JP6124865B2 - 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
- Publication number
- JP6124865B2 JP6124865B2 JP2014500754A JP2014500754A JP6124865B2 JP 6124865 B2 JP6124865 B2 JP 6124865B2 JP 2014500754 A JP2014500754 A JP 2014500754A JP 2014500754 A JP2014500754 A JP 2014500754A JP 6124865 B2 JP6124865 B2 JP 6124865B2
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- JP
- Japan
- Prior art keywords
- epoxy resin
- polyvalent hydroxy
- aralkyl
- resin
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 110
- 229920000647 polyepoxide Polymers 0.000 title claims description 110
- 229920005989 resin Polymers 0.000 title claims description 79
- 239000011347 resin Substances 0.000 title claims description 79
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims description 66
- 239000000203 mixture Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 66
- 238000005227 gel permeation chromatography Methods 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000012435 aralkylating agent Substances 0.000 claims description 26
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 43
- 150000002989 phenols Chemical class 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 229920003986 novolac Polymers 0.000 description 20
- 125000003710 aryl alkyl group Chemical group 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- -1 hydroxypropyl group Chemical group 0.000 description 12
- 239000000155 melt Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 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
- 239000000243 solution Substances 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
- 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
- 238000005259 measurement Methods 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 239000003054 catalyst Substances 0.000 description 6
- 230000000704 physical effect Effects 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
- 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 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
- 229940126062 Compound A Drugs 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen 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
- 150000003839 salts Chemical class 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- 125000003545 alkoxy 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
- 239000006185 dispersion Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 150000004780 naphthols Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- 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
- HNASEWFYPPRNKM-UHFFFAOYSA-N 1-(methoxymethyl)-4-methylbenzene Chemical compound COCC1=CC=C(C)C=C1 HNASEWFYPPRNKM-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
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-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
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-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
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 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
- 125000003118 aryl group Chemical group 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
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000005266 casting Methods 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
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 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
- 238000009472 formulation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 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
- 230000006872 improvement Effects 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 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
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000126 substance Substances 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
- 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
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- 238000010998 test method Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical class CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Images
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
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
Description
本発明は、硬化性に優れるとともに、機械的強度、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 gives a cured product having excellent curability and mechanical strength, flame retardancy, moisture resistance, and low elasticity, a polyvalent hydroxy resin suitable as an intermediate thereof, a production method thereof, and the like The present invention relates to the epoxy resin composition used and its cured product, and is suitably used for insulating materials in the electric and electronic fields such as semiconductor sealing materials and printed wiring boards.
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。
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、特許文献６にはスチレン変性ノボラックの製造方法が開示されているが、エポキシ樹脂組成物として着目されたものではない。
As an example focusing on improving heat resistance, moisture resistance and crack resistance,
さらには、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７及び８にはスチレン変性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、これらもスチレン化フェノールノボラック及びエポキシ樹脂の分子量分布に関して詳細に検討した例はない。なお、分子量分布（分散）はＭｗ／Ｍｎで表わされる。 Furthermore, as an example of an epoxy resin composition focused on improving moisture resistance and low stress properties, Patent Documents 7 and 8 disclose a styrene-modified phenol novolac resin and an epoxy resin composition using the epoxy resin. Also, there are no examples in which the molecular weight distribution of styrenated phenol novolac and epoxy resin has been studied in detail. The molecular weight distribution (dispersion) is represented by Mw / Mn.
一方、難燃性の向上に着目した例として、特許文献９にはスチレン変性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。ここでは、スチレン変性量に着目し、変性量を増加させることで水酸基当量あるいはエポキシ当量を高く調整した樹脂を用いている。そのような樹脂を用いた硬化物において、エポキシ基由来の脂肪族成分の含有率を相対的に低くすることで、高度な難燃性を発現することができるとされている。しかし、ここでも多価ヒドロキシ樹脂及びエポキシ樹脂の分子量分布に関して詳細に検討した例はなかった。 On the other hand, as an example paying attention to improvement in flame retardancy, Patent Document 9 discloses a styrene-modified phenol novolac resin and an epoxy resin composition using the epoxy resin. Here, paying attention to the amount of styrene modification, a resin whose hydroxyl equivalent or epoxy equivalent is adjusted high by increasing the modification amount is used. In a cured product using such a resin, it is said that high flame retardancy can be expressed by relatively reducing the content of an aliphatic component derived from an epoxy group. However, there has been no example in which the molecular weight distributions of the polyvalent hydroxy resin and the epoxy resin are examined in detail here.
本発明の目的は、積層、成形、注型、接着等の用途において、硬化性及び機械的物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、優れた硬化性及び機械的特性を有するとともに、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 properties such as flame retardancy, moisture resistance and low elasticity, as well as excellent curability and mechanical properties in applications such as lamination, molding, casting and adhesion. Epoxy useful for sealing electrical and electronic components, circuit board materials, etc. that have excellent curability and mechanical properties, and also provides cured products with excellent flame retardancy, moisture resistance, low elasticity, etc. The object is to provide a resin composition and to provide a cured product thereof.
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化合物と、アラルキル化剤とを反応させて、式（ａ）で表されるアラルキル化剤由来の置換基を多価ヒドロキシ化合物のベンゼン環に置換させて得られるアラルキル変性多価ヒドロキシ樹脂であって、一般式（１）の多価ヒドロキシ化合物として、ゲルパーミエーションクロマトグラフィー（GPC)で測定した面積％でｎ＝１成分が１５％以下であり、ｎ＝２及びｎ＝３成分の合計が５０％以上であり、Ｍｗ／Ｍｎが１．２以下である狭分散多価ヒドロキシ化合物を使用して得られたことを特徴とするアラルキル変性多価ヒドロキシ樹脂に関する。 That is, the present invention reacts a polyvalent hydroxy compound represented by the following general formula (1) with an aralkylating agent to convert a substituent derived from the aralkylating agent represented by the formula (a) to a polyvalent hydroxy. An aralkyl-modified polyhydroxy resin obtained by substituting the benzene ring of a compound, wherein n = 1 component in area% measured by gel permeation chromatography (GPC) as a polyvalent hydroxy compound of the general formula (1) Is obtained by using a narrow-dispersed polyvalent hydroxy compound in which the total of n = 2 and n = 3 components is 50% or more and Mw / Mn is 1.2 or less. The present invention relates to an aralkyl-modified polyvalent hydroxy resin.
本発明の別の態様は、上記一般式（１）で表される多価ヒドロキシ化合物とスチレン類とを反応させて、式（ａ2）で表されるスチレン由来の置換基を多価ヒドロキシ化合物のベンゼン環に置換させて得られるスチレン変性多価ヒドロキシ樹脂であって、一般式（１）の多価ヒドロキシ化合物として、GPCで測定した面積％でｎ＝１成分が１５％以下であり、ｎ＝２及びｎ＝３成分の合計が５０％以上であり、Ｍｗ／Ｍｎが１．２以下である狭分散多価ヒドロキシ化合物を使用して得られたことを特徴とするスチレン変性多価ヒドロキシ樹脂である。
本発明の別の態様は、上記一般式（１）で表される多価ヒドロキシ化合物と、下記式（b1）または（b2）で表されるアラルキル化剤とを反応させて、上記式（ａ）で表されるアラルキル化剤由来の置換基を多価ヒドロキシ化合物のベンゼン環に置換させて得られるアラルキル変性多価ヒドロキシ樹脂を製造するにあたり、一般式（１）の多価ヒドロキシ化合物として、GPCで測定した面積％でｎ＝１成分が１５％以下であり、ｎ＝２及びｎ＝３成分の合計が５０％以上であり、Ｍｗ／Ｍｎが１．２以下である狭分散多価ヒドロキシ化合物を使用すること、及び上記反応を１０〜１０００ｐｐｍの酸触媒の存在下、反応温度４０〜１２０℃で反応させることを特徴とするアラルキル変性多価ヒドロキシ樹脂の製造方法である。 In another embodiment of the present invention, a polyhydroxy compound represented by the above general formula (1) is reacted with an aralkylating agent represented by the following formula (b1) or (b2) to form the above formula (a In the production of an aralkyl-modified polyvalent hydroxy resin obtained by substituting a benzene ring of a polyvalent hydroxy compound with a substituent derived from an aralkylating agent represented by the formula (1), GPC N = 1 component is 15% or less in area% measured in the above, the total of n = 2 and n = 3 components is 50% or more, and the narrowly dispersed polyvalent hydroxy compound whose Mw / Mn is 1.2 or less And the above reaction is carried out at a reaction temperature of 40 to 120 ° C. in the presence of 10 to 1000 ppm of an acid catalyst.
上記アラルキル変性多価ヒドロキシ樹脂の製造方法において、多価ヒドロキシ化合物のヒドロキシ基１モルに対し、アラルキル化剤０．１〜１．５モルを反応させること、またはアラルキル化剤がスチレンであることが好ましい。 In the above method for producing an aralkyl-modified polyvalent hydroxy resin, 0.1 to 1.5 mol of an aralkylating agent is reacted with 1 mol of a hydroxy group of a polyvalent hydroxy compound, or the aralkylating agent is styrene. preferable.
本発明の別の態様は、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、硬化剤の一部又は全部として、上記のアラルキル変性多価ヒドロキシ樹脂を必須成分としてなることを特徴とするエポキシ樹脂組成物、およびその硬化物である。 Another aspect of the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the aralkyl-modified polyvalent hydroxy resin is an essential component as part or all of the curing agent. It is a composition and its cured product.
本発明の別の態様は、上記のアラルキル変性多価ヒドロキシ樹脂とエピクロルヒドリンを反応させて得られることを特徴とするエポキシ樹脂である。また、別の態様は、上記のアラルキル変性多価ヒドロキシ樹脂とエピクロルヒドリンを反応させて、アラルキル変性多価ヒドロキシ樹脂のヒドロキシ基をグリシジルエーテル基とすることを特徴とするエポキシ樹脂の製造方法である。 Another aspect of the present invention is an epoxy resin obtained by reacting the above aralkyl-modified polyvalent hydroxy resin with epichlorohydrin. Another embodiment is a method for producing an epoxy resin, characterized in that the aralkyl-modified polyvalent hydroxy resin and epichlorohydrin are reacted to make the hydroxy group of the aralkyl-modified polyvalent hydroxy resin a glycidyl ether group.
本発明の別の態様は、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、上記のエポキシ樹脂を必須成分として配合してなるエポキシ樹脂組成物、およびそのエポキシ樹脂硬化物である。 Another aspect of the present invention is an epoxy resin composition comprising the above epoxy resin as an essential component in an epoxy resin composition comprising an epoxy resin and a curing agent, and a cured epoxy resin product thereof.
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、多価ヒドロキシ化合物に対してアラルキル基を付加させ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、芳香族性に富んだアラルキル基の付加により、多価ヒドロキシ樹脂の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。 In the cured epoxy resin, the hydroxypropyl group produced by the reaction between the epoxy group and the hydroxyl group is said to burn easily. However, by adding an aralkyl group to the polyvalent hydroxy compound to increase the hydroxyl equivalent, The aliphatic carbon ratio of the flammable component derived from the group is low, and a high level of flame retardancy can be expressed. In addition, the addition of an aralkyl group rich in aromaticity further improves the aromaticity of the polyvalent hydroxy resin, and is effective in improving moisture resistance in addition to flame retardancy.
しかし一方で、アラルキル基の変性割合を増加することによる物性改善の手法は、立体障害の増加に起因した硬化性の低下や硬化物の機械的強度を低下させる傾向があった。そこで、ベースの多価ヒドロキシ化合物の分子量分布を制御することで、硬化性や機械的強度を損なわないアラルキル基変性割合において、硬化性や機械的強度に優れ、且つ難燃性、耐湿性及び低弾性にも優れたアラルキル変性多価ヒドロキシ樹脂及びエポキシ樹脂を見出すに至った。 However, on the other hand, methods for improving physical properties by increasing the modification rate of the aralkyl group tend to lower the curability due to the increase in steric hindrance and the mechanical strength of the cured product. Therefore, by controlling the molecular weight distribution of the base polyhydric hydroxy compound, the aralkyl group modification ratio that does not impair the curability and mechanical strength, the curability and mechanical strength are excellent, and flame retardancy, moisture resistance and low The inventors have found an aralkyl-modified polyvalent hydroxy resin and an epoxy resin that are excellent in elasticity.
本発明で使用する多価ヒドロキシ化合物は、一般式（１）で表わされる狭分散多価ヒドロキシ化合物であるので、多価ヒドロキシ化合物（１）又は狭分散多価ヒドロキシ化合物ともいう。また、ノボラック樹脂の１種でもあるので、フェノールノボラックともいう。 Since the polyvalent hydroxy compound used in the present invention is a narrowly dispersed polyvalent hydroxy compound represented by the general formula (1), it is also referred to as a polyvalent hydroxy compound (1) or a narrowly dispersed polyvalent hydroxy compound. Moreover, since it is also 1 type of novolak resin, it is also called a phenol novolac.
狭分散多価ヒドロキシ化合物をベースとしたアラルキル変性多価ヒドロキシ樹脂及びエポキシ樹脂を用いた場合、硬化性、機械的強度及び難燃性等に優れたエポキシ樹脂組成物を得ることができる。すなわち、多価ヒドロキシ化合物のｎ＝１（２官能）成分へのアラルキル変性物の割合が増加した場合、立体障害の増加により硬化性が低下し硬化物の機械的強度も低い傾向にある。一方、より多官能成分であるｎ＝２（３官能）及びｎ＝３（４官能）成分の割合が高い多価ヒドロキシ化合物を用いた場合、アラルキル変性された場合においても立体障害の影響は相対的に低減されることで、硬化性、機械的強度に優れた硬化物を得ることができる。また、多官能成分が増加した場合、硬化物の架橋密度が増加することで、より熱安定性に優れた硬化物となり難燃性にも優れる傾向を示す。しかし、ｎ＝４（５官能）以上成分が増加した場合、分子量が高くなるため、流動性や成形加工性に劣る傾向にある。 When an aralkyl-modified polyvalent hydroxy resin and an epoxy resin based on a narrowly dispersed polyvalent hydroxy compound are used, an epoxy resin composition excellent in curability, mechanical strength, flame retardancy, and the like can be obtained. That is, when the ratio of the aralkyl modified product to the n = 1 (bifunctional) component of the polyvalent hydroxy compound increases, the curability decreases due to an increase in steric hindrance and the mechanical strength of the cured product tends to be low. On the other hand, when a polyhydric hydroxy compound having a higher ratio of n = 2 (trifunctional) and n = 3 (tetrafunctional) components, which are more multifunctional components, is used, the effect of steric hindrance is relative even when aralkyl-modified. By being reduced, a cured product having excellent curability and mechanical strength can be obtained. Moreover, when a polyfunctional component increases, it will become the hardened | cured material which was excellent in thermal stability more, and the tendency which is excellent also in a flame retardance will increase by the crosslinking density of hardened | cured material increasing. However, when n = 4 (pentafunctional) or more components are increased, the molecular weight is increased, so that the fluidity and molding processability tend to be inferior.
よって、これらを用いて硬化性、機械的強度及び難燃性等に優れた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硬化性とともに、機械的強度、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, the epoxy resin composition excellent in sclerosis | hardenability, mechanical strength, a flame retardance, etc. using these, especially the epoxy resin composition for semiconductor sealing are obtained. That is, in addition to excellent curability in these compositions, physical properties excellent in mechanical strength, high flame retardancy, moisture resistance and low elasticity are expressed. Using this material, highly reliable electrical and electronic parts Sealing, circuit board materials, etc. are obtained.
まず、本発明のアラルキル変性多価ヒドロキシ樹脂（ＳｔＰＮ）について説明する。本発明のアラルキル変性多価ヒドロキシ樹脂は一般式（１）で表される多価ヒドロキシ化合物において、ゲルパーミエーションクロマトグラフィー（ＧＰＣ；ＲＩ）で検出した時の面積％でｎ＝１成分が１５％以下であり、ｎ＝２およびｎ＝３成分の合計が５０％以上であり、Ｍｗ／Ｍｎが１．２以下である狭分散多価ヒドロキシ化合物とアラルキル化剤を反応させることにより得ることができる。 First, the aralkyl modified polyvalent hydroxy resin (StPN) of the present invention will be described. The aralkyl-modified polyvalent hydroxy resin of the present invention is a polyvalent hydroxy compound represented by the general formula (1), wherein the area% when detected by gel permeation chromatography (GPC; RI) is 15% with n = 1 component. It can be obtained by reacting a narrowly dispersed polyvalent hydroxy compound having an n = 2 and n = 3 component of 50% or more and an Mw / Mn of 1.2 or less with an aralkylating agent. .
本発明のアラルキル変性多価ヒドロキシ樹脂をＳｔＰＮといい、これを得るために使用する一般式（１）で表される多価ヒドロキシ化合物を、多価ヒドロキシ化合物又は狭分散多価ヒドロキシ化合物という。このアラルキル変性多価ヒドロキシ樹脂のアラルキルとは、式（a）で表わされる基をいう。ＳｔＰＮを得るために使用するアラルキル化剤とは、式（ｃ1）又は（ｃ2）で表わされる化合物をいう。また、アラルキル化剤をスチレンで代表することがあり、アラルキル変性多価ヒドロキシ樹脂をスチレン変性多価ヒドロキシ樹脂ということがある。 The aralkyl-modified polyvalent hydroxy resin of the present invention is referred to as StPN, and the polyvalent hydroxy compound represented by the general formula (1) used for obtaining this is referred to as a polyvalent hydroxy compound or a narrowly dispersed polyhydroxy compound. Aralkyl in the aralkyl-modified polyvalent hydroxy resin means a group represented by the formula (a). The aralkylating agent used to obtain StPN refers to a compound represented by the formula (c1) or (c2). The aralkylating agent may be represented by styrene, and the aralkyl-modified polyvalent hydroxy resin may be referred to as a styrene-modified polyvalent hydroxy resin.
本発明に用いる狭分散多価ヒドロキシ化合物の分子量分布の範囲としては、ｎ＝１成分の含有率が１５％以下であり、より好ましくは１０％以下の範囲である。また、ｎ＝２及びｎ＝３成分の含有率の範囲は５０％以上であり、より好ましくは６０％以上、さらに好ましくは７０％以上の範囲である。ｎ＝１成分の含有率を低減させることで、硬化性、機械的強度、難燃性等の物性を向上することが出来る。さらに、分散度（Ｍｗ／Ｍｎ）の範囲は１．２以下が好ましく、より好ましくは１．１以下の範囲である。１．２を超える場合では硬化性、機械的強度等の物性に劣る傾向がある。なお、GPC面積％とwt％はほぼ比例するので、GPC面積％はwt％と見ることが可能である。 As the range of the molecular weight distribution of the narrowly dispersed polyvalent hydroxy compound used in the present invention, the content of n = 1 component is 15% or less, more preferably 10% or less. Moreover, the range of the content rate of n = 2 and n = 3 component is 50% or more, More preferably, it is 60% or more, More preferably, it is the range of 70% or more. By reducing the content of n = 1 component, physical properties such as curability, mechanical strength, and flame retardancy can be improved. Further, the dispersity (Mw / Mn) is preferably 1.2 or less, and more preferably 1.1 or less. When it exceeds 1.2, the physical properties such as curability and mechanical strength tend to be inferior. Since GPC area% and wt% are almost proportional, GPC area% can be regarded as wt%.
本発明で用いる狭分散多価ヒドロキシ化合物は、フェノール類とアルデヒド類のモル比を調整することにより得られた粗多価ヒドロキシ化合物から低分子量成分を除去することにより得ることができる。 The narrowly dispersed polyvalent hydroxy compound used in the present invention can be obtained by removing low molecular weight components from a crude polyvalent hydroxy compound obtained by adjusting the molar ratio of phenols and aldehydes.
フェノール類とアルデヒド類のモル比はフェノール類１モルに対するアルデヒド類のモル比で示され０．１〜０．９の範囲で製造されるが、モル比が小さい場合はｎ＝１〜３成分が多く生成され、モル比が大きい場合はｎ＝４以上の高分子量成分が多く生成し、ｎ＝１〜３成分は少なくなる。 The molar ratio of phenols to aldehydes is indicated by the molar ratio of aldehydes to 1 mole of phenols, and is produced in the range of 0.1 to 0.9. When many are produced and the molar ratio is large, a large amount of high molecular weight components of n = 4 or more are produced, and n = 1 to 3 components are reduced.
本発明で用いる狭分散多価ヒドロキシ化合物は、フェノール類とアルデヒド類とをリン酸類触媒の存在下、不均一系により反応させる工程により得る方法、得られた粗多価ヒドロキシ化合物からｎ＝１成分及び／又はｎ＝４成分以上の高分子量成分を各種溶媒の溶解性差を利用して除去する方法、アルカリ水溶液に二核体を溶解して除去する方法などによって得ることが出来きるが、その他の公知の分離方法によっても良い。 The narrowly dispersed polyhydroxy compound used in the present invention is a method obtained by reacting phenols and aldehydes in a heterogeneous system in the presence of a phosphoric acid catalyst, and n = 1 component from the obtained crude polyvalent hydroxy compound. And / or n = 4 or higher molecular weight components can be obtained by utilizing the difference in solubility of various solvents, or by removing the binuclear substance by dissolving in an aqueous alkali solution. A known separation method may be used.
本発明のＳｔＰＮは、一般式（１）で表される狭分散多価ヒドロキシ化合物とアラルキル化剤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アラルキル化剤との割合としては、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、多価ヒドロキシ化合物１モルに対するアラルキル化剤の使用割合が０．１〜１．５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 StPN of the present invention can be obtained by addition reaction of a narrowly dispersed polyvalent hydroxy compound represented by the general formula (1) and an aralkylating agent. At this time, the ratio of the polyvalent hydroxy compound to the aralkylating agent is, when the balance between the flame retardancy and curability of the resulting cured product is taken into consideration, the ratio of the aralkylating agent used relative to 1 mol of the polyvalent hydroxy compound is 0. The range is preferably 1 to 1.5 mol, more preferably 0.1 to 1.0 mol, and still more preferably 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、アラルキル化剤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）で表わされるアラルキル基が置換する。式（ａ）において、Ｒ3およびＲ4は水素原子又はＣ1〜6のアルキル基を示す。アルキル基は好ましくはメチル基である。より好ましくは、Ｒ3およびＲ4の一方又は両方が水素原子又はメチル基であり、更に好ましくは、一方又は両方が水素原子である。両方が水素原子である場合は、ベンジル基であり、一方が水素原子である場合は、α−アルキル置換ベンジル基である。このベンジル基又はα−アルキル置換ベンジル基のベンゼン環には、置換基Ｒ2が置換してもよい。アラルキル基の付加位置は、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, an aralkylating agent is added to the aromatic ring having an OH group in the polyvalent hydroxy compound to replace the aralkyl group represented by the above formula (a). In the formula (a), R 3 and R 4 represent a hydrogen atom or a C 1-6 alkyl group. The alkyl group is preferably a methyl group. More preferably, one or both of R 3 and R 4 are a hydrogen atom or a methyl group, and more preferably one or both are a hydrogen atom. When both are hydrogen atoms, it is a benzyl group, and when one is a hydrogen atom, it is an α-alkyl-substituted benzyl group. The benzene ring of this benzyl group or α-alkyl-substituted benzyl group may be substituted with a substituent R 2 . The aralkyl group is added at the vacant ortho and / or para position of the polyvalent hydroxy compound, but mainly at the para position.
また、本発明のＳｔＰＮ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。 The melt viscosity of StPN of the present invention at 150 ° C. 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.
アラルキル化剤の使用量によりアラルキル基の付加量が調整でき、通常多価ヒドロキシ化合物のベンゼン環に対して０．１〜２．５個付加する。これは１個のフェノール環に置換するアラルキル基の平均の数（数平均）を意味する。付加量としては多価ヒドロキシ化合物のベンゼン環１モルに対して０．１〜１．５モル、０．１〜１．０モル、０．３〜０．８モルの順に好ましい。なお、両末端のフェノール環には最大４個のアラルキル基が置換でき、中間のフェノール環には最大３個のアラルキル基が置換できるので、ｎが１の場合は最大８個のアラルキル基が置換できる。 The amount of the aralkyl group added can be adjusted by the amount of the aralkylating agent used, and usually 0.1 to 2.5 aralkyl groups are added to the benzene ring of the polyvalent hydroxy compound. This means the average number (number average) of aralkyl groups substituted on one phenol ring. The addition amount is preferably 0.1 to 1.5 mol, 0.1 to 1.0 mol, and 0.3 to 0.8 mol with respect to 1 mol of the benzene ring of the polyvalent hydroxy compound. It should be noted that a maximum of 4 aralkyl groups can be substituted for the phenol ring at both ends, and a maximum of 3 aralkyl groups can be substituted for the intermediate phenol ring, so when n is 1, a maximum of 8 aralkyl groups can be substituted. it can.
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アラルキル化剤によって定まる。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 aralkylating agent used as a reaction raw material.
一般式（１）において、ｎは１〜５の数を示すが、好ましくは、平均（数平均）として１．９〜３．４の範囲である。さらに好ましくは２．０〜３．０の範囲であるが、上記分散を満足する必要がある。別の観点からは、ｎが１〜５の成分が主成分であることがよい。主成分とは８０ｗｔ％以上、好ましくは９０ｗｔ％以上、より好ましくは実質的に全部であることをいう。一般式（１）において、Ｒ1は水素原子又は炭素数１〜６の炭化水素基、好ましくは水素原子又は炭素数１〜４のアルキル基を示す。In the general formula (1), n represents a number of 1 to 5, preferably in the range of 1.9 to 3.4 as an average (number average). More preferably, it is in the range of 2.0 to 3.0, but it is necessary to satisfy the above dispersion. From another viewpoint, it is preferable that a component having n of 1 to 5 is a main component. The main component means 80 wt% or more, preferably 90 wt% or more, more preferably substantially all. In the general formula (1), R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
次に、本発明のＳｔＰＮの製造方法について説明する。本発明のＳｔＰＮを製造する方法で用いる一般式（１）で表わされる多価ヒドロキシ化合物としては、フェノールノボラック類が適する。フェノールノボラック類は、フェノール類とアルデヒド類から得ることができる。 Next, the manufacturing method of StPN of this invention is demonstrated. Phenol novolacs are suitable as the polyvalent hydroxy compound represented by the general formula (1) used in the method for producing StPN of the present invention. Phenol novolacs can be obtained from phenols and aldehydes.
この多価ヒドロキシ化合物を得るために用いられるフェノール類としては、主としてフェノールである。このフェノール類は少量他のフェノール成分を含んでもよい。例えば、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、エチルフェノール類、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などが挙げられる。これらのフェノール類単独でもよいし、２種以上を併用してもよい。なお、少量であれば、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等の他のフェノール類又はナフトール類を配合することができる。これらを配合する場合は、３０ｗｔ％以下、好ましくは２０ｗｔ％以下にとどめることがよい。 Phenols used to obtain this polyvalent hydroxy compound are mainly phenol. These phenols may contain small amounts of other phenol components. Examples include o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tertiary butylphenols, allylphenols, phenylphenols and the like. These phenols may be used alone or in combination of two or more. In a small amount, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1, Other phenols or naphthols such as 7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol can be blended. In the case of blending these, it is preferable to keep it at 30 wt% or less, preferably 20 wt% or less.
多価ヒドロキシ化合物との反応に用いるアラルキル化剤は、上記式（ｃ1）又は（ｃ2）で表わされる化合物が使用される。式（ｃ1）で表わされる化合物をスチレン類という。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。式（ｃ1）において、Ｒ3は水素又は炭素数１〜６のアルキル基であるが、好ましくは水素である。このスチレン類は少量の他の反応成分を含んでもよく、他の反応成分としては、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があげられる。これらを配合する場合は、３０ｗｔ％以下、好ましくは２０ｗｔ％以下にとどめることがよい。As the aralkylating agent used for the reaction with the polyvalent hydroxy compound, a compound represented by the above formula (c1) or (c2) is used. The compound represented by the formula (c1) is called styrenes. Styrenes are styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms. In the formula (c1), R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms, preferably hydrogen. These styrenes may contain a small amount of other reaction components, and examples of other reaction components include unsaturated bond-containing components such as divinylbenzene, indene, coumarone, benzothiophene, indole, and vinylnaphthalene. In the case of blending these, it is preferable to keep it at 30 wt% or less, preferably 20 wt% or less.
上記式（ｃ2）において、Ｒ2、Ｒ3およびＲ4は、式（a）のＲ2、Ｒ3およびＲ4と同意である。Ｘはハロゲン原子、炭素数１〜６のアルコキシ基、又は水酸基である。式（ｃ1）において、Ｒ2、Ｒ3は、式（a）のＲ2、Ｒ3と同意である。In the above formula (c2), R 2, R 3 and R 4 are the same meaning as R 2, R 3 and R 4 of formula (a). X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group. In the formula (c1), R 2, R 3 are same meaning as R 2, R 3 of formula (a).
上記式（ｃ2）で表されるアラルキル化剤としては、Ｘがハロゲン原子の場合、ベンジルクロライド、ベンジルブロマイド、ベンジルアイオダイト、ｏ−メチルベンジルクロライド、ｍ−メチルベンジルクロライド、ｐ−メチルベンジルクロライド、ｐ−エチルベンジルクロライド、ｐ−イソプロピルベンジルクロライド、ｐ−ｔｅｒｔ−ブチルベンジルクロライド、ｐ−シクロヘキシルベンジルクロライド、ｐ−フェニルベンジルクロライド、α−メチルベンジルクロライド、α ，α−ジメチルベンジルクロライド等が挙げられ、Ｘがアルコキシ基の場合、炭素数１〜４のアルコキシ基であることが好ましく、ベンジルメチルエーテル、ｏ−メチルベンジルメチルエーテル、ｍ− メチルベンジルメチルエーテル、ｐ−メチルベンジルメチルエーテル、ｐ−エチルベンジルメチルエーテル、ベンジルエチルエーテル、ベンジルイソプロピルエーテル、ベンジルｎ−プロピルエーテル、ベンジルイソブチルエーテル、ベンジルｎ−ブチルエーテル、ｐ−メチルベンジルメチルエーテル等が挙げられ、Ｘが水酸基の場合、ベンジルアルコール、ｏ−メチルベンジルアルコール、ｍ −メチルベンジルアルコール、ｐ−メチルベンジルアルコール、ｐ−エチルベンジルアルコール、ｐ−イソプロピルベンジルアルコール、ｐ−ｔｅｒｔ−ブチルベンジルアルコール、ｐ−シクロヘキシルベンジルアルコール、ｐ−フェニルベンジルアルコール、α−メチルベンジルアルコール、α，α−ジメチルベンジルアルコール等が挙げられる。式（ｃ1）で表されるアラルキル化剤としては、スチレン、スチレンのベンゼン環にＣ1〜6のアルキル基が置換したアルキルスチレン、α-アルキルスチレン類等が挙げられるが、好ましくはアルキルスチレンまたはスチレンであり、より好ましくはスチレンである。
As the aralkylating agent represented by the above formula (c2), when X is a halogen atom, benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl chloride, p-cyclohexylbenzyl chloride, p-phenylbenzyl chloride, α-methylbenzyl chloride,
アラルキル化剤によるアラルキル化反応は酸触媒の存在下に行うことができ、その触媒量は１０〜１０００ｐｐｍ（ｗｔ）の範囲で用いられ、好ましくは１００〜５００ｐｐｍの範囲である。これより多いと多価ヒドロキシ化合物のメチレン架橋結合が開裂し易くなり、開列反応により副生した単価フェノール成分により、硬化性および耐熱性を低下させる。一方、これより少ないと反応性が低下し、未反応アラルキル化剤を多く残存させる。また、ここでいう触媒量とは反応に用いる多価ヒドロキシ化合物およびアラルキル化剤の合計重量に対する触媒の量を意味する。 The aralkylation reaction with an aralkylating agent can be performed in the presence of an acid catalyst, and the amount of the catalyst is used in the range of 10 to 1000 ppm (wt), preferably in the range of 100 to 500 ppm. If it is more than this, the methylene cross-linking bond of the polyvalent hydroxy compound will be easily cleaved, and the curability and heat resistance will be lowered by the unit price phenol component by-produced by the row opening reaction. On the other hand, if the amount is less than this, the reactivity is lowered and a large amount of unreacted aralkylating agent remains. Moreover, the catalyst amount here means the amount of the catalyst with respect to the total weight of the polyvalent hydroxy compound and the aralkylating agent used in the reaction.
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。 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、この反応における反応温度は４０〜１２０℃の範囲で行われる。これより低いと、反応性が低下し反応時間が長時間となる。また、これより高いと多価ヒドロキシ化合物のメチレン架橋結合が一部開裂し易くなり、開列反応により副生した単価フェノール成分により、硬化性および耐熱性を低下させる。 Moreover, the reaction temperature in this reaction is performed in the range of 40-120 degreeC. If it is lower than this, the reactivity is lowered and the reaction time is prolonged. On the other hand, if it is higher than this, a part of the methylene cross-linked bond of the polyvalent hydroxy compound is easily cleaved, and the curability and heat resistance are lowered by the unit price phenol component by-produced by the row opening reaction.
また、この反応は通常、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 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、アラルキル化剤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樹脂を得ることができ、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 aralkylating. A method of reacting while dropping the agent is common. 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 resin 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(ＳｔＰＮＥ)について述べる。
本発明のエポキシ樹脂(ＳｔＰＮＥ)はＳｔＰＮ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 (StPNE) of the present invention will be described.
The epoxy resin (StPNE) of the present invention can be obtained by epoxidizing StPN.
本発明のＳｔＰＮＥは、上記ＳｔＰＮ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。ＳｔＰＮ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。 The StPNE of the present invention is advantageously produced by reacting the above StPN with epichlorohydrin. The reaction of reacting StPN with epichlorohydrin can be performed in the same manner as a normal epoxidation reaction.
例えば、上記ＳｔＰＮ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、ＳｔＰＮ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ＳｔＰＮ中の水酸基１モルに対して過剰に用いられるが、通常、ＳｔＰＮ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 StPN is dissolved in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, it is 20 to 150 ° C., preferably 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 StPN hydroxyl group. In addition, epichlorohydrin is used in excess with respect to 1 mol of hydroxyl group in StPN, but is usually in the range of 1.5 to 30 mol, preferably 2 to 15 mol, relative to 1 mol of hydroxyl group in StPN. 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ＳｔＰＮＥを配合した組成物。
２）硬化剤の一部又は全部として前記ＳｔＰＮ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ＳｔＰＮＥとＳｔＰＮ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 StPNE as a part or all of an epoxy resin.
2) The composition which mix | blended the said StPN as a part or all of a hardening | curing agent.
3) The composition which mix | blended the said StPNE and StPN 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、ＳｔＰＮを必須の成分として含む。ＳｔＰＮの配合量は、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), StPN is included as an essential component. The blending amount of StPN 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ＳｔＰＮを用いる場合、通常、ＳｔＰＮの配合量は、ＳｔＰＮ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 StPN is used as the total amount of the curing agent, the amount of StPN is usually determined in consideration of the equivalent balance of the OH group of StPN 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ＳｔＰＮ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、ＳｔＰＮ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。ＳｔＰＮ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 StPN 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 StPN 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. . When the blending amount of StPN is less than this, the effect of improving low hygroscopicity, adhesion and flame retardancy is small, and when it is more than this, there is a problem that moldability and 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.
ＳｔＰＮ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。本発明のＳｔＰＮを必須成分とする組成物の場合、ＳｔＰＮの配合量は硬化剤全体中、５０〜１００％、好ましくは６０〜１００％の範囲であることがよい。以下に、ＳｔＰＮ以外の硬化剤の具体例を示す。 As the curing agent other than StPN, any of those generally known as epoxy resin curing agents can be used, and examples thereof 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. In the case of the composition containing StPN of the present invention as an essential component, the blending amount of StPN is 50 to 100%, preferably 60 to 100% in the entire curing agent. Below, the specific example of hardening | curing agents other than StPN 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、ト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 triethylenetetramine.
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）の組成物の場合、ＳｔＰＮＥ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、ＳｔＰＮＥ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ＳｔＰＮＥを必須成分とする組成物の場合、ＳｔＰＮＥの配合量はエポキシ樹脂全体中、５０〜１００％、好ましくは６０〜１００％の範囲であることがよい。 In the case of the above compositions 1) and 3), StPNE is included as an essential component. In this epoxy resin composition, you may mix | blend another kind of epoxy resin other than StPNE 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 StPNE of this invention as an essential component, the compounding quantity of StPNE is 50-100% 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, and 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, and the like, 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。水酸基当量およびエポキシ当量の単位はｇ／ｅｑ．である。 Hereinafter, the present invention will be described more specifically with reference to examples. The unit of hydroxyl equivalent and epoxy equivalent is g / eq. It is.
合成例１
１Ｌの４口フラスコに、フェノールを２５０ｇ、酸触媒としてシュウ酸二水和物０．７５ｇを仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。３７．４％ホルマリン４７．４ｇを８０℃で滴下を開始し、３０分で滴下を終了した。更に反応温度を９２℃に保ち３時間反応を行った。昇温を行い反応生成水を系外に除去しながら１１０℃まで昇温した。残存フェノールを１６０℃にて減圧下回収を行った。更に温度を上げて二核体の一部を回収した。得られた多価ヒドロキシ化合物の水酸基当量は１０４、軟化点は６８℃、１５０℃での溶融粘度は０．０７Ｐａ・ｓであった。ＧＰＣ測定によるｎ＝１成分の含有率は８．１％、ｎ＝２及びｎ＝３成分の合計の含有率は７１．７％、Ｍｗ／Ｍｎ＝１．１０であった。この樹脂を多価ヒドロキシ化合物Ａという。多価ヒドロキシ化合物ＡのＧＰＣチャートを図１に示す。Synthesis example 1
A 1 L 4-neck flask was charged with 250 g of phenol and 0.75 g of oxalic acid dihydrate as an acid catalyst, stirred while introducing nitrogen gas, heated and heated. Addition of 47.4 g of 37.4% formalin was started at 80 ° C., and the addition was completed in 30 minutes. Further, the reaction was carried out for 3 hours while maintaining the reaction temperature at 92 ° C. The temperature was raised to 110 ° C. while removing the reaction product water out of the system. The residual phenol was collected at 160 ° C. under reduced pressure. The temperature was further raised to recover a part of the binuclear body. The obtained polyvalent hydroxy compound had a hydroxyl group equivalent of 104, a softening point of 68 ° C., and a melt viscosity at 150 ° C. of 0.07 Pa · s. The content of n = 1 component by GPC measurement was 8.1%, and the total content of n = 2 and n = 3 components was 71.7%, and Mw / Mn = 1.10. This resin is referred to as polyvalent hydroxy compound A. A GPC chart of the polyvalent hydroxy compound A is shown in FIG.
合成例２
１Ｌの４口フラスコに、フェノールを２５０ｇ、７．４％ホルマリン４７．４ｇ、酸触媒として８９％リン酸１５０ｇを仕込み、攪拌混合により形成される白濁状態（２相混合物）のもとで加熱を行って昇温した。更に還流温度に保ち６時間反応を行った。次いで、メチルイソブチルケトンを添加して樹脂分を溶解させた後静置し、樹脂溶液相とリン酸水溶液相に分離させた。リン酸溶液相を除去した後更に水洗を行った。次いで、残存フェノールを１６０℃にて減圧下回収を行った。更に温度を上げて二核体の一部を回収した。得られた多価ヒドロキシ化合物の水酸基当量は１０３、軟化点は６５℃、１５０℃での溶融粘度は０．０６Ｐａ・ｓであった。ＧＰＣ測定によるｎ＝１成分の含有率は２．０％、ｎ＝２及びｎ＝３成分の合計の含有率は９１．５％、Ｍｗ／Ｍｎ＝１．０４であった。この樹脂を多価ヒドロキシ化合物Ｂという。多価ヒドロキシ化合物ＢのＧＰＣチャートを図２に示す。Synthesis example 2
A 1 L 4-neck flask is charged with 250 g of phenol, 47.4 g of 7.4% formalin, and 150 g of 89% phosphoric acid as an acid catalyst, and heated under a cloudy state (two-phase mixture) formed by stirring and mixing. Went and warmed up. The reaction was further continued for 6 hours while maintaining the reflux temperature. Next, methyl isobutyl ketone was added to dissolve the resin component, and then allowed to stand to separate into a resin solution phase and a phosphoric acid aqueous solution phase. After removing the phosphoric acid solution phase, washing with water was further performed. Subsequently, the residual phenol was collected at 160 ° C. under reduced pressure. The temperature was further raised to recover a part of the binuclear body. The obtained polyvalent hydroxy compound had a hydroxyl group equivalent of 103, a softening point of 65 ° C., and a melt viscosity at 150 ° C. of 0.06 Pa · s. The content of n = 1 component by GPC measurement was 2.0%, and the total content of n = 2 and n = 3 components was 91.5% and Mw / Mn = 1.04. This resin is referred to as polyvalent hydroxy compound B. A GPC chart of the polyvalent hydroxy compound B is shown in FIG.
実施例１
１Ｌの４口フラスコに、多価ヒドロキシ化合物成分として、合成例１で得られた多価ヒドロキシ化合物Ａを１０４ｇ、酸触媒としてｐ−トルエンスルホン酸０．０５３ｇ（３００ｐｐｍ）を仕込み１２０℃に昇温した。次に、１２０℃にて攪拌しながら、スチレン７２．８ｇ（０．７モル）を３時間かけて滴下し反応させた。さらに、１２０℃にて１時間反応後、スチレン変性多価ヒドロキシ樹脂１６８ｇを得た。その水酸基当量は１７７、軟化点は７８℃、１５０℃での溶融粘度は０．１３Ｐａ・ｓであった。この樹脂を変性多価ヒドロキシ樹脂Ａ（ＳｔＰＮ−Ａ）という。ＳｔＰＮ−ＡのＧＰＣチャートを図４に示す。Example 1
A 1 L 4-necked flask was charged with 104 g of the polyvalent hydroxy compound A obtained in Synthesis Example 1 as a polyvalent hydroxy compound component and 0.053 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst, and the temperature was raised to 120 ° C. did. Next, while stirring at 120 ° C., 72.8 g (0.7 mol) of styrene was dropped over 3 hours to be reacted. Furthermore, after reacting at 120 ° C. for 1 hour, 168 g of a styrene-modified polyvalent hydroxy resin was obtained. The hydroxyl equivalent was 177, the softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.13 Pa · s. This resin is referred to as modified polyvalent hydroxy resin A (StPN-A). A GPC chart of StPN-A is shown in FIG.
実施例２
１Ｌの４口フラスコに、多価ヒドロキシ化合物成分として、合成例２で得られた多価ヒドロキシ化合物Ｂを１０３ｇ、酸触媒としてｐ−トルエンスルホン酸０．０５３ｇ（３００ｐｐｍ）を仕込み１２０℃に昇温した。次に、１２０℃にて攪拌しながら、スチレン７２．８ｇ（０．７モル）を３時間かけて滴下し反応させた。さらに、１２０℃にて１時間反応後、アラルキルスチレン変性多価ヒドロキシ樹脂１６７ｇを得た。その水酸基当量は１７６、軟化点は７８℃、１５０℃での溶融粘度は０．１３Ｐａ・ｓであった。この樹脂を変性多価ヒドロキシ樹脂Ｂ（ＳｔＰＮ−Ｂ）という。ＳｔＰＮ−ＢのＧＰＣチャートを図５に示す。Example 2
A 1 L 4-necked flask was charged with 103 g of the polyvalent hydroxy compound B obtained in Synthesis Example 2 as a polyvalent hydroxy compound component and 0.053 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst, and the temperature was raised to 120 ° C. did. Next, while stirring at 120 ° C., 72.8 g (0.7 mol) of styrene was dropped over 3 hours to be reacted. Furthermore, after reacting at 120 ° C. for 1 hour, 167 g of an aralkylstyrene-modified polyvalent hydroxy resin was obtained. The hydroxyl equivalent was 176, the softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.13 Pa · s. This resin is called modified polyvalent hydroxy resin B (StPN-B). A GPC chart of StPN-B is shown in FIG.
実施例３
１Ｌの４口フラスコに、多価ヒドロキシ化合物成分として、合成例１で得られた多価ヒドロキシ化合物Ａを１０４ｇ、水１．０ｇを仕込み１２０℃に昇温した。次に、１２０℃にて攪拌しながら、塩化ベンジル８８．６ｇ（０．７モル）を３時間かけて滴下し反応させた。さらに、１２０℃にて１時間反応後、ベンジル変性多価ヒドロキシ樹脂１６０ｇを得た。その水酸基当量は１６８、軟化点は７０℃、１５０℃での溶融粘度は０．０９Ｐａ・ｓであった。この樹脂を変性多価ヒドロキシ樹脂Ｃ（ＳｔＰＮ−Ｃ）という。ＳｔＰＮ−ＣのＧＰＣチャートを図６に示す。Example 3
In a 1 L four-necked flask, 104 g of polyvalent hydroxy compound A obtained in Synthesis Example 1 and 1.0 g of water were charged as a polyvalent hydroxy compound component, and the temperature was raised to 120 ° C. Next, while stirring at 120 ° C., 88.6 g (0.7 mol) of benzyl chloride was dropped over 3 hours to be reacted. Furthermore, after reacting at 120 ° C. for 1 hour, 160 g of a benzyl-modified polyvalent hydroxy resin was obtained. The hydroxyl equivalent was 168, the softening point was 70 ° C., and the melt viscosity at 150 ° C. was 0.09 Pa · s. This resin is referred to as modified polyvalent hydroxy resin C (StPN-C). A GPC chart of StPN-C is shown in FIG.
比較例１
１Ｌの４口フラスコに、多価ヒドロキシ化合物成分としてフェノールノボラック（昭和電工製；ＢＲＧ−５５５（多価ヒドロキシ化合物Ｃともいい、図３にＧＰＣチャートを示す。）、ＧＰＣ測定によるｎ＝１成分の含有率；２５．４％、ｎ＝２及びｎ＝３成分の合計の含有率；３２．１％、Ｍｗ／Ｍｎ＝１．４５、水酸基当量１０５、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０．０５５ｇ（３００ｐｐｍ）を仕込み１２０℃に昇温した。次に、１２０℃にて攪拌しながら、スチレン７３ｇ（０．７モル）を３時間かけて滴下し反応させた。さらに、１２０℃にて１時間反応後、スチレン変性多価ヒドロキシ樹脂１７０ｇを得た。その水酸基当量は１７８、軟化点は７８℃、１５０℃での溶融粘度は０．１３Ｐａ・ｓであった。この樹脂を変性多価ヒドロキシ樹脂Ｄ（ＳｔＰＮ−Ｄ）という。ＳｔＰＮ−ＤのＧＰＣチャートを図７に示す。Comparative Example 1
In a 1 L 4-neck flask, phenol novolac (manufactured by Showa Denko; BRG-555 (also referred to as polyvalent hydroxy compound C, GPC chart shown in FIG. 3)) as a polyvalent hydroxy compound component, n = 1 component by GPC measurement Content: 25.4%, total content of n = 2 and n = 3 components; 32.1%, Mw / Mn = 1.45, hydroxyl equivalent 105, softening point 67 ° C., melt viscosity at 150 ° C. 0.08 Pa · s) was charged with 105 g, and 0.055 g (300 ppm) of p-toluenesulfonic acid was charged as an acid catalyst, and the temperature was raised to 120 ° C. Next, with stirring at 120 ° C., 73 g (0.7 mol) of styrene was dropped over 3 hours to be reacted. Furthermore, after reacting at 120 ° C. for 1 hour, 170 g of a styrene-modified polyvalent hydroxy resin was obtained. The hydroxyl equivalent was 178, the softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.13 Pa · s. This resin is referred to as modified polyvalent hydroxy resin D (StPN-D). A GPC chart of StPN-D is shown in FIG.
実施例４
四つ口セパラブルフラスコに実施例１で得たＳｔＰＮ−Ａ１５０ｇ、エピクロルヒドリン４７０ｇ、ジエチレングリコールジメチルエーテル７１ｇ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７０．６ｇ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Ａ（ＳｔＰＮＥ−Ａ）１６８ｇを得た。得られた樹脂のエポキシ当量は２４１、軟化点は５６℃、１５０℃における溶融粘度は０．１２Ｐａ・ｓであった。ＳｔＰＮＥ−ＡのＧＰＣチャートを図８に示す。Example 4
In a four-necked separable flask, 150 g of StPN-A obtained in Example 1, 470 g of epichlorohydrin and 71 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, 70.6 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water and epichlorohydrin refluxed 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 168 g of epoxy resin A (StPNE-A). The epoxy equivalent of the obtained resin was 241, the softening point was 56 ° C., and the melt viscosity at 150 ° C. was 0.12 Pa · s. A GPC chart of StPNE-A is shown in FIG.
実施例５
四つ口セパラブルフラスコに実施例２で得たＳｔＰＮ−Ｂ１５０ｇ、エピクロルヒドリン４７３ｇ、ジエチレングリコールジメチルエーテル７１ｇ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７１．０ｇ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Ｂ（ＳｔＰＮＥ−Ｂ）１６５ｇを得た。得られた樹脂のエポキシ当量は２４５、軟化点は５５℃、１５０℃における溶融粘度は０．１１Ｐａ・ｓであった。ＳｔＰＮＥ−ＢのＧＰＣチャートを図９に示す。Example 5
In a four-neck separable flask, 150 g of StPN-B obtained in Example 2, 473 g of epichlorohydrin, and 71 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, 71.0 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and water and epichlorohydrin distilled under reflux were separated in the dropping 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 165 g of epoxy resin B (StPNE-B). The epoxy equivalent of the obtained resin was 245, the softening point was 55 ° C., and the melt viscosity at 150 ° C. was 0.11 Pa · s. A GPC chart of StPNE-B is shown in FIG.
実施例６
四つ口セパラブルフラスコに実施例３で得たＳｔＰＮ−Ｃ１５０ｇ、エピクロルヒドリン４９５ｇ、ジエチレングリコールジメチルエーテル７４ｇ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７４．４ｇ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Ｃ（ＳｔＰＮＥ−Ｃ）１８５ｇを得た。得られた樹脂のエポキシ当量は２３６、軟化点は５２℃、１５０℃における溶融粘度は０．０８Ｐａ・ｓであった。ＳｔＰＮＥ−ＣのＧＰＣチャートを図１０に示す。Example 6
In a four-neck separable flask, 150 g of StPN-C obtained in Example 3, 495 g of epichlorohydrin, and 74 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, 74.4 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 185 g of epoxy resin C (StPNE-C). The epoxy equivalent of the obtained resin was 236, the softening point was 52 ° C., and the melt viscosity at 150 ° C. was 0.08 Pa · s. A GPC chart of StPNE-C is shown in FIG.
比較例２
四つ口セパラブルフラスコに比較例１で得たＳｔＰＮ−Ｄ１５０ｇ、エピクロルヒドリン４６８ｇ、ジエチレングリコールジメチルエーテル７０ｇ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７０．３ｇ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１８５ｇを得た（ＳｔＰＮＥ−Ｄ）。得られた樹脂のエポキシ当量は２４６、軟化点は５６℃、１５０℃における溶融粘度は０．１０Ｐａ・ｓであった。ＳｔＰＮＥ−ＤのＧＰＣチャートを図１１に示す。Comparative Example 2
In a four-necked separable flask, 150 g of StPN-D obtained in Comparative Example 1, 468 g of epichlorohydrin, and 70 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, 70.3 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the 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 185 g of an epoxy resin (StPNE-D). The epoxy equivalent of the obtained resin was 246, the softening point was 56 ° C., and the melt viscosity at 150 ° C. was 0.10 Pa · s. A GPC chart of StPNE-D is shown in FIG.
実施例７〜９及び例１０〜１１（比較）
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ＳｔＰＮ−Ａ、実施例２で得たＳｔＰＮ−Ｂ、実施例３で得たＳｔＰＮ−Ｃ、比較例１で得たＳｔＰＮ−Ｄの他、フェノールノボラック（ＰＮ；ＰＳＭ−４２６１（群栄化学工業製）；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。詳細を次に示し、結果を表２に示す。Examples 7-9 and Examples 10-11 (comparison)
Using an o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) as an epoxy resin component, StPN-A obtained in Example 1 and StPN-B obtained in Example 2 as a curing agent, In addition to StPN-C obtained in Example 3 and StPN-D obtained in Comparative Example 1, phenol novolak (PN; PSM-4261 (manufactured by Gunei Chemical Industry); 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. Details are shown below, and the results are shown in Table 2.
１）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定
東ソー株式会社製 ＴＳＫｇｅｌＧ４０００ＨＸＬ、ＴＳＫｇｅｌＧ３０００ＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬを直列に備えたものを使用し、カラム温度は４０℃にした。また、溶離液にはテトラヒドロフランを用い、１ｍｌ／ｍｉｎの流速とし、検出器はＲＩ（示差屈折計）検出器を用いた。サンプル０．１ｇを１０ｍｌのＴＨＦに溶解した。標準ポリスチレンによる検量線により重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）を求めた後、分散度（Ｍｗ／Ｍｎ）を求めた。1) Gel permeation chromatography (GPC) measurement Tosoh Corporation TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL were used in series, and the column temperature was 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector. 0.1 g of sample was dissolved in 10 ml of THF. After determining the weight average molecular weight (Mw) and the number average molecular weight (Mn) by a calibration curve using standard polystyrene, the degree of dispersion (Mw / Mn) was determined.
２）軟化点
自動軟化点測定装置（明峰社製、ＡＳＰ−Ｍ４ＳＰ）を用い、ＪＩＳ−Ｋ−２２０７に従い環球法にて測定した。2) Softening point It measured with the ring and ball method according to JIS-K-2207 using the automatic softening point measuring apparatus (Akemine company make, ASP-M4SP).
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）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。6) 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 at a rate of 2 revolutions per second using a fluororesin rod. The gelation time required for stirring and curing of the epoxy resin composition was examined.
７）熱時硬度
金型温度１７５℃、硬化時間９０秒で成形し、型開き１０秒後にショアＤ硬度計を用いて測定したショアＤ硬度の値を熱時硬度とした。7) Hot hardness Hardness at the mold temperature of 175 ° C. and curing time of 90 seconds, and the Shore D hardness measured using a Shore D hardness meter 10 seconds after mold opening was defined as hot hardness.
８）ガラス転移点（Ｔｇ）、線膨張係数（ＣＴＥ）
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。8) Glass transition point (Tg), linear expansion coefficient (CTE)
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.
９）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。9) Bending strength and bending elasticity According to JISK6911, it measured at normal temperature by the three-point bending test method.
１０）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。10) Water absorption rate The conditions of 25 ° C. and 50% relative humidity were taken as the standard state, and the weight change rate after 100 hours of moisture absorption at 85 ° C. and 85% relative humidity.
１１）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。11) 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１２〜１４及び例１５〜１６（比較）
エポキシ樹脂成分として、実施例４で得たＳｔＰＮＥ−Ａ、実施例５で得たＳｔＰＮＥ−Ｂ、実施例６で得たＳｔＰＮＥ−Ｃ、比較例２で得たＳｔＰＮＥ−Ｄ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℃）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 12-14 and Examples 15-16 (comparison)
As epoxy resin components, StPNE-A obtained in Example 4, StPNE-B obtained in Example 5, StPNE-C obtained in Example 6, StPNE-D obtained in Comparative Example 2, and o-cresol A novolak type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) is used, and a phenol aralkyl resin (PA; MEH-7800SS (Maywa Kasei), OH equivalent 175, softening point 67 ° C.) is used as a curing agent component. It was. 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.
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、硬化性及び機械的物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 and mechanical properties, and also excellent in flame retardancy, moisture resistance, and low elasticity. -It can be suitably used for applications such as sealing electronic parts 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.
Claims (9)
で表される多価ヒドロキシ化合物と、アラルキル化剤とを反応させて、式（ａ）で表されるアラルキル化剤由来の置換基を多価ヒドロキシ化合物のベンゼン環に置換させ、アラルキル変性多価ヒドロキシ樹脂とするに当たり、一般式（１）で表される多価ヒドロキシ化合物として、ゲルパーミエーションクロマトグラフィーで測定した面積％でｎ＝１成分が２％以下であり、ｎ＝２及びｎ＝３成分の合計が７０％以上であり、Ｍｗ／Ｍｎが１．１以下である狭分散多価ヒドロキシ化合物を使用することを特徴とするアラルキル変性多価ヒドロキシ樹脂の製造方法。 The following general formula (1)
The aralkylating agent represented by formula (a) is substituted with the benzene ring of the polyhydric hydroxy compound, and the aralkyl-modified polyvalent compound is reacted with the aralkylating agent represented by formula (a). In making the hydroxy resin , as the polyvalent hydroxy compound represented by the general formula (1), n = 1 component is 2% or less in area% measured by gel permeation chromatography, n = 2 and n = 3 A method for producing an aralkyl-modified polyvalent hydroxy resin , comprising using a narrowly dispersed polyvalent hydroxy compound having a total of 70% or more and Mw / Mn of 1.1 or less.
で表されるアラルキル化剤を使用し、１０〜１０００ｐｐｍの酸触媒の存在下、反応温度４０〜１２０℃で反応させることを特徴とする請求項１に記載のアラルキル変性多価ヒドロキシ樹脂の製造方法。 As the aralkylating agent, the following formula (c1) or (c2)
The method for producing an aralkyl-modified polyvalent hydroxy resin according to claim 1 , wherein the reaction is carried out at a reaction temperature of 40 to 120 ° C. in the presence of 10 to 1000 ppm of an acid catalyst. .
An epoxy resin composition is obtained by the method for producing an epoxy resin composition according to claim 8, and this is cured, thereby producing a cured epoxy resin product .
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| JP2012037210 | 2012-02-23 | ||
| PCT/JP2013/054278 WO2013125620A1 (en) | 2012-02-23 | 2013-02-21 | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof |
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| TWI595019B (en) * | 2012-11-12 | 2017-08-11 | Ｄｉｃ股份有限公司 | Phenolic hydroxyl group-containing resin, epoxy resin, curable resin composition,cured product thereof and semiconductor encapsulating material |
| JP6406847B2 (en) * | 2014-03-26 | 2018-10-17 | 新日鉄住金化学株式会社 | Modified polyvalent hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof |
| CN109071780B (en) * | 2016-04-28 | 2022-04-08 | 昭和电工材料株式会社 | Epoxy resin composition and electronic component device |
| JP7142233B2 (en) * | 2017-12-14 | 2022-09-27 | パナソニックＩｐマネジメント株式会社 | EPOXY RESIN COMPOSITION FOR ENCAPSULATION, CURED PRODUCT AND SEMICONDUCTOR DEVICE |
| TWI751064B (en) * | 2021-03-29 | 2021-12-21 | 長春人造樹脂廠股份有限公司 | Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof |
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| JPS4852895A (en) | 1971-11-05 | 1973-07-25 | ||
| JPS62119220A (en) * | 1985-11-18 | 1987-05-30 | Arakawa Chem Ind Co Ltd | Production of polyhydroxyl compound |
| JPH0356526A (en) * | 1989-07-25 | 1991-03-12 | Denki Kagaku Kogyo Kk | Epoxy resin composition for sealing semiconductor |
| JP3196141B2 (en) * | 1991-11-14 | 2001-08-06 | 東都化成株式会社 | Epoxy resin composition |
| JP3146320B2 (en) | 1991-11-18 | 2001-03-12 | 東都化成株式会社 | Epoxy resin composition |
| EP0549968A1 (en) * | 1991-12-20 | 1993-07-07 | Hoechst Aktiengesellschaft | Surface-active compounds based on modified oxalkylated novolaks, their preparation and their application |
| JPH06128183A (en) * | 1992-02-27 | 1994-05-10 | Mitsui Toatsu Chem Inc | Method for simultaneous production of bisphenol f and novolak type phenolic resin |
| JP3587570B2 (en) * | 1994-10-20 | 2004-11-10 | 三井化学株式会社 | Benzylated polyphenols, their epoxy resins, their production methods and uses |
| JP3579800B2 (en) * | 1994-12-14 | 2004-10-20 | 東都化成株式会社 | Low dielectric epoxy resin composition |
| JPH10158352A (en) * | 1996-11-28 | 1998-06-16 | Dainippon Ink & Chem Inc | Production of phenol resin |
| JPH11140166A (en) | 1997-11-11 | 1999-05-25 | Shin Etsu Chem Co Ltd | Epoxy resin composition for semiconductor sealing and semiconductor device |
| JP3349963B2 (en) | 1998-10-21 | 2002-11-25 | 日本電気株式会社 | Flame-retardant epoxy resin composition and semiconductor device using the same |
| JP2000273280A (en) * | 1999-03-26 | 2000-10-03 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP4188022B2 (en) | 2002-07-30 | 2008-11-26 | 新日鐵化学株式会社 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product using them |
| JP2004067968A (en) | 2002-08-09 | 2004-03-04 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg, and laminated plate |
| JP2004323630A (en) | 2003-04-23 | 2004-11-18 | Lignyte Co Ltd | Preparation method for phenol resin |
| JP2005344081A (en) | 2004-06-07 | 2005-12-15 | Nippon Steel Chem Co Ltd | Epoxy resin composition and cured product thereof |
| JP2008106219A (en) * | 2006-03-29 | 2008-05-08 | Sumitomo Bakelite Co Ltd | Method for producing phenol resin |
| JP5228328B2 (en) * | 2007-02-01 | 2013-07-03 | 宇部興産株式会社 | Low melt viscosity phenol novolac resin, process for producing the same, and cured epoxy resin using the same |
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| JP5462559B2 (en) * | 2009-09-08 | 2014-04-02 | 新日鉄住金化学株式会社 | Polyvalent hydroxy compounds, production method thereof, epoxy resin composition and cured product thereof |
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| TW201345958A (en) | 2013-11-16 |
| CN104334597B (en) | 2016-06-22 |
| TWI548681B (en) | 2016-09-11 |
| WO2013125620A1 (en) | 2013-08-29 |
| JPWO2013125620A1 (en) | 2015-07-30 |
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