more per weight of the resin component excluding the filler. More preferably 5J/g or more, particularly preferably 10J/g or more. If this is less than the above, the effect of improving the heat resistance, low thermal expansion and thermal conductivity as a molded article is small. The heat of fusion referred to herein means the amount of heat absorption obtained by measurement with a differential scanning thermal analyzer using a precisely weighed sample of about 10mg under a nitrogen flow at a temperature rise rate of 10 ℃/min.
The cured product of the present invention can be obtained by performing a heating reaction by the molding method. In general, the molding temperature is 80℃to 350℃but in order to increase the crystallinity of the molded article, it is desirable to carry out the reaction at a temperature lower than the melting point of the molded article. The preferred forming temperature is in the range of 130 ℃ to 280 ℃, more preferably 160 ℃ to 250 ℃. In addition, the molding time is preferably 30 seconds to 1 hour, more preferably 1 minute to 30 minutes. Further, after the molding, the crystallinity can be further improved by annealing (post-curing). Typically, the annealing temperature is in the range of 130 ℃ to 250 ℃ for a time in the range of 1 hour to 20 hours, but it is desirable to perform post-curing at a temperature 5 ℃ to 40 ℃ below the endothermic peak temperature in differential thermal analysis for 1 hour to 24 hours.
Examples (example)
The invention is illustrated by the following examples.
Synthesis example 1 (Multi-hydroxy resin A)
A1L separable flask was charged with 140g (0.75 mol) of 4,4' -dihydroxybiphenyl, 600g of diethylene glycol dimethyl ether, and 3.8g of p-toluenesulfonic acid, and the mixture was heated to 90 ℃. While stirring, 18.3g (0.225 mol) of 37% formaldehyde was added thereto, and the mixture was reacted at 90℃for 1 hour. Thereafter, the temperature was raised to 135℃while distilled off water, and the reaction was continued for 3 hours. After neutralization with 10% aqueous sodium hydrogencarbonate solution at 90 ℃, the temperature was raised to 140 ℃ under reduced pressure, and the solvent was distilled off to obtain 178g of a solid resin (polyhydroxy resin a). The hydroxyl equivalent weight was 100g/eq. And the melting point was 241 ℃. The ratio of each component in the general formula (3) determined by GPC measurement is: n=0 is 49.4%, n=1 is 22.8%, n=2 is 12.7%, n=3 is 7.2%, n=4 is 4.4%, and n+.5 is 3.5%.
Synthesis example 2 (Multi-hydroxy resin B)
Reaction was carried out in the same manner as in Synthesis example 1 except that 24.5g (0.30 mol) of 37% formaldehyde was used, to obtain 169g of a solid resin (polyhydroxyresin B). The hydroxyl equivalent weight was 103g/eq. And the melting point was 227 ℃. The ratio of each component in the general formula (3) determined by GPC measurement is: n=0 is 39.3%, n=1 is 21.8%, n=2 is 13.9%, n=3 is 9.4%, n=4 is 5.9%, and n+.5 is 9.7%.
Synthesis example 3 (Multi-hydroxy resin C)
A1L separable flask was charged with 140g (0.75 mol) of 4,4 '-dihydroxybiphenyl, 31.0g (0.225 mol) of terephthalyl alcohol, 3.8g of p-toluenesulfonic acid, and 300g of diethylene glycol dimethyl ether, and after stirring under a nitrogen stream and raising the temperature to 150 ℃, a solution in which 75.3g (0.30 mol) of 4,4' -dichloromethylbenzene was dissolved in 260g of diethylene glycol dimethyl ether was added dropwise, the temperature was raised to 130℃and the reaction was carried out for 2 hours. After the reaction, the mixture was added dropwise to a large amount of pure water, and recovered by reprecipitation to obtain 168g of a pale yellow and crystalline resin (polyhydroxyresin C). The hydroxyl equivalent of the resin obtained was 125g/eq. The peak temperature (melting point) in the differential scanning calorimetry (Differential Scanning Calorimetry, DSC) assay was 240.1 ℃. The ratio of each component in the general formula (3) determined by GPC measurement is: n=0 is 44.3%, n=1 is 25.4%, n=2 is 16.1%, n=3 is 7.2%, n=4 is 4.3%, and n+.5 is 2.7%.
Synthesis example 4 (Multi-hydroxy resin D)
A1L separable flask was charged with 140g (0.75 mol) of 4,4 '-dihydroxybiphenyl and 600g of diethylene glycol dimethyl ether, the temperature was raised to 150℃under stirring under a nitrogen stream, a solution in which 75.3g (0.30 mol) of 4,4' -dichloromethyl biphenyl was dissolved in 260g of diethylene glycol dimethyl ether was added dropwise, and the mixture was heated to 170℃and reacted for 2 hours. After the reaction, the mixture was added dropwise to a large amount of pure water, and recovered by reprecipitation to obtain 170g of a pale yellow and crystalline resin (polyhydroxyresin D). The hydroxyl equivalent of the resin obtained was 139g/eq. The peak temperature (melting point) in the DSC measurement was 242.4 ℃. The ratio of each component in the general formula (3) determined by GPC measurement is: n=0 is 31.2%, n=1 is 21.2%, n=2 is 13.4%, n=3 is 10.6%, n=4 is 7.6%, and n+.5 is 15.4%.
Synthesis example 5 (epoxy resin A)
50g of a polyhydric hydroxyl resin A and 690g of epichlorohydrin were charged, and 40.5g of a 48.8% aqueous sodium hydroxide solution was added dropwise under reduced pressure (about 130 Torr) at 60℃over 3 hours. During this time, the water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for 1 hour, and after dehydration, epichlorohydrin was distilled off under reduced pressure. Thereafter, 500mL of toluene was added to dissolve the resin, and after removing salts by filtration and washing with water, 48.8g of an epoxy resin was obtained by distillation. This is a biphenyl epoxy resin (epoxy resin a) in which X is a methylene bond in the general formula (1). The epoxy equivalent was 156g/eq., the hydrolyzable chlorine was 280ppm, the melting point was 143℃and the viscosity at 150℃was 21 mPas. The ratio of each component in the general formula (1) determined by GPC measurement is: n=0 is 57.0%, n=1 is 21.0%, n=2 is 7.0%, n=3 is 5.3%, and n+.4 is 9.6%.
Synthesis example 6 (epoxy resin B)
46.2g of an epoxy resin was obtained in the same manner as in Synthesis example 5 except that 50g of the polyhydric resin B, 500g of epichlorohydrin and 39.7g of a 48.8% aqueous sodium hydroxide solution were used. This is a biphenyl epoxy resin (epoxy resin B) in which X is a methylene bond in the general formula (1). The epoxy equivalent was 144g/eq, the hydrolyzable chlorine was 320ppm, the melting point was 144℃and the viscosity at 150℃was 34 mPas. The ratio of each component in the general formula (1) determined by GPC measurement is: n=0 is 50.0%, n=1 is 21.7%, n=2 is 7.1%, n=3 is 6.8%, n=4 is 5.1%, and n+.5 is 9.3%.
Synthesis example 7 (epoxy resin C)
55.9g of an epoxy resin was obtained in the same manner as in Synthesis example 5 except that 50g of the polyhydric resin C, 400g of epichlorohydrin and 32.7g of a 48.8% aqueous sodium hydroxide solution were used. This is a biphenyl epoxy resin (epoxy resin C) in which X in the general formula (1) is a para-xylene bond. The epoxy equivalent was 174g/eq, the hydrolyzable chlorine was 260ppm, the melting point was 142℃and the viscosity at 150℃was 0.42 Pa.s. The ratio of each component in the general formula (1) determined by GPC measurement is: n=0 is 39.4%, n=1 is 19.5%, n=2 is 11.5%, n=3 is 7.8%, n=4 is 5.3%, n+.5 is 15.6%.
Synthesis example 8 (epoxy resin D)
58.9g of an epoxy resin was obtained in the same manner as in Synthesis example 5 except that 50g of the polyhydric hydroxyl resin D, 350g of epichlorohydrin and 29.4g of a 48.8% aqueous sodium hydroxide solution were used. This is a biphenyl epoxy resin (epoxy resin D) in which X in the general formula (1) is a4, 4' -biphenylene bond. The epoxy equivalent was 195g/eq, the hydrolyzable chlorine was 250ppm, the melting point was 127℃and the viscosity at 150℃was 0.29 Pa.s. The ratio of each component in the general formula (1) determined by GPC measurement is: n=0 is 28.0%, n=1 is 18.4%, n=2 is 12.5%, n=3 is 8.8%, n=4 is 6.4%, n=5 is 5.0%, n+.5 is 20.9%.
Examples 1 to 6 and comparative examples 1 to 3
As the epoxy resins, epoxy resins A to D and phenol novolac type epoxy resins (epoxy resin E: manufactured by Nitro iron chemical & materials, YPN-638, epoxy equivalent 221) synthesized in Synthesis examples 5 to 8 were used, as the hardener, 4 '-dihydroxydiphenyl ether (hardener A: Y= -O-, hydroxyl equivalent 101 g/eq.) of formula (2), 4' -dihydroxybiphenyl (hardener B: Y=single bond of formula (2), hydroxyl equivalent 93 g/eq.), bisphenol A (hardener C), phenol novolac (hardener D: manufactured by AICA) industries, BRG-557, OH equivalent 103, softening point 84 ℃ C.) and triphenylphosphine were used as the hardening accelerator.
The components shown in Table 1 were prepared, thoroughly mixed by a mixer, kneaded by a heated roll for about 5 minutes, and the obtained products were cooled and pulverized to obtain epoxy resin compositions of examples 1 to 6 and comparative examples 1 to 3, respectively. After molding at 175℃for 3 minutes using the epoxy resin composition, the cured product was obtained by post-curing at 180℃for 4 hours, and the physical properties were evaluated. The results are summarized in table 1. In addition, the numerals of the respective components in table 1 represent parts by weight.
[ evaluation ]
(1) Coefficient of thermal expansion (linear expansion coefficient), glass transition temperature (Tg)
The measurement was performed at a temperature rise rate of 10℃per minute using a TMA7100 type thermo-mechanical measurement apparatus manufactured by Hitachi High-Tech Science.
(2) Modulus of elasticity at high temperature
A DMA6100 type measuring apparatus manufactured by Hitachi High-Tech Science was used to measure dynamic viscoelasticity at a frequency of 10Hz under a nitrogen stream at a temperature rising rate of 2 ℃/min, and the storage elastic modulus at 260℃was read.
(3) Thermal diffusivity
The measurement was performed by a xenon flash method using an LFA447 type thermal conductivity meter manufactured by relaxation resistance (NETZSCH).
(4) Melting point, heat of fusion (DSC method)
The measurement was performed by a DSC7020 type differential scanning calorimeter manufactured by Hitachi High-Tech Science (Hitachi High-Tech Science) under a nitrogen flow using a precisely weighed sample of about 10mg at a temperature rising rate of 10 ℃/min.
(5) Thermal decomposition temperature and carbon residue rate
The thermal decomposition temperature (10% weight loss temperature) and the carbon residue were determined under a nitrogen flow at a heating rate of 10℃per minute by a TG/DTA7300 type thermal gravimetric measuring instrument manufactured by Hitachi High-Tech Science.
(6) Water absorption rate
A disk having a diameter of 50mm and a thickness of 3mm was molded and post-cured, and the resultant was subjected to moisture absorption at 85℃and a relative humidity of 85% for 100 hours, whereby the weight change rate was determined.
TABLE 1
(remark)
N.D. is undetected (Not Detect)
Claims (5)
1. An epoxy resin composition comprising an epoxy resin and a hardener, wherein 50wt% or more of the epoxy resin component is a multifunctional epoxy resin represented by the following general formula (1),
wherein X independently represents-CH 2 -、-CH(Me)-、-CH(φ)-、-CH 2 -φ-CH 2 -、-CH(Me)-φ-CH(Me)-、-C(Me) 2 -φ-C(Me) 2 -、-CH 2 -φ-φ-CH 2 -、-CH(Me)-φ-φ-CH(Me)-、-C(Me) 2 -φ-φ-C(Me) 2 -; here, phi represents a phenylene group, n represents a number of 0 to 10,
50% by weight of the hardener component is a difunctional phenol compound represented by the following general formula (2),
wherein Y represents a single bond, -CH 2 -, -O-, -CO-; -phi-; here, Φ represents a phenylene group; m represents a number of 0 to 2.
2. A cured product obtained by curing the epoxy resin composition according to claim 1.
3. A cured product which is crystalline and is obtained by curing the epoxy resin composition according to claim 1.
4. The cured product according to claim 3, wherein the peak endothermic temperature (melting point) of melting accompanying crystallization in scanning differential thermal analysis is 170℃to 350 ℃.
5. The cured product according to claim 3 or 4, wherein the heat of fusion in the scanning calorimetry is 3J/g or more in terms of resin component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022055923A JP2023148076A (en) | 2022-03-30 | 2022-03-30 | Epoxy resin composition and cured product |
| JP2022-055923 | 2022-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116891564A true CN116891564A (en) | 2023-10-17 |
Family
ID=88288587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310298292.0A Pending CN116891564A (en) | 2022-03-30 | 2023-03-24 | Epoxy resin composition and cured product |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2023148076A (en) |
| CN (1) | CN116891564A (en) |
| TW (1) | TW202337944A (en) |
-
2022
- 2022-03-30 JP JP2022055923A patent/JP2023148076A/en active Pending
-
2023
- 2023-03-24 CN CN202310298292.0A patent/CN116891564A/en active Pending
- 2023-03-27 TW TW112111583A patent/TW202337944A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW202337944A (en) | 2023-10-01 |
| JP2023148076A (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5166610B2 (en) | Epoxy resin, production method thereof, epoxy resin composition and cured product using the same | |
| JP5330013B2 (en) | Epoxy resin composition and cured product | |
| JPWO2014065152A1 (en) | Epoxy resin composition, method for producing cured epoxy resin, and semiconductor device | |
| WO2007043684A9 (en) | Phenol polymer, production method thereof and use thereof | |
| JP5209556B2 (en) | Epoxy resin composition and molded article | |
| JP6605828B2 (en) | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| KR20130099116A (en) | Polyhydric hydroxy resin, epoxy resin, production method therefor, epoxy resin composition and cured product thereof | |
| JP5079721B2 (en) | Epoxy resin composition and molded article | |
| JP5457304B2 (en) | Phenolic resin, epoxy resin, production method thereof, epoxy resin composition and cured product | |
| JP6139997B2 (en) | Epoxy resin, epoxy resin composition, and cured product thereof | |
| WO2013125620A1 (en) | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof | |
| JP5091052B2 (en) | Epoxy resin composition and molded article | |
| JP6052868B2 (en) | Epoxy resin curing agent, production method, and use thereof | |
| JP6620981B2 (en) | Thermosetting molding material, method for producing the same, and semiconductor sealing material | |
| JP5734603B2 (en) | Phenolic resin, epoxy resin, production method thereof, epoxy resin composition and cured product | |
| JP6783121B2 (en) | Allyl group-containing resin, its manufacturing method, resin varnish and laminated board manufacturing method | |
| CN116891564A (en) | Epoxy resin composition and cured product | |
| JP6292925B2 (en) | Epoxy resin composition and cured product thereof | |
| JP5199847B2 (en) | Epoxy resin composition and molded article | |
| WO2014010559A1 (en) | Epoxy resin, epoxy resin composition, method for curing same, and cured product thereof | |
| JPH05194713A (en) | Epoxy resin composition | |
| JP2012197366A (en) | Epoxy resin composition and molding | |
| JP7158228B2 (en) | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| JP2022016887A (en) | Epoxy resin composition and cured product | |
| JP2023118298A (en) | Epoxy resin composition and cured material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |