JP5548562B2 - Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof - Google Patents
Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof Download PDFInfo
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- JP5548562B2 JP5548562B2 JP2010202915A JP2010202915A JP5548562B2 JP 5548562 B2 JP5548562 B2 JP 5548562B2 JP 2010202915 A JP2010202915 A JP 2010202915A JP 2010202915 A JP2010202915 A JP 2010202915A JP 5548562 B2 JP5548562 B2 JP 5548562B2
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- Prior art keywords
- epoxy resin
- polyvalent hydroxy
- resin composition
- group
- resin
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims description 100
- 229920000647 polyepoxide Polymers 0.000 title claims description 100
- 239000000203 mixture Substances 0.000 title claims description 55
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims description 46
- 229920005989 resin Polymers 0.000 title claims description 41
- 239000011347 resin Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 19
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 28
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 19
- 229920003986 novolac Polymers 0.000 description 18
- 150000002989 phenols Chemical class 0.000 description 14
- 150000003440 styrenes Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- -1 hydroxypropyl group Chemical group 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 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 9
- 238000000034 method Methods 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 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
- 239000004593 Epoxy Substances 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 125000005504 styryl group Chemical group 0.000 description 6
- 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 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000243 solution 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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 150000001896 cresols Chemical class 0.000 description 3
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000001993 wax 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-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
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- 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
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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Images
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- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Description
本発明は、硬化性に優れるとともに、難燃性、耐湿性、低弾性にも優れた硬化物を与えるエポキシ樹脂、その中間体として適する多価ヒドロキシ樹脂、それらの製造方法、これら用いたエポキシ樹脂組成物並びにその硬化物に関するものであり、半導体封止材、プリント配線板等の電気電子分野の絶縁材料等に好適に使用される。 The present invention is an epoxy resin that is excellent in curability and gives a cured product that is also excellent in flame retardancy, moisture resistance, and low elasticity, a polyvalent hydroxy resin suitable as an intermediate thereof, a production method thereof, and an epoxy resin used in these The present invention relates to a composition and a cured product thereof, and is suitably used as an insulating material in the electrical and electronic field such as a semiconductor sealing material and a printed wiring board.
エポキシ樹脂は工業的に幅広い用途で使用されてきているが、その要求性能は近年ますます高度化している。例えば、エポキシ樹脂を主剤とする樹脂組成物の代表的分野に半導体封止材料があるが、半導体素子の集積度の向上に伴い、パッケージサイズは大面積化、薄型化に向かうとともに、実装方式も表面実装化への移行が進展しており、半田耐熱性に優れた材料の開発が望まれている。従って、封止材料としては、低吸湿化に加え、リードフレーム、チップ等の異種材料界面での接着性・密着性の向上が強く求められている。回路基板材料においても同様に、半田耐熱性向上の観点から低吸湿性、高耐熱性、高密着性の向上に加え、誘電損失低減の観点から低誘電性に優れた材料の開発が望まれている。これらの要求に対応するため、様々な新規構造のエポキシ樹脂及び硬化剤が検討されている。更に最近では、環境負荷低減の観点から、ハロゲン系難燃剤排除の動きがあり、より難燃性に優れたエポキシ樹脂及び硬化剤が求められている。 Epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a typical field of a resin composition mainly composed of an epoxy resin, but as the integration degree of semiconductor elements is improved, the package size is becoming larger and thinner, and the mounting method is also increased. The transition to surface mounting is progressing, and the development of materials with excellent solder heat resistance is desired. Therefore, as a sealing material, in addition to reducing moisture absorption, improvement in adhesion and adhesion at the interface between different materials such as lead frames and chips is strongly demanded. Similarly, for circuit board materials, in addition to improving low heat absorption, high heat resistance, and high adhesion from the viewpoint of improving solder heat resistance, it is desirable to develop materials with excellent low dielectric properties from the viewpoint of reducing dielectric loss. Yes. In order to meet these requirements, various new structures of epoxy resins and curing agents have been studied. Furthermore, recently, from the viewpoint of reducing environmental impact, there has been a movement to eliminate halogen-based flame retardants, and epoxy resins and curing agents with more excellent flame retardancy have been demanded.
従って、上記背景から種々のエポキシ樹脂及びエポキシ樹脂硬化剤が検討されている。エポキシ樹脂硬化剤の一例として、ナフタレン系樹脂が知られており、特許文献１にはナフトールアラルキル樹脂を半導体封止材への応用が示されており、難燃性、低吸湿性、低熱膨張性等に優れることが記載されている。また、特許文献２にはビフェニル構造を有する硬化剤が提案され、難燃性向上に有効であることが記載されている。しかし、ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂ともに、硬化性に劣る欠点があり、また、難燃性向上の効果についても十分ではない場合があった。
Therefore, various epoxy resins and epoxy resin curing agents have been studied from the above background. As an example of an epoxy resin curing agent, a naphthalene-based resin is known, and
一方、エポキシ樹脂についても、これらの要求を満足するものは未だ知られていない。例えば、周知のビスフェノール型エポキシ樹脂は、常温で液状であり、作業性に優れていることや、硬化剤、添加剤等との混合が容易であることから広く使用されているが、耐熱性、耐湿性の点で問題がある。また、耐熱性を改良したものとして、ｏ−クレゾールノボラック型エポキシ樹脂が知られているが、難燃性に関しては不十分である。 On the other hand, an epoxy resin that satisfies these requirements is not yet known. For example, the well-known bisphenol type epoxy resin is in a liquid state at room temperature and is widely used because it is excellent in workability and easy to mix with a curing agent, an additive, etc. There is a problem in terms of moisture resistance. In addition, an o-cresol novolac type epoxy resin is known as an improved heat resistance, but the flame retardancy is insufficient.
ハロゲン系難燃剤を用いることなく難燃性を向上させるための方策として、リン酸エステル系の難燃剤を添加する方法が開示されている。しかし、リン酸エステル系の難燃剤を用いる方法では、耐湿性が十分ではない。また、高温、多湿な環境下ではリン酸エステルが加水分解を起こし、絶縁材料としての信頼性を低下させる問題があった。 As a measure for improving flame retardancy without using a halogen flame retardant, a method of adding a phosphate ester flame retardant is disclosed. However, the method using a phosphate ester flame retardant does not have sufficient moisture resistance. In addition, the phosphoric acid ester is hydrolyzed under a high temperature and humidity environment, and there is a problem that the reliability as an insulating material is lowered.
リン原子やハロゲン原子を含むことなく、難燃性を向上させるものとして、特許文献２及び３ではビフェニル構造を有するアラルキル型エポキシ樹脂を半導体封止材へ応用した例が開示されている。特許文献４には、ナフタレン構造を有するアラルキル型エポキシ樹脂を使用する例が開示されている。しかしながら、これらのエポキシ樹脂は、難燃性、耐湿性又は耐熱性のいずれかにおいて性能が十分でない。 Patent Documents 2 and 3 disclose an example in which an aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant as a material that improves flame retardancy without containing a phosphorus atom or a halogen atom. Patent Document 4 discloses an example in which an aralkyl type epoxy resin having a naphthalene structure is used. However, these epoxy resins have insufficient performance in any of flame retardancy, moisture resistance or heat resistance.
一方、耐熱性、耐湿性、耐クラック性の向上に着目した例として、特許文献５にはベンジル化ポリフェノール及びそのエポキシ樹脂が開示されているが、これらは難燃性に着目したものではない。また、これらはフェノールノボラックを出発原料として用い、続いてベンジルクロライドを付加反応させることにより得られる樹脂であるが、かさ高いベンジル基がヒドロキシ基やエポキシ基等の官能基のオルト位に置換されることにより、立体障害を引き起こし硬化性を低下させる問題があった。 On the other hand, as an example focusing on improving heat resistance, moisture resistance, and crack resistance, Patent Document 5 discloses benzylated polyphenol and its epoxy resin, but these do not focus on flame retardancy. These are resins obtained by using phenol novolac as a starting material, followed by addition reaction of benzyl chloride, but the bulky benzyl group is replaced with the ortho position of a functional group such as a hydroxy group or an epoxy group. As a result, there is a problem of causing steric hindrance and reducing curability.
また、耐湿性、低応力性の向上に着目したエポキシ樹脂組成物の例として、特許文献６及び７にはモノスチレン化フェノールノボラック樹脂及びそのエポキシ樹脂を用いるエポキシ樹脂組成物が開示されているが、これらも難燃性に着目したものではない。また、これらもかさ高いスチレニル基が官能基近傍に置換されることにより、立体障害による硬化性低下を生じる問題があった。 In addition, as examples of epoxy resin compositions focused on improving moisture resistance and low stress properties, Patent Documents 6 and 7 disclose a monostyrenated phenol novolac resin and an epoxy resin composition using the epoxy resin. These are also not focused on flame retardancy. In addition, these also have a problem in that the bulky styryl group is substituted in the vicinity of the functional group, resulting in a decrease in curability due to steric hindrance.
本発明の目的は、積層、成形、注型、接着等の用途において、硬化性に優れるとともに、難燃性、耐湿性、低弾性等にも優れた性能を有するエポキシ樹脂を提供すること、優れた硬化性有するとともに、難燃性、耐湿性、低弾性等にも優れた硬化物を与える電気・電子部品類の封止、回路基板材料等に有用なエポキシ樹脂組成物を提供すること、及びその硬化物を提供することにある。 The object of the present invention is to provide an epoxy resin having excellent performance in flame retardancy, moisture resistance, low elasticity and the like, as well as excellent curability in applications such as lamination, molding, casting and adhesion, Providing an epoxy resin composition useful for sealing electrical and electronic parts, circuit board materials, etc., which has a high curability and gives a cured product excellent in flame retardancy, moisture resistance, low elasticity, etc., and It is to provide the cured product.
すなわち、本発明は、下記一般式（１）で表される多価ヒドロキシ樹脂である。
また、本発明は、下記一般式（２）で表される多価ヒドロキシ化合物のヒドロキシ基１モルに対し、スチレン類０．１〜２．５モルを、酸触媒の存在下に反応させることを特徴とする上記式（ａ）で表される置換基が多価ヒドロキシ化合物のベンゼン環に置換した構造を有する多価ヒドロキシ樹脂の製造方法である。
更に、本発明は、下記一般式（３）で表されるエポキシ樹脂である。
また、本発明は、上記の多価ヒドロキシ樹脂とエピクロルヒドリンを反応させることを特徴とするエポキシ樹脂の製造方法である。 Moreover, this invention is a manufacturing method of the epoxy resin characterized by making said polyhydric hydroxy resin and epichlorohydrin react.
更に、本発明は、エポキシ樹脂及び硬化剤よりなるエポキシ樹脂組成物において、上記の多価ヒドロキシ樹脂及び上記のエポキシ樹脂の一方又は両方を必須成分として配合してなるエポキシ樹脂組成物である。また、本発明は上記のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物である。 Furthermore, this invention is an epoxy resin composition which mix | blends one or both of said polyhydric hydroxy resin and said epoxy resin as an essential component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent. Moreover, this invention is an epoxy resin hardened | cured material formed by hardening | curing said epoxy resin composition.
本発明のエポキシ樹脂及び多価ヒドロキシ樹脂は、エポキシ樹脂組成物に応用した場合、硬化性に優れるとともに、難燃性、耐湿性及び低弾性にも優れた硬化物を与え、電気・電子部品類の封止、回路基板材料等の用途に好適に使用することが可能である。特に、硬化性および難燃性に優れ、優れた成形性を確保しつつ、環境負荷のある難燃剤の使用を不要とさせ又は減少させる。 When applied to an epoxy resin composition, the epoxy resin and polyvalent hydroxy resin of the present invention give a cured product that is excellent in curability, flame retardancy, moisture resistance, and low elasticity, and electrical / electronic components. Can be suitably used for applications such as sealing and circuit board materials. In particular, the curability and flame retardancy are excellent, and the use of a flame retardant having an environmental load is made unnecessary or reduced while ensuring excellent moldability.
まず、本発明の多価ヒドロキシ樹脂（以下、ＳｔＣＮと略す）について説明する。本発明のＳｔＣＮは一般式（１）で表され、これは一般式（２）で表される多価ヒドロキシ化合物とスチレン類を反応させることにより得ることができる。 First, the polyvalent hydroxy resin (hereinafter abbreviated as StCN) of the present invention will be described. The StCN of the present invention is represented by the general formula (1), which can be obtained by reacting the polyvalent hydroxy compound represented by the general formula (2) with styrene.
本発明のＳｔＣＮは、多価ヒドロキシ化合物のベンゼン環にスチレン類を付加させることによって、水酸基当量を任意に調整することができる。ここで、スチレン類を付加させるとは、多価ヒドロキシ化合物のベンゼン環の水素と式（a）で表わされる置換基（スチレニル基）を置換させることをいう。つまり、エポキシ樹脂硬化物においては、エポキシ基と水酸基との反応により生成するヒドロキシプロピル基が燃え易いとされているが、水酸基当量を高くすることで、エポキシ基由来の易燃成分の脂肪族炭素率は低くなり、高度な難燃性を発現させることができる。また、芳香族性に富んだスチレンを付加させることにより、芳香族性はより一層向上し、難燃性に加え耐湿性の向上にも効果的である。 StCN of the present invention can arbitrarily adjust the hydroxyl equivalent by adding styrenes to the benzene ring of the polyvalent hydroxy compound. Here, adding styrenes means substituting the hydrogen of the benzene ring of a polyvalent hydroxy compound and the substituent (styryl group) represented by the formula (a). In other words, in the epoxy resin cured product, the hydroxypropyl group generated by the reaction between the epoxy group and the hydroxyl group is said to burn easily, but by increasing the hydroxyl equivalent, aliphatic carbon of the flammable component derived from the epoxy group The rate is low and a high degree of flame retardancy can be expressed. Moreover, by adding styrene rich in aromaticity, the aromaticity is further improved, and it is effective in improving moisture resistance in addition to flame retardancy.
よって、これらを用いて高難燃性のエポキシ樹脂組成物、特に半導体封止用エポキシ樹脂組成物が得られる。すなわち、それらの組成物における優れた成形性とともに、高難燃性、耐湿性や低弾性に優れた物性が発現され、この材料を用いて信頼性の高い電気・電子部品類の封止、回路基板材料等が得られる。 Therefore, a highly flame-retardant epoxy resin composition, especially an epoxy resin composition for semiconductor encapsulation is obtained using these. In other words, high moldability in these compositions, as well as excellent physical properties such as high flame resistance, moisture resistance and low elasticity are manifested. Using this material, highly reliable sealing of electrical and electronic parts, circuits A substrate material or the like is obtained.
本発明のＳｔＣＮは、多価ヒドロキシ化合物としてクレゾールノボラックを用いることにより、置換基（ａ）の導入による立体障害の増加を抑制することができ、エポキシ樹脂の硬化剤として用いた場合、良好な硬化性を維持することができる。すなわち、ヒドロキシ基近傍のオルト位にかさ高い置換基（ａ）が置換された場合、立体障害の増加により硬化性が低下するのに対し、あらかじめ立体障害の低いメチル基がヒドロキシ基近傍に置換されている場合には、かさ高い置換基（ａ）の導入による立体障害の増加を抑制することができるため、良好な硬化性を維持することができる。 The StCN of the present invention can suppress an increase in steric hindrance due to the introduction of the substituent (a) by using cresol novolak as a polyvalent hydroxy compound, and when used as a curing agent for an epoxy resin, it exhibits good curing. Sex can be maintained. That is, when a bulky substituent (a) is substituted at the ortho position in the vicinity of the hydroxy group, the curability decreases due to an increase in steric hindrance, whereas a methyl group having low steric hindrance is substituted in the vicinity of the hydroxy group in advance. In this case, since an increase in steric hindrance due to the introduction of the bulky substituent (a) can be suppressed, good curability can be maintained.
本発明のＳｔＣＮは、一般式（２）で表される多価ヒドロキシ化合物とスチレン類とを付加反応させることにより得られる。この際、多価ヒドロキシ化合物とスチレン類との割合としては、得られる硬化物の難燃性と硬化性のバランスを考慮すると、一般式（２）中フェノール成分、又はＯＨ基１モルに対するスチレン類の使用割合が０．１〜２．５モルの範囲が好ましく、より好ましくは０．１〜１．０モル、更に好ましくは０．３〜０．８モルの範囲である。この範囲より少ない場合は、原料の多価ヒドロキシ化合物の性質が改良されないままの状態であり、この範囲より多い場合は、官能基密度が低くなり過ぎて硬化性が低下する傾向がある。 The StCN of the present invention can be obtained by addition reaction of a polyvalent hydroxy compound represented by the general formula (2) and styrenes. At this time, as a ratio of the polyvalent hydroxy compound and the styrenes, considering the balance between flame retardancy and curability of the obtained cured product, the styrenes relative to 1 mol of the phenol component in the general formula (2) or the OH group Is preferably in the range of 0.1 to 2.5 mol, more preferably in the range of 0.1 to 1.0 mol, and still more preferably in the range of 0.3 to 0.8 mol. When the amount is less than this range, the properties of the starting polyvalent hydroxy compound are not improved. When the amount is more than this range, the functional group density tends to be too low and the curability tends to decrease.
この反応では、スチレン類が多価ヒドロキシ化合物中のＯＨ基を有する芳香族環に付加して上記式（ａ）で表わされるスチレニル基が置換する。また、スチレン類の付加位置は、多価ヒドロキシ化合物の空位のオルソ及び／又はパラ位であるが、主としてパラ位である。 In this reaction, styrenes are added to the aromatic ring having an OH group in the polyvalent hydroxy compound to replace the styryl group represented by the above formula (a). The addition position of styrenes is the vacant ortho and / or para position of the polyvalent hydroxy compound, but is mainly the para position.
また、本発明のＳｔＣＮの１５０℃における溶融粘度は０．０１〜１０．０Ｐａ・ｓの範囲のものが好ましい。作業性の面から、溶融粘度は上記範囲において低い程好ましい。 Further, the melt viscosity at 150 ° C. of the StCN of the present invention is preferably in the range of 0.01 to 10.0 Pa · s. From the viewpoint of workability, the melt viscosity is preferably as low as possible within the above range.
さらには、軟化点は４０〜１５０℃であることがよく、好ましくは５０〜１００℃の範囲である。ここで、軟化点は、ＪＩＳ−Ｋ−２２０７の環球法に基づき測定される軟化点を指す。これより低いと、これをエポキシ樹脂に配合したとき、硬化物の耐熱性が低下し、これより高いと成形時の流動性が低下する。 Further, the softening point is preferably 40 to 150 ° C, and preferably in the range of 50 to 100 ° C. Here, the softening point refers to a softening point measured based on the ring and ball method of JIS-K-2207. When lower than this, when this is mix | blended with an epoxy resin, the heat resistance of hardened | cured material will fall, and when higher than this, the fluidity | liquidity at the time of shaping | molding will fall.
上記一般式（１）において、Ｒ1は上記式（ａ）で表されるスチレニル基を示す。ｐは０．１〜２．５の数を示すが、これは１個のクレゾール環に置換するスチレニル基の平均の数（数平均）を意味する。ｐは０．１〜２モル、０．１〜１．０モル、０．３〜１モル、０．３〜０．８モルの順に好ましい。なお、両末端のクレゾール環には最大３個のスチレニル基が置換でき、中間のクレゾール環には最大２個のスチレニル基が置換できるので、ｎが１の場合は最大６個のスチレニル基が置換できる。
別の観点からは、本発明のＳｔＣＮは、1分子あたりのスチレニル基の置換数（数平均）は、１以上であることが好ましく、より好ましくは２以上、更に好ましくは２.６〜４である。
In the general formula (1), R 1 represents a styryl group represented by the above formula (a). p shows the number of 0.1-2.5, and this means the average number (number average) of the styrenyl group substituted by one cresol ring. p is preferably in the order of 0.1 to 2 mol, 0.1 to 1.0 mol, 0.3 to 1 mol, and 0.3 to 0.8 mol. It should be noted that a maximum of 3 styrenyl groups can be substituted for the cresol ring at both ends, and a maximum of 2 styrenyl groups can be substituted for the intermediate cresol ring. it can.
From another point of view, in the StCN of the present invention, the number of substitutions (number average) of styryl groups per molecule is preferably 1 or more, more preferably 2 or more, still more preferably 2.6 to 4. is there.
式（ａ）において、Ｒ2は水素又は炭素数１〜６の炭化水素基を示すが、好ましくは水素又は炭素数１〜３のアルキル基であり、より好ましくは水素である。このＲ2は反応原料として使用するスチレン類によって定まる。 In the formula (a), R 2 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen. This R 2 is determined by the styrenes used as reaction raw materials.
一般式（１）において、ｎは１〜２０の数を示すが、好ましくは、数平均として１．５〜５．０の範囲である。 In General formula (1), n shows the number of 1-20, Preferably, it is the range of 1.5-5.0 as a number average.
次に、本発明のＳｔＣＮの製造方法について説明する。本発明のＳｔＣＮの製造方法は、一般式（２）で表される多価ヒドロキシ化合物のヒドロキシ基１モルに対し、スチレン類０．１〜２．５モルを、酸触媒の存在下に反応させることにより行う。一般式（２）で表わされる多価ヒドロキシ化合物としては、クレゾールノボラックが代表的である。スチレン類の使用量は、上記ヒドロキシ基１モルに対し、０．１〜２．５であるが、０．１〜１．０が好ましく、０．３〜０．８がより好ましい。 Next, the manufacturing method of StCN of this invention is demonstrated. In the method for producing StCN of the present invention, 0.1 to 2.5 mol of styrene is reacted in the presence of an acid catalyst with respect to 1 mol of the hydroxy group of the polyvalent hydroxy compound represented by the general formula (2). By doing. A typical example of the polyvalent hydroxy compound represented by formula (2) is cresol novolac. Although the usage-amount of styrene is 0.1-2.5 with respect to 1 mol of said hydroxy groups, 0.1-1.0 are preferable and 0.3-0.8 are more preferable.
この多価ヒドロキシ化合物は、クレゾール類をメチレンで連結した構造を有するが、クレゾール類としては、ｏ−クレゾール又はｏ−クレゾールを主成分とするクレゾールであることがよい。ｏ−クレゾールを主成分とする場合、５０％以上、好ましくは７０％以上がｏ−クレゾールであることがよい。ｏ−クレゾール以外のｍ−クレゾール及びｐ−クレゾールを含んでもよいが、５０％以下であることが好ましい。このクレゾール類は少量の他のフェノール成分を１種以上含んでもよい。例えば、フェノール、エチルフェノール類、イソプロピルフェノール類、ターシャリーブチルフェノール類、アリルフェノール類、フェニルフェノール類、２，６−キシレノール、２，６−ジエチルフェノール、ハイドロキノン、レゾルシン、カテコール、１−ナフトール、２−ナフトール、１，５−ナフタレンジオール、１，６−ナフタレンジオール、１，７−ナフタレンジオール、２，６−ナフタレンジオール、２，７−ナフタレンジオールなどが挙げられる。 This polyvalent hydroxy compound has a structure in which cresols are linked with methylene, and the cresols are preferably o-cresol or cresol containing o-cresol as a main component. When o-cresol is the main component, 50% or more, preferably 70% or more is o-cresol. Although m-cresol and p-cresol other than o-cresol may be included, it is preferably 50% or less. These cresols may contain one or more small amounts of other phenol components. For example, phenol, ethylphenols, isopropylphenols, tertiary butylphenols, allylphenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, 1-naphthol, 2- Examples include naphthol, 1,5-naphthalene diol, 1,6-naphthalene diol, 1,7-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, and the like.
多価ヒドロキシ化合物との反応に用いるスチレン類は、スチレン又は炭素数１〜６の炭化水素基が置換したスチレンである。このスチレン類は少量の他の反応成分を含んでもよい。他の反応成分として、α−メチルスチレン、ジビニルベンゼン、インデン、クマロン、ベンゾチオフェン、インドール、ビニルナフタレン等の不飽和結合含有成分を含む場合、得られる多価ヒドロキシ樹脂にはこれらから生ずる基が芳香環上に置換した化合物が含まれることになる。本発明の多価ヒドロキシ樹脂の製造方法で得られるＳｔＣＮは、このような置換基を有するものを含み得る。同様に、本発明のエポキシ樹脂の製造方法で得られるエポキシ樹脂は、このような置換基を有するものを含み得る。 Styrenes used for the reaction with the polyvalent hydroxy compound are styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms. The styrenes may contain small amounts of other reaction components. When other reactive components include unsaturated bond-containing components such as α-methylstyrene, divinylbenzene, indene, coumarone, benzothiophene, indole, and vinylnaphthalene, the resulting polyvalent hydroxy resin has aromatic groups. A substituted compound on the ring will be included. StCN obtained by the method for producing a polyvalent hydroxy resin of the present invention may include those having such a substituent. Similarly, the epoxy resin obtained by the method for producing an epoxy resin of the present invention may include those having such a substituent.
この反応は酸触媒の存在下に行うことができる。この酸触媒としては、周知の無機酸、有機酸より適宜選択することができる。例えば、塩酸、硫酸、燐酸等の鉱酸や、ギ酸、シュウ酸、トリフルオロ酢酸、ｐ−トルエンスルホン酸、ジメチル硫酸、ジエチル硫酸等の有機酸や、塩化亜鉛、塩化アルミニウム、塩化鉄、三フッ化ホウ素等のルイス酸あるいはイオン交換樹脂、活性白土、シリカ−アルミナ、ゼオライト等の固体酸等が挙げられる。 This reaction can be carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride. Examples thereof include Lewis acids such as boron fluoride or ion exchange resins, activated clays, silica-alumina, solid acids such as zeolite, and the like.
また、この反応は通常、１０〜２５０℃で１〜２０時間行われる。更に、反応の際には、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、メチルセロソルブ、エチルセロソルブ等のアルコール類や、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、ジメチルエーテル、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、ベンゼン、トルエン、クロロベンゼン、ジクロロベンゼン等の芳香族化合物等を溶媒として使用することができる。 Moreover, this reaction is normally performed at 10-250 degreeC for 1 to 20 hours. Further, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, diisopropyl ether, Ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the solvent.
この反応を実施する具体的方法としては、全原料を一括装入し、そのまま所定の温度で反応させるか、又は、多価ヒドロキシ化合物と触媒を装入し、所定の温度に保ちつつ、スチレン類を滴下させながら反応させる方法が一般的である。この際、滴下時間は、５時間以下が好ましく、通常、１〜１０時間である。反応後、溶媒を使用した場合は、必要により、触媒成分を取り除いた後、溶媒を留去させて本発明のＳｔＣＮを得ることができ、溶媒を使用しない場合は、直接熱時排出することによって目的物を得ることができる。 As a specific method for carrying out this reaction, all raw materials are charged in a lump and reacted at a predetermined temperature as it is, or a polyvalent hydroxy compound and a catalyst are charged and maintained at a predetermined temperature while maintaining styrenes. A method of reacting while dropping is generally used. At this time, the dropping time is preferably 5 hours or less, and usually 1 to 10 hours. If a solvent is used after the reaction, the catalyst component can be removed if necessary, and then the solvent can be distilled off to obtain the StCN of the present invention. If the solvent is not used, it can be discharged directly when heated. The object can be obtained.
次に、本発明のエポキシ樹脂について述べる。
本発明のエポキシ樹脂(ＳｔＣＮＥと略す)は一般式（３）で表される。また、は。ＳｔＣＮＥは、一般式（１）で表される多価ヒドロキシ樹脂（ＳｔＣＮ）をエポキシ化することにより得ることができる。
Next, the epoxy resin of the present invention will be described.
The epoxy resin (abbreviated as StCNE) of the present invention is represented by the general formula (3). Also, StCNE can be obtained by epoxidizing the polyvalent hydroxy resin (StCN) represented by the general formula (1).
一般式（３）において、一般式（１）と共通な記号は同じ意味を有する。Ｇはグリシジル基を表すが、一般式（１）の水酸基が反応して生じる。Ｒ1はスチレニル基である。 In the general formula (3), symbols common to the general formula (1) have the same meaning. G represents a glycidyl group, which is generated by the reaction of the hydroxyl group of the general formula (1). R 1 is a styryl group.
本発明のＳｔＣＮＥは、上記一般式（１）で表されるＳｔＣＮと、エピクロルヒドリンを反応させることより製造することが有利であるが、この反応に限らない。 The StCNE of the present invention is advantageously produced by reacting StCN represented by the general formula (1) with epichlorohydrin, but is not limited to this reaction.
ＳｔＣＮをエピクロルヒドリンと反応させる反応の他、ＳｔＣＮとハロゲン化アリルを反応させ、アリルエーテル化合物とした後、過酸化物と反応させる方法をとることもできる。上記ＳｔＣＮをエピクロルヒドリンと反応させる反応は、通常のエポキシ化反応と同様に行うことができる。 In addition to the reaction of reacting StCN with epichlorohydrin, StCN and allyl halide can be reacted to form an allyl ether compound and then reacted with peroxide. The reaction of reacting StCN with epichlorohydrin can be performed in the same manner as a normal epoxidation reaction.
例えば、上記ＳｔＣＮを過剰のエピクロルヒドリンに溶解した後、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物の存在下に、２０〜１５０℃、好ましくは、３０〜８０℃の範囲で１〜１０時間反応させる方法が挙げられる。この際のアルカリ金属水酸化物の使用量は、ＳｔＣＮの水酸基１モルに対して、０．８〜１．５モル、好ましくは、０．９〜１．２モルの範囲である。また、エピクロルヒドリンはＳｔＣＮ中の水酸基１モルに対して過剰に用いられるが、通常、ＳｔＣＮ中の水酸基１モルに対して、１．５〜３０モル、好ましくは、２〜１５モルの範囲である。反応終了後、過剰のエピクロルヒドリンを留去し、残留物をトルエン、メチルイソブチルケトン等の溶剤に溶解し、濾過し、水洗して無機塩を除去し、次いで溶剤を留去することにより目的のエポキシ樹脂を得ることができる。 For example, after the above StCN is dissolved in an excess of epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, it is 20 to 150 ° C, preferably 1 to 10 in the range of 30 to 80 ° C. The method of making it react for time is mentioned. The amount of alkali metal hydroxide used in this case is in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, relative to 1 mol of StCN hydroxyl group. Epichlorohydrin is used in excess with respect to 1 mol of the hydroxyl group in StCN, but is usually in the range of 1.5 to 30 mol, preferably 2 to 15 mol, with respect to 1 mol of the hydroxyl group in StCN. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy is removed by distilling off the solvent. A resin can be obtained.
本発明のエポキシ樹脂組成物は、少なくともエポキシ樹脂及び硬化剤を含むものであるが、次の３種類がある。
１）エポキシ樹脂の一部又は全部として前記ＳｔＣＮＥを配合した組成物。
２）硬化剤の一部又は全部として前記ＳｔＣＮを配合した組成物。
３）エポキシ樹脂及び硬化剤の一部又は全部として前記ＳｔＣＮＥとＳｔＣＮを配合した組成物。
The epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following three types.
1) The composition which mix | blended the said StCNE as a part or all of an epoxy resin.
2) The composition which mix | blended said StCN as a part or all of a hardening | curing agent.
3) The composition which mix | blended said StCNE and StCN as a part or all of an epoxy resin and a hardening | curing agent.
上記２）及び３）の組成物の場合、ＳｔＣＮを必須の成分として含む。この場合のＳｔＣＮ配合量は、通常、エポキシ樹脂１００重量部に対して２〜２００重量部、好ましくは５〜８０重量部の範囲である。これより少ないと難燃性及び耐湿性向上の効果が小さく、これより多いと成形性及び硬化物の強度が低下する問題がある。 In the case of the above compositions 2) and 3), StCN is included as an essential component. In this case, the StCN compounding amount is usually in the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. If it is less than this, the effect of improving flame retardancy and moisture resistance is small, and if it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.
硬化剤の全量としてＳｔＣＮを用いる場合、通常、ＳｔＣＮの配合量は、ＳｔＣＮのＯＨ基とエポキシ樹脂中のエポキシ基の当量バランスを考慮して配合する。エポキシ樹脂及び硬化剤の当量比は、通常、０．２〜５．０の範囲であり、好ましくは０．５〜２．０の範囲である。これより大きくても小さくても、エポキシ樹脂組成物の硬化性が低下するとともに、硬化物の耐熱性、力学強度等が低下する。 When using StCN as the total amount of the curing agent, the compounding amount of StCN is usually compounded in consideration of the equivalent balance of the OH group of StCN and the epoxy group in the epoxy resin. The equivalent ratio of the epoxy resin and the curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength and the like of the cured product are lowered.
硬化剤としてＳｔＣＮ以外の硬化剤を併用することができる。その他の硬化剤の配合量は、ＳｔＣＮの配合量が、通常、エポキシ樹脂１００重量部に対して２〜２００重量部、好ましくは５〜８０重量部の範囲が保たれる範囲内で決定される。ＳｔＣＮの配合量がこれより少ないと低吸湿性、密着性及び難燃性向上の効果が小さく、これより多いと成形性及び硬化物の強度が低下する問題がある。この場合においても、エポキシ樹脂と硬化剤（合計）の当量比は上記の範囲とされる。 A curing agent other than StCN can be used in combination as the curing agent. The blending amount of the other curing agent is determined so that the blending amount of StCN is normally 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. . If the amount of StCN is less than this, the effect of improving low hygroscopicity, adhesion and flame retardancy is small, and if it is more than this, there is a problem that the moldability and the strength of the cured product are lowered. Also in this case, the equivalent ratio of the epoxy resin and the curing agent (total) is in the above range.
ＳｔＣＮ以外の硬化剤としては、一般にエポキシ樹脂の硬化剤として知られているものはすべて使用でき、ジシアンジアミド、酸無水物類、多価フェノール類、芳香族及び脂肪族アミン類等がある。これらの中でも、半導体封止材等の高い電気絶縁性が要求される分野においては、多価フェノール類を硬化剤として用いることが好ましい。以下に、硬化剤の具体例を示す。 As the curing agent other than StCN, any of those generally known as epoxy resin curing agents can be used, and examples include dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. Among these, polyhydric phenols are preferably used as a curing agent in a field where high electrical insulation properties such as a semiconductor sealing material are required. Below, the specific example of a hardening | curing agent is shown.
酸無水物硬化剤としては、例えば、無水フタル酸、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、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチル無水ハイミック酸、無水ドデシニルコハク酸、無水ナジック酸、無水トリメリット酸等がある。 Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecynyl succinic anhydride, nadic anhydride, There are trimellitic anhydride and the like.
多価フェノール類としては、例えば、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、４，４'−ビフェノール、２，２'−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類、あるいは、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、フェノールノボラック、ｏ-クレゾールノボラック、ナフトールノボラック、ポリビニルフェノール等に代表される３価以上のフェノール類がある。更には、フェノール類、ナフトール類、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、４，４'−ビフェノール、２，２'−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類と、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｐ−キシリレンジクロライド、ビスクロロメチルビフェニル、ビスクロロメチルナフタレン等の縮合剤により合成される多価フェノール性化合物等がある。 Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol, or , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, There are phenols. Furthermore, divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, There are polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, bischloromethylnaphthalene, and the like.
アミン類としては、４，４'−ジアミノジフェニルメタン、４，４'−ジアミノジフェニルプロパン、４，４'−ジアミノジフェニルスルホン、ｍ−フェニレンジアミン、ｐ−キシリレンジアミン等の芳香族アミン類、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、リエチレンテトラミン等の脂肪族アミン類がある。
上記組成物には、これら硬化剤の１種又は２種以上を混合して用いることができる。
Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and reethylenetetramine.
One or more of these curing agents can be mixed and used in the composition.
上記組成物に使用されるエポキシ樹脂としては、１分子中にエポキシ基を２個以上有するもの中から選択される。例えば、ビスフェノールＡ、ビスフェノールＦ、３，３'，５，５'−テトラメチル−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、２，２' −ビフェノール、３，３'，５，５'−テトラメチル−４，４'−ジヒドロキシビフェノール、レゾルシン、ナフタレンジオール類等の２価のフェノール類のエポキシ化物、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、フェノールノボラック、ｏ−クレゾールノボラック等の３価以上のフェノール類のエポキシ化物、ジシクロペンタジエンとフェノール類の共縮合樹脂のエポキシ化物、フェノール類とパラキシリレンジクロライド等から合成されるフェノールアラルキル樹脂類のエポキシ化物、フェノール類とビスクロロメチルビフェニル等から合成されるビフェニルアラルキル型フェノール樹脂のエポキシ化物、ナフトール類とパラキシリレンジクロライド等から合成されるナフトールアラルキル樹脂類のエポキシ化物等が挙げられる。これらのエポキシ樹脂は１種又は２種以上を混合して用いることができる。 The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3 ′, 5,5′-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- Epoxidized dihydric phenols such as 4,4′-dihydroxybiphenol, resorcin, naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane , Epoxidized trihydric or higher phenols such as phenol novolac and o-cresol novolac, epoxidized co-condensation resin of dicyclopentadiene and phenol, phenol aralkyl resin synthesized from phenol and paraxylylene dichloride, etc. Epoxidized products, phenols and bisque Examples thereof include an epoxidized product of biphenyl aralkyl type phenolic resin synthesized from rolomethylbiphenyl, an epoxidized product of naphthol aralkyl resin synthesized from naphthols and paraxylylene dichloride, and the like. These epoxy resins can be used alone or in combination of two or more.
上記１）及び３）のエポキシ組成物の場合、ＳｔＣＮＥを必須の成分として含む。このエポキシ樹脂組成物中には、エポキシ樹脂成分として、ＳｔＣＮＥ以外に別種のエポキシ樹脂を配合してもよい。この場合のエポキシ樹脂としては、分子中にエポキシ基を２個以上有する通常のエポキシ樹脂はすべて使用できる。例を挙げれば、ビスフェノールＡ、ビスフェノールＳ、フルオレンビスフェノール、４，４'−ビフェノール、２，２'−ビフェノール、ハイドロキノン、レゾルシン等の２価のフェノール類、あるいは、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、フェノールノボラック、ｏ−クレゾールノボラック等の３価以上のフェノール類、フェノール系アラルキル樹脂類、ビフェニルアラルキル樹脂類、ナフトール系アラルキル樹脂類又はテトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類から誘導されるグルシジルエーテル化物等がある。これらのエポキシ樹脂は、１種又は２種以上を混合して用いることができる。そして、本発明のＳｔＣＮＥを必須成分とする組成物の場合、ＳｔＣＮＥの配合量はエポキシ樹脂全体中、５〜１００％、好ましくは６０〜１００％の範囲であることがよい。 In the case of the epoxy compositions 1) and 3), StCNE is included as an essential component. In this epoxy resin composition, you may mix | blend another kind of epoxy resin other than StCNE as an epoxy resin component. As the epoxy resin in this case, all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. Examples include divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane. , 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolak and other trivalent or higher phenols, phenol-based aralkyl resins, biphenyl aralkyl resins, naphthol-based aralkyl resins Alternatively, there are glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or in combination of two or more. And in the case of the composition which has StCNE of this invention as an essential component, the compounding quantity of StCNE is 5-100% in the whole epoxy resin, Preferably it is good to be the range of 60-100%.
本発明のエポキシ樹脂組成物中には、ポリエステル、ポリアミド、ポリイミド、ポリエーテル、ポリウレタン、石油樹脂、インデン樹脂、インデン・クマロン樹脂、フェノキシ樹脂等のオリゴマー又は高分子化合物を他の改質剤等として適宜配合してもよい。添加量は、通常、エポキシ樹脂１００重量部に対して、２〜３０重量部の範囲である。 In the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, etc. is used as another modifier. You may mix | blend suitably. The addition amount is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.
また、本発明のエポキシ樹脂組成物には、無機充填剤、顔料、難然剤、揺変性付与剤、カップリング剤、流動性向上剤等の添加剤を配合できる。無機充填剤としては、例えば、球状あるいは、破砕状の溶融シリカ、結晶シリカ等のシリカ粉末、アルミナ粉末、ガラス粉末、又はマイカ、タルク、炭酸カルシウム、アルミナ、水和アルミナ等が挙げられ、半導体封止材に用いる場合の好ましい配合量は７０重量％以上であり、更に好ましくは８０重量％以上である。 In addition, the epoxy resin composition of the present invention can contain additives such as inorganic fillers, pigments, refractory agents, thixotropic agents, coupling agents, fluidity improvers and the like. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a stopper is 70% by weight or more, more preferably 80% by weight or more.
顔料としては、有機系又は無機系の体質顔料、鱗片状顔料等がある。揺変性付与剤としては、シリコン系、ヒマシ油系、脂肪族アマイドワックス、酸化ポリエチレンワックス、有機ベントナイト系等を挙げることができる。 Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite.
更に、本発明のエポキシ樹脂組成物には必要に応じて硬化促進剤を用いることができる。例を挙げれば、アミン類、イミダゾール類、有機ホスフィン類、ルイス酸等があり、具体的には、１，８−ジアザビシクロ（５，４，０）ウンデセン−７、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノールなどの三級アミン、２−メチルイミダゾール、２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニル−４−メチルイミダゾール、２−へプタデシルイミダゾールなどのイミダゾール類、トリブチルホスフィン、メチルジフェニルホスフイン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィンなどの有機ホスフィン類、テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・エチルトリフェニルボレート、テトラブチルホスホニウム・テトラブチルボレートなどのテトラ置換ホスホニウム・テトラ置換
ボレート、２−エチル−４−メチルイミダゾール・テトラフェニルボレート、Ｎ−メチルモルホリン・テトラフェニルボレートなどのテトラフェニルボロン塩などがある。添加量としては、通常、エポキシ樹脂１００重量部に対して、０．２から５重量部の範囲である。
Furthermore, a curing accelerator can be used in the epoxy resin composition of the present invention as necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenyl Tetraphenyl such as ruphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, tetrasubstituted phosphonium / tetrasubstituted borate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. There is boron salt. The addition amount is usually in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.
更に必要に応じて、本発明の樹脂組成物には、カルナバワックス、ＯＰワックス等の離型剤、γ-グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、三酸化アンチモン等の難燃剤、シリコンオイル等の低応力化剤、ステアリン酸カルシウム等の滑剤等を使用できる。 Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and trioxide. Flame retardants such as antimony, low stress agents such as silicone oil, lubricants such as calcium stearate, etc. can be used.
本発明のエポキシ樹脂組成物は、有機溶剤を溶解させたワニス状態とした後に、ガラスクロス、アラミド不織布、液晶ポリマー等のポリエステル不織布、等の繊維状物に含浸させた後に溶剤除去を行い、プリプレグとすることができる。また、場合により銅箔、ステンレス箔、ポリイミドフィルム、ポリエステルフィルム等のシート状物上に塗布することにより積層物とすることができる。 The epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, and then impregnated into a fibrous material such as glass cloth, aramid nonwoven fabric, polyester nonwoven fabric such as liquid crystal polymer, etc., and then the solvent is removed, It can be. Moreover, it can be set as a laminated body by apply | coating on sheet-like materials, such as copper foil, stainless steel foil, a polyimide film, and a polyester film depending on the case.
本発明のエポキシ樹脂組成物を加熱硬化させれば、エポキシ樹脂硬化物とすることができ、この硬化物は硬化性、難燃性、低吸湿性、低弾性等の点で優れたものとなる。この硬化物は、エポキシ樹脂組成物を注型、圧縮成形、トランスファー成形等の方法により、成形加工して得ることができる。この際の温度は通常、１２０〜２２０℃の範囲である。 If the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained. This cured product is excellent in terms of curability, flame retardancy, low hygroscopicity, low elasticity, and the like. . This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, transfer molding or the like. The temperature at this time is usually in the range of 120 to 220 ° C.
以下、実施例により本発明を更に具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
実施例１
（多価ヒドロキシ樹脂の合成）
１Ｌの４口フラスコに、多価ヒドロキシ化合物としてｏ−クレゾールノボラック（水酸基当量は１１２ｇ／ｅｑ．、軟化点５８℃、１５０℃での溶融粘度０．０３Ｐａ・ｓ）を１１２ｇ、酸触媒としてｐ−トルエンスルホン酸０．０９ｇを仕込み１５０℃に昇温した。次に、１５０℃にて攪拌しながら、スチレン類としてスチレン５２ｇ（０．５モル）を３時間かけて滴下し反応させた。さらに１５０℃にて１時間反応後、ＭＩＢＫ３２４ｇに溶解させ、８０℃にて５回水洗を行った。続いて、ＭＩＢＫを減圧留去した後、多価ヒドロキシ樹脂（ＳｔＣＮ−Ａ）１５８ｇを得た。その水酸基当量は１６４ｇ／ｅｑ．、軟化点は７２℃、１５０℃での溶融粘度は０．０６Ｐａ・ｓ、ｐは０．５であった（平均値）。ＳｔＣＮ−Ａの1Ｈ−ＮＭＲスペクトルを図１、赤外吸収スペクトルを図２、ＧＰＣチャートを図３に示す。
Example 1
(Synthesis of polyvalent hydroxy resin)
To a 1 L 4-neck flask, 112 g of o-cresol novolak (hydroxyl equivalent is 112 g / eq., Softening point 58 ° C., melt viscosity 0.03 Pa · s at 150 ° C.) as a polyvalent hydroxy compound, p- Toluenesulfonic acid 0.09g was charged and heated to 150 ° C. Next, with stirring at 150 ° C., 52 g (0.5 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Furthermore, after reacting at 150 ° C. for 1 hour, it was dissolved in 324 g of MIBK and washed with water 5 times at 80 ° C. Subsequently, MIBK was distilled off under reduced pressure, and then 158 g of a polyvalent hydroxy resin (StCN-A) was obtained. Its hydroxyl equivalent is 164 g / eq. The softening point was 72 ° C., the melt viscosity at 150 ° C. was 0.06 Pa · s, and p was 0.5 (average value). FIG. 1 shows the 1 H-NMR spectrum of StCN-A, FIG. 2 shows the infrared absorption spectrum, and FIG. 3 shows the GPC chart.
参考例１
多価ヒドロキシ化合物として、フェノールノボラック（昭和高分子製；ＢＲＧ−５５５、水酸基当量１０５ｇ／ｅｑ．、軟化点６７℃、１５０℃での溶融粘度０．０８Ｐａ・ｓ）を１０５ｇ、酸触媒としてｐ−トルエンスルホン酸０．０８ｇを仕込み１５０℃に昇温した。次に、１５０℃にて攪拌しながら、スチレン類としてスチレン５２ｇ（０．５モル）を３時間かけて滴下し反応させた。その後、実施例１と同様な処理を行った後、多価ヒドロキシ樹脂（ＳｔＰＮ）１５０ｇを得た。その軟化点は７５℃、１５０℃での溶融粘度は０．１１Ｐａ・ｓ、水酸基当量は１５７ｇ／ｅｑ．、ｐは０．５であった。
Reference example 1
As a polyvalent hydroxy compound, 105 g of phenol novolak (manufactured by Showa Polymer; BRG-555, hydroxyl group equivalent of 105 g / eq., Softening point 67 ° C., melt viscosity 0.080 Pa · s at 150 ° C.), p-as an acid catalyst 0.08 g of toluenesulfonic acid was charged and the temperature was raised to 150 ° C. Next, with stirring at 150 ° C., 52 g (0.5 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Thereafter, the same treatment as in Example 1 was performed, and then 150 g of a polyvalent hydroxy resin (StPN) was obtained. Its softening point is 75 ° C., melt viscosity at 150 ° C. is 0.11 Pa · s, and hydroxyl equivalent is 157 g / eq. , P was 0.5.
実施例２
（エポキシ樹脂の合成）
四つ口セパラブルフラスコに実施例１で得たＳｔＣＮ−Ａ１５０ｇ、エピクロルヒドリン５０８ｇ、ジエチレングリコールジメチルエーテル７６ｇを入れ撹拌溶解させた。均一に溶解後、１３０ｍｍＨｇの減圧下６５℃に保ち、４８％水酸化ナトリウム水溶液７６．２ｇを４時間かけて滴下し、この滴下中に還流留出した水とエピクロルヒドリンを分離槽で分離しエピクロルヒドリンは反応容器に戻し、水は系外に除いて反応した。反応終了後、濾過により生成した塩を除き、更に水洗したのちエピクロルヒドリンを留去し、エポキシ樹脂（ＳｔＣＮＥ−Ａ）１９１ｇを得た。得られた樹脂のエポキシ当量は２５２ｇ／ｅｑ．、軟化点は５３℃、１５０℃における溶融粘度は０．０８Ｐａ・ｓであった。ＳｔＣＮＥ−Ａの1Ｈ−ＮＭＲスペクトルを図４、赤外吸収スペクトルを図５、ＧＰＣチャートを図６に示す。
Example 2
(Synthesis of epoxy resin)
In a four-necked separable flask, 150 g of StCN-A obtained in Example 1, 508 g of epichlorohydrin, and 76 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 76.2 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and water and epichlorohydrin distilled off during the addition were separated in a separation tank, and epichlorohydrin was The mixture was returned to the reaction vessel, and water was removed from the system to react. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 191 g of an epoxy resin (StCNE-A). The epoxy equivalent of the obtained resin was 252 g / eq. The softening point was 53 ° C. and the melt viscosity at 150 ° C. was 0.08 Pa · s. FIG. 4 shows the 1 H-NMR spectrum of StCNE-A, FIG. 5 shows the infrared absorption spectrum, and FIG. 6 shows the GPC chart.
参考例２
四つ口セパラブルフラスコに参考例１で得たＳｔＰＮ１５０ｇ、エピクロルヒドリン５３０ｇ、ジエチレングリコールジメチルエーテル８０ｇを入れ撹拌溶解させた。均一に溶解後、１３０ｍｍＨｇの減圧下６５℃に保ち、４８％水酸化ナトリウム水溶液７９．６ｇを４時間かけて滴下し、この滴下中に還流留出した水とエピクロルヒドリンを分離槽で分離しエピクロルヒドリンは反応容器に戻し、水は系外に除いて反応した。反応終了後、濾過により生成した塩を除き、更に水洗したのちエピクロルヒドリンを留去し、エポキシ樹脂１９４ｇを得た（ＳｔＰＮＥ）。得られた樹脂のエポキシ当量は２３５ｇ／ｅｑ．、軟化点は５３℃、１５０℃における溶融粘度は０．０９Ｐａ・ｓであった。
Reference example 2
In a four-necked separable flask, 150 g of StPN obtained in Reference Example 1, 530 g of epichlorohydrin, and 80 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 79.6 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours. The mixture was returned to the reaction vessel, and water was removed from the system to react. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 194 g of an epoxy resin (StPNE). The epoxy equivalent of the obtained resin was 235 g / eq. The softening point was 53 ° C., and the melt viscosity at 150 ° C. was 0.09 Pa · s.
実施例３及び比較例１、２
エポキシ樹脂成分としてｏ-クレゾールノボラック型エポキシ樹脂（ＯＣＮＥ；エポキシ当量２００、軟化点６５℃）を使用し、硬化剤として実施例１で得たＳｔＣＮ−Ａ、参考例１で得たＳｔＰＮの他、フェノールノボラック（ＰＮ；ＰＳＭ−４２６１（群栄化学製）；ＯＨ当量１０３、軟化点 ８２℃）を使用した。充填剤としてシリカ（平均粒径１８μｍ）、硬化促進剤としてトリフェニルホスフィンを表１に示す配合で混練しエポキシ樹脂組成物を得た。このエポキシ樹脂組成物を用いて１７５℃にて成形し、１７５℃にて１２時間ポストキュアを行い、硬化物試験片を得た後、各種物性測定に供した。
Example 3 and Comparative Examples 1 and 2
Using an o-cresol novolak type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) as an epoxy resin component, StCN-A obtained in Example 1 as a curing agent, StPN obtained in Reference Example 1, Phenol novolac (PN; PSM-4261 (manufactured by Gunei Chemical); OH equivalent 103, softening point 82 ° C.) was used. Silica (average particle size 18 μm) as a filler and triphenylphosphine as a curing accelerator were kneaded with the formulation shown in Table 1 to obtain an epoxy resin composition. This epoxy resin composition was molded at 175 ° C. and post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements.
吸水率は、直径５０mm、厚さ３mmの円形の試験片を用いて、８５℃、８５％ＲＨの条件で１００時間吸湿させた後の重量変化率とした。接着強度は、銅板２枚の間に２５ｍｍ×１２．５ｍｍ×０．５ｍｍの成形物を圧縮成形機により１７５℃で成形し、１８０℃にて１２時間ポストキュアを行った後、引張剪断強度を求めることにより評価した。測定条件の詳細を次に示し、結果を表２に示す。 The water absorption was defined as the rate of change in weight after absorbing moisture for 100 hours at 85 ° C. and 85% RH using a circular test piece having a diameter of 50 mm and a thickness of 3 mm. The adhesive strength was obtained by molding a molded product of 25 mm × 12.5 mm × 0.5 mm between two copper plates at 175 ° C. with a compression molding machine, post-curing at 180 ° C. for 12 hours, and then adjusting the tensile shear strength. Evaluated by seeking. Details of the measurement conditions are shown below, and the results are shown in Table 2.
１）多価ヒドロキシ樹脂、エポキシ樹脂の分子量分布
ＧＰＣ測定装置（日本ウォーターズ製、５１５Ａ型ＧＰＣ）を用い、カラムにＴＳＫｇｅｌ Ｇ２０００ＨＸＬ（東ソー製）３本、ＴＳＫｇｅｌ Ｇ４０００ＨＸＬ（東ソー製）１本を使用し、検出器をＲＩとし、溶媒にテトラヒドロフラン、流量１．０ｍｌ／ｍｉｎ、カラム温度３８℃として測定した。
1) Molecular weight distribution of polyhydric hydroxy resin and epoxy resin Using GPC measuring device (manufactured by Nihon Waters, 515A type GPC), three TSKgel G2000HXL (manufactured by Tosoh) and one TSKgel G4000HXL (manufactured by Tosoh) are used. The detector was RI, the solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, and the column temperature was 38 ° C.
２）軟化点
ＪＩＳ−Ｋ−２２０７に従い環球法にて測定した。
2) Softening point It measured by the ring and ball method according to JIS-K-2207.
３）溶融粘度
ＢＲＯＯＫＦＩＥＬＤ製、ＣＡＰ２０００Ｈ型回転粘度計を用いて、１５０℃にて測定した。
3) Melt viscosity The viscosity was measured at 150 ° C. using a CAP2000H rotational viscometer manufactured by BROOKFIELD.
４）水酸基当量の測定
電位差滴定装置を用い、１，４−ジオキサンを溶媒に用い、１．５ｍｏｌ／Ｌ塩化アセチルでアセチル化を行い、過剰の塩化アセチルを水で分解して０．５ｍｏｌ／Ｌ−水酸化カリウムを使用して滴定した。
4) Measurement of hydroxyl group equivalent Using a potentiometric titrator, 1,4-dioxane is used as a solvent, acetylation is performed with 1.5 mol / L acetyl chloride, and excess acetyl chloride is decomposed with water to 0.5 mol / L. -Titration using potassium hydroxide.
５）エポキシ当量の測定
電位差滴定装置を用い、溶媒としてメチルエチルケトンを使用し、臭素化テトラエチルアンモニウム酢酸溶液を加え、電位差滴定装置にて０．１ｍｏｌ／Ｌ過塩素酸−酢酸溶液を用いて測定した。
5) Measurement of epoxy equivalent Using a potentiometric titrator, methyl ethyl ketone was used as a solvent, a brominated tetraethylammonium acetic acid solution was added, and the potential was measured using a 0.1 mol / L perchloric acid-acetic acid solution.
６）1Ｈ−ＮＭＲスペクトル
日本電子製、ＪＮＭ−ＬＡ４００型測定装置により、溶媒として重クロロホルムを用いて測定した。
6) 1 H-NMR spectrum The 1 H-NMR spectrum was measured using a JNM-LA400 type measuring apparatus, using deuterated chloroform as a solvent.
７）赤外吸収スペクトル
日本電子製、ＪＩＲ−１００型測定装置により、ＫＢｒ錠剤法により測定した。
7) Infrared absorption spectrum It measured with the KBr tablet method by the JEOL make and JIR-100 type | mold measuring apparatus.
８）ゲルタイム
１７５℃に加熱しておいたゲル化試験機（日新科学（株）製）のプレート上にエポキシ樹脂組成物を添加し、フッ素樹脂棒を用いて一秒間に２回転の速度で攪拌し、エポキシ樹脂組成物が硬化するまでに要したゲル化時間を調べた。
8) Gel time An epoxy resin composition is added onto a plate of a gelation tester (manufactured by Nisshin Kagaku Co., Ltd.) that has been heated to 175 ° C., and is rotated twice per second using a fluororesin rod. The gelation time required for stirring and curing of the epoxy resin composition was examined.
９）線膨張係数（ＣＴＥ、ガラス転移点（Ｔｇ）
セイコーインスツル製ＴＭＡ１２０Ｃ型熱機械測定装置により、昇温速度１０℃／分の条件で、Ｔｇを求め、α１（Ｔｇ以下のＣＴＥ）は３０〜５０℃の範囲の平均値を、またα２（Ｔｇ以上のＣＴＥ）はＴｇプラス２０℃〜４０℃の範囲の平均値から求めた。
9) Linear expansion coefficient (CTE, glass transition point (Tg)
Using a TMA120C type thermomechanical measuring device manufactured by Seiko Instruments Inc., Tg was obtained under the condition of a heating rate of 10 ° C./min. Α1 (CTE of Tg or less) was an average value in the range of 30 to 50 ° C., and α2 (Tg The above CTE) was determined from the average value in the range of Tg plus 20 ° C to 40 ° C.
１０）曲げ強度及び曲げ弾性
ＪＩＳＫ ６９１１に従い、３点曲げ試験法で常温にて測定した。
10) Bending strength and bending elasticity According to JISK6911, it measured at normal temperature by the three-point bending test method.
１１）接着強度
銅板２枚の間に２５ｍｍ×１２．５ｍｍ×０．５ｍｍの成形物を圧縮成形機により１７５℃で成形し、１８０℃にて１２時間ポストキュアを行った後、引張剪断強度を求めることにより評価した。
11) Adhesive strength A molded product of 25 mm × 12.5 mm × 0.5 mm was formed between two copper plates at 175 ° C. with a compression molding machine, post-cured at 180 ° C. for 12 hours, and then subjected to tensile shear strength. Evaluated by seeking.
１２）吸水率
２５℃、相対湿度５０％の条件を標準状態とし、８５℃、相対湿度８５％の条件で１００時間吸湿させた後の重量変化率とした。
12) Water absorption rate The conditions of 25 ° C. and 50% relative humidity were taken as the standard state, and the weight change rate after absorbing for 100 hours under the conditions of 85 ° C. and 85% relative humidity.
１３）難燃性
厚さ１／１６インチの試験片を成形し、ＵＬ９４Ｖ-０規格によって評価し、５本の試験片での合計の燃焼時間で表した。
13) Flame retardance A test piece having a thickness of 1/16 inch was molded, evaluated according to the UL94V-0 standard, and represented by the total burning time of five test pieces.
実施例４、５及び比較例３〜５
エポキシ樹脂成分として、実施例２で得たＳｔＣＮＥ−Ａ、参考例２で得たＳｔＰＮＥの他、ｏ−クレゾールノボラック型エポキシ樹脂（ＯＣＮＥ；エポキシ当量２００、軟化点６５℃）を用い、硬化剤成分として、フェノールアラルキル樹脂（ＰＡ；ＭＥＨ−７８００ＳＳ（明和化成製）、ＯＨ当量１７５、軟化点６７℃）又はフェノールノボラック（ＰＮ；ＰＳＭ−４２６１（群栄化学製）、ＯＨ当量１０３、軟化点 ８２℃）を用いた。更に、充填剤として球状シリカ（平均粒径 １８μｍ）、硬化促進剤としてトリフェニルホスフィンを用い、表３に示す配合でエポキシ樹脂組成物を得た。表中の数値は配合における重量部を示す。
Examples 4 and 5 and Comparative Examples 3 to 5
As the epoxy resin component, in addition to StCNE-A obtained in Example 2, StPNE obtained in Reference Example 2, o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) is used as a curing agent component. As phenol aralkyl resin (PA; MEH-7800SS (Maywa Kasei), OH equivalent 175, softening point 67 ° C.) or phenol novolak (PN; PSM-4261 (Gunei Chemical)), OH equivalent 103, softening point 82 ° C. ) Was used. Furthermore, spherical silica (average particle size 18 μm) was used as a filler, triphenylphosphine was used as a curing accelerator, and an epoxy resin composition was obtained with the formulation shown in Table 3. The numerical value in a table | surface shows the weight part in a mixing | blending.
このエポキシ樹脂組成物を用いて１７５℃で成形し、更に１７５℃にて１２時間ポストキュアを行い、硬化物試験片を得た後、各種物性測定に供した。結果を表４に示す。 This epoxy resin composition was molded at 175 ° C., and further post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. The results are shown in Table 4.
Claims (8)
（Ｒ1は下記式（ａ）で表される置換基を示し、ｎは１〜２０の数を示す。また、ｐは０．１〜２．５の数を示す。）
（Ｒ2は水素又は炭素数１〜３のアルキル基を示す。） A polyvalent hydroxy resin represented by the following general formula (1).
(R 1 represents a substituent represented by the following formula (a), n represents a number of 1 to 20, and p represents a number of 0.1 to 2.5.)
(R 2 represents hydrogen or an alkyl group having 1 to 3 carbon atoms .)
（ここで、Ｒ2は水素原子又は炭素数１〜３のアルキル基を示し、ｎは１〜２０の数を示す。） Represented by the formula (a) by reacting 0.1 to 2.5 mol of styrene in the presence of an acid catalyst with respect to 1 mol of the hydroxy group of the polyvalent hydroxy compound represented by the following general formula (2). A method for producing a polyvalent hydroxy resin, comprising substituting a substituted benzene ring of a polyvalent hydroxy compound.
(Here, R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents a number of 1 to 20)
An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the polyvalent hydroxy resin according to claim 1 is an essential component as part or all of the curing agent.
（ここで、Ｇはグリシジル基を示し、Ｒ1は下記式（ａ）で表される置換基を示し、Ｒ2は水素又は炭素数１〜３のアルキル基を示し、ｐは０．１〜２．５の数を示す。ｎは１〜２０の数を示す。） An epoxy resin represented by the following general formula (3).
(Here, G represents a glycidyl group, R 1 represents a substituent represented by the following formula (a), R 2 represents hydrogen or an alkyl group having 1 to 3 carbon atoms , and p represents 0.1 to 0.1). 2.5 represents a number, and n represents a number from 1 to 20.)
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