JP6113454B2 - Epoxy resin composition and cured product - Google Patents
Epoxy resin composition and cured product Download PDFInfo
- Publication number
- JP6113454B2 JP6113454B2 JP2012225828A JP2012225828A JP6113454B2 JP 6113454 B2 JP6113454 B2 JP 6113454B2 JP 2012225828 A JP2012225828 A JP 2012225828A JP 2012225828 A JP2012225828 A JP 2012225828A JP 6113454 B2 JP6113454 B2 JP 6113454B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- phosphorus
- epoxy
- general formula
- resin composition
- 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 175
- 229920000647 polyepoxide Polymers 0.000 title claims description 175
- 239000000203 mixture Substances 0.000 title claims description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims description 81
- 239000011574 phosphorus Substances 0.000 claims description 72
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 56
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 239000004593 Epoxy Substances 0.000 claims description 34
- -1 phosphorus compound Chemical class 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000004437 phosphorous atom Chemical group 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000001723 curing Methods 0.000 description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 19
- 239000010959 steel Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 150000002440 hydroxy compounds Chemical class 0.000 description 17
- 229920003986 novolac Polymers 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 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 14
- 125000000524 functional group Chemical group 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 150000003440 styrenes Chemical class 0.000 description 13
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 12
- 150000002989 phenols Chemical class 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 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 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-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
- 229930185605 Bisphenol Natural products 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 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
- 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
- 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 compound 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 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 238000002835 absorbance Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- UXMYUFHUUYBDLL-UHFFFAOYSA-N 2,2-dimethyl-3-(oxiran-2-ylmethoxy)propan-1-ol Chemical compound OCC(C)(C)COCC1CO1 UXMYUFHUUYBDLL-UHFFFAOYSA-N 0.000 description 1
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical class CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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- 238000009499 grossing Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Epoxy Resins (AREA)
Description
本発明は、低誘電性および難燃性に優れるとともに、接着性にも優れた硬化物を与えるエポキシ樹脂組成物及びその硬化物に関するものである。 The present invention relates to an epoxy resin composition that provides a cured product that is excellent in low dielectric properties and flame retardancy, and also has excellent adhesion, and a cured product thereof.
近年、特に先端材料分野の進歩にともない、より高性能なベース樹脂の開発が求められている。例えば、半導体封止の分野においては、近年の高密度実装化に対応したパッケージの薄形化、大面積化、更には表面実装方式の普及により、パッケージクラックの問題が深刻化しており、ベース樹脂には、耐湿性、耐熱性、金属基材との接着性等の向上が強く求められている。また、プリント配線板の分野においては、近年、大量情報を高速処理するために、多層化、薄型化、回路のファインピッチ化等が行われてきた。しかし、更なる高速処理を実現するため、より誘電特性に優れた配線板材料が求められている。更に、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ベース樹脂が求められている。 In recent years, particularly with the advancement of the advanced material field, development of higher performance base resins has been demanded. For example, in the field of semiconductor encapsulation, the problem of package cracking has become serious due to the reduction in the size and area of packages corresponding to recent high-density mounting, and the spread of surface mounting methods. There is a strong demand for improvement in moisture resistance, heat resistance, adhesion to metal substrates, and the like. In the field of printed wiring boards, in recent years, in order to process a large amount of information at high speed, multilayering, thinning, fine pitching of circuits, and the like have been performed. However, in order to realize further high-speed processing, a wiring board material having more excellent dielectric characteristics is required. Furthermore, from the viewpoint of reducing the environmental load, there is a movement to eliminate halogen-based flame retardants, and there is a demand for a base resin that is more excellent in flame retardancy.
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、特許文献１にはリン含有エポキシ樹脂組成物が開示されており、積層板のマトリックス樹脂として応用した場合、絶縁信頼性を低下させることなく優れた難燃性が発現されている。しかし、リン含有エポキシ樹脂においては、リン酸エステル構造に起因した分極した構造をとっており、そのため低誘電性において十分ではなかった。 As a measure for improving flame retardancy without using a halogen-based flame retardant, Patent Document 1 discloses a phosphorus-containing epoxy resin composition, and when applied as a matrix resin of a laminate, insulation reliability is disclosed. Excellent flame retardancy is exhibited without lowering. However, the phosphorus-containing epoxy resin has a polarized structure due to the phosphate ester structure, and thus is not sufficient in low dielectric properties.
これまでに特許文献２にはスチレン化フェノールノボラック型エポキシ樹脂を含有するエポキシ樹脂組成物が開示されているが、低吸水性、低応力性の向上に着目した発明であり、難燃性に着目したものではない。一方、誘電特性の向上に着目した例として、特許文献３には同様なスチレン化フェノールノボラック型エポキシ樹脂を含有するエポキシ樹脂組成物が開示されているが、難燃性と誘電特性とを両立させたものではなかった。 So far, Patent Document 2 discloses an epoxy resin composition containing a styrenated phenol novolac type epoxy resin, but it is an invention that focuses on improving low water absorption and low stress, and focuses on flame retardancy. It was n’t. On the other hand, as an example paying attention to the improvement of dielectric properties, Patent Document 3 discloses an epoxy resin composition containing a similar styrenated phenol novolac type epoxy resin, but it achieves both flame retardancy and dielectric properties. It was not.
さらに、特許文献４にはスチレン変性フェノールノラックエポキシ樹脂とリン含有エポキシ樹脂の含むエポキシ樹脂組成物が開示されており、誘電特性及び難燃性が向上することが開示されているが、難燃性が十分でなかった。 Further, Patent Document 4 discloses an epoxy resin composition containing a styrene-modified phenol nolac epoxy resin and a phosphorus-containing epoxy resin, which discloses that the dielectric properties and flame retardancy are improved. Sex was not enough.
特許文献５にはエポキシ樹脂とスチレン変性フェノールノボラック樹脂を硬化剤として含むエポキシ樹脂組成物が開示されているが、リン含有エポキシ樹脂に関しては検討されておらず、その効果に関して十分な知見は開示されていない。 Patent Document 5 discloses an epoxy resin composition containing an epoxy resin and a styrene-modified phenol novolac resin as a curing agent. However, a phosphorus-containing epoxy resin has not been studied, and sufficient knowledge about its effect is disclosed. Not.
従って、本発明の目的は、非ハロゲンでの難燃性を確保するとともに、低誘電性、難燃性等に優れた性能を有し、積層、成形、注型、接着等の用途に有用なエポキシ樹脂組成物及びその硬化物を提供するものである。 Therefore, the object of the present invention is to ensure non-halogen flame retardancy, and has excellent performance in low dielectric properties, flame retardancy, etc., and is useful for applications such as lamination, molding, casting and adhesion. An epoxy resin composition and a cured product thereof are provided.
すなわち、本発明はエポキシ樹脂、及び硬化剤、又はこれらと充填材を含有するエポキシ樹脂組成物において、エポキシ樹脂成分としてリン含有率が１.０〜５．０重量％であるリン含有エポキシ樹脂を含有し、硬化剤成分として下記一般式（１）で示される多価ヒドロキシ樹脂を含有することを特徴とするエポキシ樹脂組成物である。 That is, the present invention relates to an epoxy resin and a curing agent, or an epoxy resin composition containing these and a filler, and a phosphorus-containing epoxy resin having a phosphorus content of 1.0 to 5.0% by weight as an epoxy resin component. An epoxy resin composition comprising a polyvalent hydroxy resin represented by the following general formula (1) as a curing agent component.
上記エポキシ樹脂組成物は、次のいずれか１つ以上を満足することが好ましい。
1) リン含有エポキシ樹脂が、１分子中に２個以上のエポキシ基を有するエポキシ樹脂（ａ）と、一般式（３）及び／又は一般式（５）で示されるリン化合物類（ｂ）を含む原料とを反応して得られるリン含有エポキシ樹脂であること、
1) The phosphorus-containing epoxy resin comprises an epoxy resin (a) having two or more epoxy groups in one molecule and a phosphorus compound (b) represented by the general formula (3) and / or the general formula (5). A phosphorus-containing epoxy resin obtained by reacting a raw material containing,
2) リン含有エポキシ樹脂が、１分子中に２個以上のエポキシ基を有するエポキシ樹脂（ａ）と、一般式（３）及び／又は一般式（５）で示されるリン化合物類（ｂ）とを反応して得られるリン含有エポキシ樹脂であり、このリン含有エポキシ樹脂のエポキシ当量が下記式（６）で求められる理論エポキシ当量（Ｔ）の５０〜９５％の範囲であること。
Ｔ＝［（ａ1）+（ｂ1）］/（Ａ−Ｂ） （6）
ここで、（ａ1）はエポキシ樹脂（ａ）の量（ｇ）であり、（ｂ1）はリン化合物類（ｂ）の量（ｇ）である。Ａは式（７）で求められる値であり、Ｂは式（８）で求められる値である。
Ａ＝（ａ1）/エポキシ樹脂のエポキシ当量 （7）
Ｂ＝（ｂ1）/リン化合物類の水酸基当量 （8）
2) The phosphorus-containing epoxy resin comprises an epoxy resin (a) having two or more epoxy groups in one molecule, and a phosphorus compound (b) represented by the general formula (3) and / or the general formula (5) The epoxy equivalent of this phosphorus-containing epoxy resin is in the range of 50 to 95% of the theoretical epoxy equivalent (T) determined by the following formula (6).
T = [(a1) + (b1)] / (AB) (6)
Here, (a1) is the amount (g) of the epoxy resin (a), and (b1) is the amount (g) of the phosphorus compounds (b). A is a value obtained by equation (7), and B is a value obtained by equation (8).
A = (a1) / Epoxy equivalent of epoxy resin (7)
B = (b1) / hydroxyl equivalent of phosphorus compounds (8)
3) エポキシ樹脂成分として、更に一般式（９）で示されるエポキシ樹脂を５〜５０重量％含むこと、
4) 充填材が繊維状ガラスであること。 4) The filler is fibrous glass.
また、本発明は上記エポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物である。 Moreover, this invention is an epoxy resin hardened | cured material formed by hardening | curing the said epoxy resin composition.
本発明のエポキシ樹脂組成物は、リン含有エポキシ樹脂、特定の構造の多価ヒドロキシ樹脂、充填材を必須成分とすることで、低誘電性および難燃性、更には接着性にも優れた硬化物を与え、プリント基板用樹脂組成物、電子部品用封止材用樹脂組成物等の電子材料用途に好適に使用することが可能である。 The epoxy resin composition of the present invention includes a phosphorus-containing epoxy resin, a polyvalent hydroxy resin having a specific structure, and a filler as essential components, so that it has a low dielectric property, flame retardancy, and excellent adhesiveness. It can be used suitably for electronic material applications such as a resin composition for printed circuit boards and a resin composition for encapsulants for electronic parts.
本発明のエポキシ樹脂組成物は、エポキシ樹脂、及び硬化剤を必須成分とする。望ましくは、エポキシ樹脂、硬化剤、及び充填材を必須成分とする。これらの必須成分を５０重量％以上、好ましくは８０重量％以上、より好ましくは９５重量％以上含む。 The epoxy resin composition of the present invention contains an epoxy resin and a curing agent as essential components. Desirably, an epoxy resin, a curing agent, and a filler are essential components. These essential components are contained in an amount of 50% by weight or more, preferably 80% by weight or more, more preferably 95% by weight or more.
まず、本発明のエポキシ樹脂組成物中において、硬化剤成分として使用される一般式（１）で表される多価ヒドロキシ樹脂（ＳｔＰＮともいう）について説明する。この多価ヒドロキシ樹脂は下記一般式（16）で表される多価ヒドロキシ化合物（多価ヒドロキシ化合物（16）ともいう）とスチレン類を付加反応させることにより得ることができる。一般式（１）と一般式（16）において共通する記号は同じ意味を有する。一般式（１）において、ｐは０.１〜２．５の数を示すが、ベンゼン環１個当たりのＲ2の平均の数（数平均）を意味する。
一般式（１）で表されるＳｔＰＮは、スチレン類が付加した多価ヒドロキシ樹脂である。ＳｔＰＮは、多価ヒドロキシ化合物（16）のベンゼン環に対し、スチレン類を付加させることによって、水酸基当量を任意に調整することができる。ここで、スチレン類を付加させるとは、多価ヒドロキシ化合物（16）のベンゼン環の水素と式（２）で表される置換基（α-メチルベンジル基またはスチレニル基ともいう）を置換させることをいう。つまり、エポキシ樹脂硬化物においては、エポキシ基と水酸基との反応により生成するヒドロキシプロピル基が燃え易いとされているが、多価ヒドロキシ化合物に対してスチレン類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、芳香族性に富んだスチレン類の付加により、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。 StPN represented by the general formula (1) is a polyvalent hydroxy resin to which styrenes are added. StPN can arbitrarily adjust the hydroxyl equivalent by adding styrenes to the benzene ring of the polyvalent hydroxy compound (16). Here, addition of styrenes means substitution of hydrogen on the benzene ring of the polyvalent hydroxy compound (16) and a substituent represented by the formula (2) (also referred to as α-methylbenzyl group or styryl group). Say. In other words, in the epoxy resin cured product, the hydroxypropyl group generated by the reaction between the epoxy group and the hydroxyl group is said to burn easily, but by adding styrene to the polyvalent hydroxy compound to increase the hydroxyl equivalent. In addition, the aliphatic carbon ratio of the flammable component derived from the epoxy group is lowered, and high flame retardancy can be exhibited. Moreover, the addition of styrenes rich in aromaticity further improves the aromaticity of the polyvalent hydroxy resin, and is effective in improving moisture resistance in addition to flame retardancy.
また、一般式（１）の多価ヒドロキシ化合物を用いることで、エポキシ樹脂硬化物中の極性基であるヒドロキシプロピル基を低減できることから、難燃性、耐湿性に加えて誘電率、誘電正接の低減にも効果が現れる。 Moreover, since the hydroxypropyl group which is a polar group in the cured epoxy resin can be reduced by using the polyvalent hydroxy compound of the general formula (1), in addition to flame retardancy and moisture resistance, a dielectric constant and a dielectric loss tangent. The effect also appears in the reduction.
本発明で使用するＳｔＰＮの製法には制限はないが、多価ヒドロキシ化合物（16）とスチレン類とを付加反応させる方法が優れる。この際、多価ヒドロキシ化合物（16）とスチレン類との割合としては、得られる硬化物の難燃性と硬化性のバランスを考慮すると、多価ヒドロキシ化合物１モルに対するスチレン類の使用割合が０．２〜２．５モルの範囲が好ましく、より好ましくは０．６〜２．０モル、更に好ましくは０．９〜１．５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。 Although there is no restriction | limiting in the manufacturing method of StPN used by this invention, The method of addition-reacting a polyvalent hydroxy compound (16) and styrenes is excellent. At this time, the ratio of the polyhydroxy compound (16) and the styrenes is 0 when the ratio of the styrenes to 1 mol of the polyhydroxy compound is 0, considering the balance between flame retardancy and curability of the resulting cured product. The range is preferably from 2 to 2.5 mol, more preferably from 0.6 to 2.0 mol, still more preferably from 0.9 to 1.5 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.
また、ＳｔＰＮの軟化点は４０〜１３０℃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。これより低いと保存時のブロッキングの問題があり、これより高いとエポキシ樹脂組成物調整時の混練性と成形性に問題がある。 The softening point of StPN is preferably 40 to 130 ° 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. If it is lower than this, there is a problem of blocking during storage, and if it is higher than this, there is a problem in kneadability and moldability at the time of preparing the epoxy resin composition.
一般式（２）において、Ｒ3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Ｒ3は反応原料として使用するスチレン類によって定まる。 In the general formula (2), R 3 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, and more preferably hydrogen. This R 3 is determined by the styrenes used as reaction raw materials.
一般式（１）及び（16）において、ｎは１〜２０の数を示すが、好ましくは、平均（数平均）として１．５〜７．０の範囲である。 In general formula (1) and (16), n shows the number of 1-20, Preferably, it is the range of 1.5-7.0 as an average (number average).
多価ヒドロキシ化合物（16）は、フェノール類とホルマリンを反応させることにより得られる。このフェノール類は、フェノール又は炭素数１〜６の炭化水素基で置換されたフェノール類であるが、好ましくはフェノール又は炭素数１〜４のアルキル基で置換されたフェノール類であり、より好ましくはフェノールである。フェノール類としてフェノールを使用する場合、少量の他のフェノール成分を含んでもよい。他のフェノール成分としては、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、２，６−キシレノール、２，６−ジエチルフェノール、ハイドロキノン、レゾルシン、カテコール、１−ナフトール、２−ナフトール、１，５−ナフタレンジオール、１，６−ナフタレンジオール、１，７−ナフタレンジオール、２，６−ナフタレンジオール、２，７−ナフタレンジオールなどが挙げられる。これらのフェノール類又はナフトール類は２種以上を含んでもよい。 The polyvalent hydroxy compound (16) can be obtained by reacting phenols with formalin. These phenols are phenols or phenols substituted with a hydrocarbon group having 1 to 6 carbon atoms, preferably phenols or phenols substituted with an alkyl group having 1 to 4 carbon atoms, more preferably Phenol. When phenol is used as the phenol, it may contain a small amount of other phenol components. Other phenol components include, for example, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tertiary butylphenols, allylphenols, phenylphenols, 2,6-xylenol, 2, 6-diethylphenol, hydroquinone, resorcin, catechol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7 -Naphthalene diol etc. are mentioned. These phenols or naphthols may contain 2 or more types.
多価ヒドロキシ化合物との反応に用いるスチレン類は、スチレン又は炭素数１〜６の炭化水素基が置換したスチレンであるが、好ましくはスチレンである。このスチレン類は少量の他の反応成分を含んでもよく、スチレン類としてスチレンを使用する場合、他の反応成分として、α−メチルスチレン、ジビニルベンゼン、インデン、クマロン、ベンゾチオフェン、インドール、ビニルナフタレン等の不飽和結合含有成分を含むことができ、この場合、得られる多価ヒドロキシ樹脂にはこれらから生ずる基が芳香環上に置換した化合物が含まれることになる。 The styrene used for the reaction with the polyvalent hydroxy compound is styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms, and is preferably styrene. These styrenes may contain a small amount of other reaction components. When styrene is used as the styrenes, other reaction components include α-methylstyrene, divinylbenzene, indene, coumarone, benzothiophene, indole, vinylnaphthalene, etc. In this case, the resulting polyvalent hydroxy resin contains a compound in which a group derived therefrom is substituted on the aromatic ring.
多価ヒドロキシ化合物とのスチレン類との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。これより多いとフェノールノボラックのメチレン架橋結合が開裂し易くなり、開裂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、未反応スチレンモノマーを多く残存させる。 The reaction of polyvalent hydroxy compounds with styrenes can be carried out in the presence of an acid catalyst, and the amount of the catalyst used is in the range of 10 to 1000 ppm, preferably in the range of 100 to 500 ppm. If it is more than this, the methylene crosslinks of phenol novolac will be easily cleaved, and the unit price phenol component by-produced by the cleavage reaction will lower the curability and heat resistance. On the other hand, if it is less than this, the reactivity is lowered, and a large amount of unreacted styrene monomer remains.
この酸触媒としては、周知の無機酸、有機酸より適宜選択することができる。例えば、塩酸、硫酸、燐酸等の鉱酸や、ギ酸、シュウ酸、トリフルオロ酢酸、ｐ−トルエンスルホン酸、ジメチル硫酸、ジエチル硫酸等の有機酸や、塩化亜鉛、塩化アルミニウム、塩化鉄、三フッ化ホウ素等のルイス酸あるいはイオン交換樹脂、活性白土、シリカ−アルミナ、ゼオライト等の固体酸等が挙げられる。 The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride. Examples thereof include Lewis acids such as boron fluoride or ion exchange resins, activated clays, silica-alumina, solid acids such as zeolite, and the like.
また、この反応は通常、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、スチレン類を滴下させながら反応させる方法が一般的である。この際、滴下時間は、５時間以下が好ましく、通常、１〜１０時間である。反応後、溶媒を使用した場合は、必要により、触媒成分を取り除いた後、溶媒を留去させて本発明に使用する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 maintaining styrenes. A method of reacting while dropping is generally used. At this time, the dropping time is preferably 5 hours or less, and usually 1 to 10 hours. After the reaction, if a solvent is used, the catalyst component can be removed if necessary, and then the solvent can be distilled off to obtain the resin used in the present invention. If the solvent is not used, it is discharged directly when heated. The object can be obtained.
本発明のエポキシ樹脂組成物に使用されるリン含有エポキシ樹脂について説明する。このリン含有エポキシ樹脂はリン含有率（P/リン含有エポキシ樹脂）が１．０〜５．０重量％である。 The phosphorus containing epoxy resin used for the epoxy resin composition of this invention is demonstrated. This phosphorus-containing epoxy resin has a phosphorus content (P / phosphorus-containing epoxy resin) of 1.0 to 5.0% by weight.
リン含有エポキシ樹脂の製法は上記特許文献等により公知である。製法には制限はないが、好ましくはリン含有エポキシ樹脂が、１分子中に２個以上のエポキシ基を有するエポキシ樹脂（ａ）と、上記一般式（３）及び／又は一般式（４）で示されるリン化合物類（ｂ）、またはこれを含むエポキシ基と反応性の原料とを反応して得られるリン含有エポキシ樹脂である。リン化合物類（ｂ）以外のエポキシ基と反応性の原料としては、フェノール性水酸基、アミノ基、酸無水物基を有する化合物等がある。 The manufacturing method of a phosphorus containing epoxy resin is well-known by the said patent document. Although there is no restriction | limiting in a manufacturing method, Preferably phosphorus containing epoxy resin is epoxy resin (a) which has two or more epoxy groups in 1 molecule, and said general formula (3) and / or general formula (4). It is a phosphorus-containing epoxy resin obtained by reacting the shown phosphorus compound (b) or an epoxy group containing the phosphorus compound and a reactive raw material. Examples of raw materials reactive with epoxy groups other than phosphorus compounds (b) include compounds having phenolic hydroxyl groups, amino groups, and acid anhydride groups.
一般式（３）において、Ｘは式（４）で示される基であり、ｑは０または１であり、Ｒ4及びＲ5は独立に炭素数１〜６の炭化水素基であるが、Ｒ4とＲ5が結合してリン原子及び酸素原子と共に環状になっていてもよい。環状になる場合は、-Ｒ4-Ｐ-（Ｏ）ｑ-Ｒ5-の両末端が結合して環を形成する。式（４）において、Ｙは炭素数６〜２０のアリーレン基である。 In the general formula (3), X is a group represented by the formula (4), q is 0 or 1, and R 4 and R 5 are each independently a hydrocarbon group having 1 to 6 carbon atoms. 4 and R 5 may be bonded to form a ring together with a phosphorus atom and an oxygen atom. In the case of a ring, both ends of —R 4 —P— (O) q—R 5 — are bonded to form a ring. In Formula (4), Y is an arylene group having 6 to 20 carbon atoms.
一般式（５）において、Ｘは水素又は上記式（４）で示される基であり、ｒは０または１であり、Ｒ6及びＲ7は独立に炭素数１〜６の炭化水素基を表すが、Ｒ6とＲ7が結合してリン原子及び酸素原子と共に環状になっていてもよい。 In the general formula (5), X is hydrogen or a group represented by the above formula (4), r is 0 or 1, and R 6 and R 7 independently represent a hydrocarbon group having 1 to 6 carbon atoms. However, R 6 and R 7 may be bonded to form a ring together with a phosphorus atom and an oxygen atom.
エポキシ樹脂とリン化合物類からリン含有エポキシ樹脂を得る代表的な反応式のいくつかを下記に示す。
上記一般式（３）及び／又は一般式（４）で示されるリン化合物は一般的なエポキシ樹脂との相溶性に乏しくエポキシ樹脂中に均一に分散し難いため、エポキシ樹脂と反応させることで相溶性を向上させ、硬化物物性の均一性をはかることができる。また、リン化合物類（ｂ）以外にエポキシ樹脂と反応し得る多官能の化合物を併用することで、エポキシ樹脂部分の鎖長の延長が可能で、より相溶性に優れたリン含有エポキシ樹脂とすることができる。 The phosphorus compound represented by the general formula (3) and / or the general formula (4) has poor compatibility with general epoxy resins and is difficult to uniformly disperse in the epoxy resin. Solubility can be improved and uniformity of cured product properties can be achieved. In addition to the phosphorus compounds (b), a polyfunctional compound capable of reacting with the epoxy resin is used in combination, so that the chain length of the epoxy resin portion can be extended, and a phosphorus-containing epoxy resin having better compatibility is obtained. be able to.
更に、好ましくはリン含有エポキシ樹脂のエポキシ当量が上記式（６）で求められる理論エポキシ当量（Ｔ）の５０％から９５％の範囲である。
一般式（６）において、（ａ1）はエポキシ樹脂（ａ）の量（ｇ）であり、（ｂ1）はリン化合物類（ｂ）の量（ｇ）である。Ａは式（７）で求められる値であり、Ｂは式（８）で求められる値である。ここで、エポキシ当量及び水酸基当量の単位は、ｇ/eqである。
Furthermore, the epoxy equivalent of the phosphorus-containing epoxy resin is preferably in the range of 50% to 95% of the theoretical epoxy equivalent (T) determined by the above formula (6).
In the general formula (6), (a1) is the amount (g) of the epoxy resin (a), and (b1) is the amount (g) of the phosphorus compounds (b). A is a value obtained by equation (7), and B is a value obtained by equation (8). Here, the unit of epoxy equivalent and hydroxyl equivalent is g / eq.
リン化合物類（ｂ）以外にエポキシ樹脂と反応し得る多官能の化合物を併用する場合は、量及び水酸基当量は、リン化合物類（ｂ）を含む原料の量及び原料中の全官能基（エポキシ樹脂と反応性の官能基）の当量として式（６）の計算を行う。例えば、フェノール化合物の場合は水酸基当量、酸無水物の場合は酸無水物当量、アミン化合物やリン原子に直結した水素を有するリン化合物等の場合は活性水素当量とする。 When a polyfunctional compound capable of reacting with an epoxy resin is used in addition to the phosphorus compound (b), the amount and the hydroxyl equivalent amount are determined based on the amount of the raw material including the phosphorus compound (b) and the total functional groups in the raw material (epoxy Formula (6) is calculated as the equivalent of the resin and the reactive functional group. For example, in the case of a phenol compound, the hydroxyl group equivalent, in the case of an acid anhydride, the acid anhydride equivalent, and in the case of an amine compound or a phosphorus compound having hydrogen directly bonded to a phosphorus atom, the active hydrogen equivalent is used.
リン含有エポキシ樹脂を製造するために使用するエポキシ樹脂（ａ）は、エポトート ＹＤ−１２８、エポトート ＹＤ−８１２５（新日鐵化学株式会社製 ビスフェノールＡ型エポキシ樹脂）、エポトート ＹＤＦ−１７０、エポトート ＹＤＦ−８１７０（新日鐵化学株式会社製 ビスフェノールＦ型エポキシ樹脂）、ＹＳＬＶ−８０ＸＹ（新日鐵化学株式会社製 テトラメチルビスフェノールＦ型エポキシ樹脂）、エポトート ＹＤＣ−１３１２（ヒドロキノン型エポキシ樹脂）、ｊＥＲ ＹＸ４０００Ｈ（三菱化学株式会社製 ビフェニル型エポキシ樹脂）、エポトート ＹＤＰＮ―６３８（新日鐵株式会社製 フェノールノボラック型エポキシ樹脂）、エポトート ＹＤＣＮ−７０１（新日鐵化学株式会社製 クレゾールノボラック型エポキシ樹脂）、エポトート ＴＸ−１２１０（新日鐵化学株式会社製 置換フェノール型エポキシ樹脂）、エポトート ＺＸ−１２０１（新日鐵化学株式会社製 ビスフェノールフルオレン型エポキシ樹脂）、ＴＸ−０７１０（新日鐵化学株式会社製 ビスフェノールＳ型エポキシ樹脂）、エピクロン ＥＸＡ−１５１５（大日本化学工業株式会社製 ビスフェノールＳ型エポキシ樹脂）、ＮＣ−３０００（日本化薬株式会社製 ビフェニルアラルキルフェノール型エポキシ樹脂）、エポトート ＺＸ−１３５５、エポトート ＺＸ−１７１１（新日鐵化学株式会社製 ナフタレンジオール型エポキシ樹脂）、エポトート ＥＳＮ−１５５（新日鐵化学株式会社製 β−ナフトールアラルキル型エポキシ樹脂）、エポトート ＥＳＮ−３５５、エポトート ＥＳＮ−３７５（新日鐵化学株式会社製 ジナフトールアラルキル型エポキシ樹脂）、エポトート ＥＳＮ４７５Ｖ，エポトート ＥＳＮ−４８５（新日鐵化学株式会社製 α−ナフトールアラルキル型エポキシ樹脂）、ＥＰＰＮ−５０１Ｈ（日本化薬株式会社製 トリスフェニルメタン型エポキシ樹脂）、スミエポキシ ＴＭＨ−５７４（住友化学株式会社製 トリスフェニルメタン型エポキシ樹脂）、ＹＳＬＶ−１２０ＴＥ（新日鐵化学株式会社製 ビスチオエーテル型エポキシ樹脂）、エポトート ＺＸ−１６８４（新日鐵化学株式会社製 レゾルシノール型エポキシ樹脂）、デナコール ＥＸ−２０１（ナガセケムテックス株式会社製 レゾルシノール型エポキシ樹脂）、エピクロン ＨＰ−７２００Ｈ（ＤＩＣ株式会社製 ジシクロペンタジエン型エポキシ樹脂）等の多価フェノール樹脂のフェノール化合物とエピハロヒドリンとから製造されるエポキシ樹脂、ＴＸ−０９２９、ＴＸ−０９３４、ＴＸ−１０３２（新日鐵化学株式会社製 アルキレングリコール型エポキシ樹脂）等のアルコール化合物とエピハロヒドリンとから製造されるエポキシ樹脂、セロキサイド２０２１（ダイセル化学工業株式会社製 脂肪族環状エポキシ樹脂）、エポトート ＹＨ−４３４、（新日鐵化学株式会社製 ジアミノジフェニルメタンテトラグリシジルアミン）等のアミン化合物とエピハロヒドリンとから製造されるエポキシ樹脂、ｊＥＲ ６３０（三菱化学株式会社製 アミノフェノール型エポキシ樹脂）、エポトート ＦＸ−２８９Ｂ、エポトート ＦＸ−３０５、ＴＸ−０９３２Ａ（新日鐵化学株式会社製 リン含有エポキシ樹脂）等のエポキシ樹脂をリン含有フェノール化合物等の変性剤と反応して得られるリン含有エポキシ樹脂、ウレタン変性エポキシ樹脂、オキサゾリドン環含有エポキシ樹脂等が挙げられるが、これらに限定されるものではない。また、これらのエポキシ樹脂は単独で使用しても２種類以上を併用して使用してもよい。 The epoxy resin (a) used for producing the phosphorus-containing epoxy resin is Epototo YD-128, Epototo YD-8125 (Bisphenol A type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo YDF-170, Epototo YDF- 8170 (Bisphenol F type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YSLV-80XY (Tetramethylbisphenol F type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo YDC-1312 (hydroquinone type epoxy resin), jER YX4000H ( Biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Nippon Steel Corp.), Epotot YDCN-701 (Cresol novolak type epoxy manufactured by Nippon Steel Chemical Co., Ltd.) ), Epototo TX-1210 (substitute phenol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX-1201 (bisphenol fluorene type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), TX-0710 (Nippon Steel Chemical Co., Ltd.) Bisphenol S-type epoxy resin), Epicron EXA-1515 (Dainippon Kagaku Co., Ltd. bisphenol S-type epoxy resin), NC-3000 (Nippon Kayaku Co., Ltd. biphenylaralkylphenol-type epoxy resin), Epototo ZX- 1355, Epototo ZX-1711 (Naphthalenediol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epotot ESN-155 (β-naphthol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ESN-355, Epototo E SN-375 (manufactured by Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl type epoxy resin), Epototo ESN475V, Epototo ESN-485 (manufactured by Nippon Steel Chemical Co., Ltd., α-naphthol aralkyl type epoxy resin), EPPN-501H (Nippon Kayaku) Trisphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd. Trisphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd., YSLV-120TE (Bisthioether type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX- 1684 (Resorcinol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Denacol EX-201 (Resorcinol type epoxy resin manufactured by Nagase ChemteX Corporation), Epicron HP-7200H (Dicyclopentadie manufactured by DIC Corporation) Type epoxy resins) and other epoxy resins produced from phenolic compounds of polyhydric phenol resins and epihalohydrins, TX-0929, TX-0934, TX-1032 (alkylene glycol type epoxy resins manufactured by Nippon Steel Chemical Co., Ltd.), etc. Epoxy resins produced from alcohol compounds and epihalohydrins, Celoxide 2021 (aliphatic cyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), Epototo YH-434, and amines such as Diaminodiphenylmethane tetraglycidylamine manufactured by Nippon Steel Chemical Co., Ltd. Epoxy resin produced from a compound and epihalohydrin, jER 630 (Aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epototo FX-289B, Epototo FX-305, TX-0932A (Nippon Steel Chemical Co., Ltd.) Examples include, but are not limited to, phosphorus-containing epoxy resins, urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins, and the like obtained by reacting an epoxy resin such as a phosphorus-containing epoxy resin manufactured by a company with a modifier such as a phosphorus-containing phenol compound. Is not to be done. These epoxy resins may be used alone or in combination of two or more.
一般式（３）及び／又は一般式（４）で表されるリン化合物類（ｂ）を含む原料（反応性の原料という。）は、エポキシ樹脂と反応性の他のリン化合物を含むことがよい。鎖長延長剤として作用するリン化合物を含むことにより、鎖長が長くなりエポキシとの相溶性が増大する。上記他のリン化合物の具体例としては、１０−（２，５−ジヒドロキシフェニル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（三光株式会社製 商品名ＨＣＡ−ＨＱ）、１０−（１，４−ジオキシナフタレン）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（以下ＨＣＡ−ＮＱと記す）、ジフェニルホスフィニルヒドロキノン（北興化学工業株式会社製 商品名ＰＰＱ）、ジフェニルホスフェニル−１，４−ジオキシナフタリン、１，４−シクロオクチレンホスフィニル−１，４−フェニルジオール（日本化学工業株式会社製 商品名ＣＰＨＯ−ＨＱ）、１，５−シクロオクチレンホスフィニル−１，４−フェニルジオール（日本化学工業株式会社製 商品名ＣＰＨＯ−ＨＱ）等のリン含有フェノール類、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（三光株式会社製 商品名ＨＣＡ）やジフェニルホスフィン等のリン原子に直結した活性水素基を有するリン化合物類を挙げることができるが、これらに限定されるものではない。また、これらのリン化合物は２種類以上を併用して使用することもできる。 The raw material containing the phosphorus compounds (b) represented by the general formula (3) and / or the general formula (4) (referred to as a reactive raw material) may contain other phosphorus compounds reactive with the epoxy resin. Good. By including a phosphorus compound that acts as a chain extender, the chain length increases and compatibility with the epoxy increases. Specific examples of the other phosphorus compounds include 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ, manufactured by Sanko Co., Ltd.), 10 -(1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA-NQ), diphenylphosphinyl hydroquinone (trade name PPQ, manufactured by Hokuko Chemical Co., Ltd.) ), Diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol (trade name CPHO-HQ, manufactured by Nippon Chemical Industry Co., Ltd.), 1,5-cyclo Phosphorus such as octylenephosphinyl-1,4-phenyldiol (trade name CPHO-HQ, manufactured by Nippon Chemical Industry Co., Ltd.) Phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA manufactured by Sanko Co., Ltd.), phosphorus compounds having an active hydrogen group directly connected to a phosphorus atom, such as diphenylphosphine However, it is not limited to these. These phosphorus compounds can be used in combination of two or more.
また、これらのリン含有フェノール化合物は９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（三光株式会社製 商品名ＨＣＡ）やジフェニルホスフィン等のリン原子に直結した活性水素基を有するリン化合物と、１，４−ベンゾキノンや１，４−ナフトキノン等のキノン類との反応で得ることができる。ＨＣＡ−ＨＱについては特開昭６０−１２６２９３、ＨＣＡ−ＮＱについては特開昭６１−２３６７８７、ＰＰＱについてはｚｈ．Ｏｂｓｈｃｈ．Ｋｈｉｍ，４２（１１），第２４１５−２４１８頁（１９７２）に合成方法が示されているが、これに限定されるものではなく、公知慣用の方法を用いることができる。 In addition, these phosphorus-containing phenol compounds are active hydrogen groups directly bonded to phosphorus atoms such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA manufactured by Sanko Co., Ltd.) and diphenylphosphine. It can be obtained by a reaction between a phosphorus compound having quinone and quinones such as 1,4-benzoquinone and 1,4-naphthoquinone. For HCA-HQ, see JP-A-60-126293, for HCA-NQ, JP-A-61-2236787, and for PPQ, zh. Obshch. Khim, 42 (11), pp. 2415-2418 (1972) shows a synthesis method, but the method is not limited to this, and a known and commonly used method can be used.
また、前記リン含有化合物以外のエポキシ基と反応性の官能基を有する化合物類としては、例えば、カテコール、レゾルシノール、ヒドロキノン等のヒドロキシベンゼン類、ビフェノール類、ビナフトール類、トリスフェノール類、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ショウノール ＢＲＧ−５５５（昭和電工株式会社製 フェノールノボラック樹脂）、クレゾールノボラック樹脂、アルキルフェノールノボラック樹脂、アラルキルフェノールノボラック樹脂、トリアジン環含有フェノールノボラック樹脂、ビフェニルアラルキルフェノール樹脂、レヂトップ ＴＰＭ−１００（群栄化学工業株式会社製 トリスヒドロキシフェニルメタン型ノボラック樹脂）、アラルキルナフタレンジオール樹脂等の一分子中に２個以上のフェノール性水酸基と有する化合物類、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジド類、イミダゾール化合物類及びその塩類、ジシアンジアミド、アミノ安息香酸エステル類、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、メタキシレンジアミン、イソホロンジアミン等の脂肪族アミン類、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ジアミノエチルベンゼン等の芳香族アミン類、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、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、無水メチルナジック酸等の酸無水物類等が挙げられ、これらを２種類以上使用してもよい。これらの化合物の使用量は、使用されるエポキシ樹脂中のエポキシ基１当量に対して官能基が０．５当量以下となる様に用いるのが好ましく、さらに好ましくは０．２当量以下である。また、これら化合物をリン含有化合物と併用する場合、これら化合物の反応性基の当量も式（８）のリン化合物の水酸基当量に含め計算し、エポキシ当量が前記５０〜９５％の範囲とすることが好ましい。 Examples of compounds having a functional group reactive with an epoxy group other than the phosphorus-containing compound include, for example, hydroxybenzenes such as catechol, resorcinol, hydroquinone, biphenols, binaphthols, trisphenols, bisphenol A, bisphenol F, bisphenol S, shounol BRG-555 (Phenol novolak resin manufactured by Showa Denko KK), cresol novolak resin, alkylphenol novolak resin, aralkylphenol novolac resin, triazine ring-containing phenol novolak resin, biphenylaralkylphenol resin, Residtop TPM-100 2 or more in one molecule such as trishydroxyphenylmethane type novolak resin (manufactured by Gunei Chemical Industry Co., Ltd.), aralkyl naphthalene diol resin, etc. Compounds having phenolic hydroxyl groups, hydrazides such as adipic acid dihydrazide, sebacic acid dihydrazide, imidazole compounds and salts thereof, dicyandiamide, aminobenzoic acid esters, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaxylenediamine , Aliphatic amines such as isophoronediamine, aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, diaminoethylbenzene, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl Acid anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, etc. are used, and two or more of these are used. May be. The amount of these compounds used is preferably such that the functional group is 0.5 equivalent or less, more preferably 0.2 equivalent or less, relative to 1 equivalent of the epoxy group in the epoxy resin used. When these compounds are used in combination with phosphorus-containing compounds, the equivalents of the reactive groups of these compounds are also included in the hydroxyl equivalents of the phosphorus compound of formula (8), and the epoxy equivalent is within the range of 50 to 95%. Is preferred.
エポキシ樹脂が理論エポキシ当量（Ｔ）の５０〜９５％の範囲であるとは、エポキシ樹脂（ａ）とリン化合物類（ｂ）を含む原料との反応において、反応性原料の官能基を残存させることで可能となる。その残存した官能基は硬化反応において硬化剤と共にエポキシ基との反応が進行し、優れた硬化物物性を発現する。 The epoxy resin being in the range of 50 to 95% of the theoretical epoxy equivalent (T) means that the functional group of the reactive raw material remains in the reaction between the epoxy resin (a) and the raw material containing the phosphorus compound (b). This is possible. The remaining functional group undergoes a reaction with an epoxy group together with a curing agent in the curing reaction, and exhibits excellent physical properties of the cured product.
また、リン含有エポキシ樹脂は、エポキシ樹脂類（ａ）のエポキシ基１当量に対して、反応性の原料の反応性官能基を０．１０当量から０．９４当量の範囲で反応して得られるが、好ましくは０．２０当量から０．７０当量、より好ましくは０．２０当量から０．６０当量の範囲である。反応性官能基を有する化合物類（ｂ）が０．１０当量より少ないと難燃性が不十分となり、０．９４当量を超えて反応させると得られるリン含有エポキシ樹脂のワニス粘度が高くなる。 Further, the phosphorus-containing epoxy resin is obtained by reacting the reactive functional group of the reactive raw material in the range of 0.10 equivalent to 0.94 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin (a). Is preferably in the range of 0.20 equivalents to 0.70 equivalents, more preferably 0.20 equivalents to 0.60 equivalents. When the compound (b) having a reactive functional group is less than 0.10 equivalent, the flame retardancy becomes insufficient, and when the reaction exceeds 0.94 equivalent, the varnish viscosity of the phosphorus-containing epoxy resin obtained increases.
リン含有エポキシ樹脂のエポキシ当量は、好ましくは理論エポキシ当量（T）の５０％〜９５％の範囲であるが、７０％〜９５％の範囲がより好ましく、さらには７５％〜９０％の範囲である。５０％より小さいと難溶性のリン含有フェノール化合物が多く残存してしまい、溶剤溶解性が乏しくなってしまう。９５％より大きいと、エポキシ樹脂ワニスとした時の粘度が高く作業性に悪影響が出てしまう。理論エポキシ当量（T）の５０％〜９０％の範囲にした場合は、反応性の原料由来の反応性官能基が残存し、硬化反応の際に硬化剤成分として反応に寄与する。 The epoxy equivalent of the phosphorus-containing epoxy resin is preferably in the range of 50% to 95% of the theoretical epoxy equivalent (T), more preferably in the range of 70% to 95%, and further in the range of 75% to 90%. is there. If it is less than 50%, a large amount of poorly soluble phosphorus-containing phenolic compounds will remain, resulting in poor solvent solubility. If it is greater than 95%, the viscosity of the epoxy resin varnish is high and the workability is adversely affected. When it is in the range of 50% to 90% of the theoretical epoxy equivalent (T), the reactive functional group derived from the reactive raw material remains and contributes to the reaction as a curing agent component during the curing reaction.
リン含有エポキシ樹脂を得る反応の反応温度は１００℃〜２５０℃、さらには１３０℃〜１８０℃が好ましい。１００℃以下では反応の進行が著しく遅く、２５０℃以上では理論エポキシ当量の５０％から９５％の範囲とするための反応制御が困難である。 The reaction temperature of the reaction for obtaining the phosphorus-containing epoxy resin is preferably 100 ° C to 250 ° C, more preferably 130 ° C to 180 ° C. At 100 ° C. or lower, the progress of the reaction is remarkably slow, and at 250 ° C. or higher, it is difficult to control the reaction so that the theoretical epoxy equivalent is in the range of 50% to 95%.
また、リン含有エポキシ樹脂を得る反応では、必要に応じて反応を促進するために反応触媒を使用することができる。使用できる触媒としては、トリフェニルホスフィン、トリス（２，６−ジメトキシフェニル）ホスフィン等のホスフィン類、ｎ−ブチルトリフェニルホスホニウムブロミド、エチルトリフェニルホスホニウムヨージド等の四級ホスホニウム塩類、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール等のイミダゾール類、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムブロミド等の四級アンモニウム塩類、トリエチルアミン、ベンジルジメチルアミン等の三級アミン類等、公知慣用の触媒が挙げられ、これらに限定されるものではない。より好ましい触媒としてホスフィン類が挙げられ、特に好ましい触媒としては酸素を含有しても良い炭化水素基が置換したホスフィン類である。これら触媒の使用量は、反応性の原料に対して０．００５％から１％の範囲が好ましい。 In the reaction for obtaining a phosphorus-containing epoxy resin, a reaction catalyst can be used to accelerate the reaction as necessary. Catalysts that can be used include phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, quaternary phosphonium salts such as n-butyltriphenylphosphonium bromide and ethyltriphenylphosphonium iodide, 2-ethyl- Examples of known catalysts include imidazoles such as 4-methylimidazole and 2-phenylimidazole, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide, and tertiary amines such as triethylamine and benzyldimethylamine. It is not limited to these. More preferable catalysts include phosphines, and particularly preferable catalysts are phosphines substituted with a hydrocarbon group which may contain oxygen. The amount of these catalysts used is preferably in the range of 0.005% to 1% with respect to the reactive raw material.
エポキシ樹脂と反応性の原料の反応は無溶媒でも、溶媒中でも行うことができるが、溶媒中で行う場合は、非プロトン性溶媒中で行うことが好ましく、例えば、トルエン、キシレン、メタノール、エタノール、２−ブトキシエタノール、ジアルキルエーテル、グリコールエーテル、プロピレングリコールモノメチルエーテル、ジオキサン等が挙げられる。これらの反応溶媒は単独で、あるいは２種類以上を同時に使用してもよい。これらの反応溶媒の使用量は反応物全重量中の５０％以下が好ましい。 The reaction between the epoxy resin and the reactive raw material can be performed in the absence of a solvent or in a solvent, but when performed in a solvent, it is preferably performed in an aprotic solvent, such as toluene, xylene, methanol, ethanol, Examples include 2-butoxyethanol, dialkyl ether, glycol ether, propylene glycol monomethyl ether, and dioxane. These reaction solvents may be used alone or in combination of two or more. The amount of these reaction solvents used is preferably 50% or less based on the total weight of the reaction product.
また、リン含有エポキシ樹脂を得る反応は、触媒量を調整することでエポキシ当量を理論エポキシ当量の５０％〜９５％の範囲にすることができるが、反応温度を調整したり、反応を段階的に行う等の公知慣用の製造方法を用いることができ、これらに限定されるものではない。 In addition, the reaction for obtaining the phosphorus-containing epoxy resin can adjust the catalyst amount to make the epoxy equivalent in the range of 50% to 95% of the theoretical epoxy equivalent, but the reaction temperature can be adjusted or the reaction can be performed stepwise. However, it is not limited to these methods.
本発明のエポキシ樹脂組成物は、エポキシ樹脂として前記のリン含有エポキシ樹脂を必須成分として含み、硬化剤として一般式（1）の多価ヒドロキシ樹脂を、そして充填材を必須成分とするが、必要に応じて他のエポキシ樹脂、エポキシ樹脂硬化剤、硬化促進剤、充填剤等を含んでもよい。 The epoxy resin composition of the present invention contains the above-mentioned phosphorus-containing epoxy resin as an essential component as an epoxy resin, a polyvalent hydroxy resin of the general formula (1) as a curing agent, and a filler as an essential component. Depending on the above, other epoxy resins, epoxy resin curing agents, curing accelerators, fillers and the like may be included.
本発明のエポキシ樹脂組成物に使用するエポキシ樹脂は、前記リン含有エポキシ樹脂を必須成分として含有するが、このリン含有エポキシ樹脂の他に、物性を損なわない範囲で他のエポキシ樹脂を含有することができる。他のエポキシ樹脂としては、２官能以上のエポキシ樹脂が好ましく、上記リン含有エポキシ樹脂の合成に使用するエポキシ樹脂などが挙げられるが、これらに限定されるものではない。また、これらのエポキシ樹脂は２種類以上を併用して使用してもよい。全エポキシ樹脂成分中に、前記リン含有エポキシ樹脂を５０ｗｔ％以上、好ましくは７０ｗｔ％以上含むことがよい。 The epoxy resin used in the epoxy resin composition of the present invention contains the phosphorus-containing epoxy resin as an essential component, but contains other epoxy resins in addition to the phosphorus-containing epoxy resin as long as the physical properties are not impaired. Can do. The other epoxy resin is preferably a bifunctional or higher functional epoxy resin, and examples thereof include, but are not limited to, an epoxy resin used for the synthesis of the phosphorus-containing epoxy resin. Moreover, you may use these epoxy resins in combination of 2 or more types. The total epoxy resin component may contain the phosphorus-containing epoxy resin in an amount of 50 wt% or more, preferably 70 wt% or more.
本発明のエポキシ樹脂組成物における硬化剤の使用量は、エポキシ樹脂の理論エポキシ当量１当量に対して硬化剤の官能基が０．５〜１．３当量の範囲が好ましく、０．７〜１．１当量がさらに好ましい。全硬化剤中に、一般式（1）の多価ヒドロキシ樹脂を１５ｗｔ％以上、好ましくは２５ｗｔ％以上、より好ましくは５０ｗｔ％以上含むことがよい。 The amount of the curing agent used in the epoxy resin composition of the present invention is preferably in the range of 0.5 to 1.3 equivalents of the functional group of the curing agent with respect to 1 equivalent of the theoretical epoxy equivalent of the epoxy resin, and 0.7 to 1 More preferred is 1 equivalent. The total curing agent may contain 15 wt% or more, preferably 25 wt% or more, more preferably 50 wt% or more of the polyvalent hydroxy resin of the general formula (1).
また、流動性や粘度等を調整する場合には、本発明のエポキシ樹脂組成物の物性を損ねない範囲で稀釈剤を使用することが可能である。希釈剤は反応性希釈剤が好ましいが、非反応性希釈剤でも構わない。反応性希釈剤としては、アリルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル等の単官能、レゾルシノールグリシジルエーテル、ネオペンチルグリコールグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル等の二官能、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル等の多官能グリシジルエーテル類が挙げられる。非反応性希釈剤としては、ベンジルアルコール、ブチルジグリコール、パインオイル等が挙げられる。 Moreover, when adjusting fluidity | liquidity, a viscosity, etc., it is possible to use a diluent in the range which does not impair the physical property of the epoxy resin composition of this invention. The diluent is preferably a reactive diluent, but may be a non-reactive diluent. As reactive diluent, monofunctional such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, bifunctional such as resorcinol glycidyl ether, neopentyl glycol glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol And polyfunctional glycidyl ethers such as polyglycidyl ether, trimethylolpropane polyglycidyl ether, and pentaerythritol polyglycidyl ether. Non-reactive diluents include benzyl alcohol, butyl diglycol, pine oil and the like.
また、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使用することが可能である。例えば、ホスフィン類、四級ホスホニウム塩類、三級アミン類、四級アンモニウム塩類、イミダゾール化合物類、三フッ化ホウ素錯体類、３−（３，４−ジクロロジフェニル）−１，１−ジメチルウレア、３−（４−クロロフェニル）−１，１−ジメチルウレア、３−フェニル−１，１−ジメチルウレア等が挙げられる。これら硬化促進剤は使用するエポキシ樹脂、併用するエポキシ樹脂硬化剤の種類、成形方法、硬化温度、要求特性によるが、エポキシ樹脂に対して重量比で０．０１％から２０％の範囲が好ましく、さらには０．１％から１０％が好ましい。 Moreover, it is possible to use a hardening accelerator as needed for the epoxy resin composition of the present invention. For example, phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3- (3,4-dichlorodiphenyl) -1,1-dimethylurea, 3 -(4-Chlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea and the like. These curing accelerators depend on the epoxy resin to be used, the type of epoxy resin curing agent to be used together, the molding method, the curing temperature, and the required characteristics, but preferably in the range of 0.01% to 20% by weight with respect to the epoxy resin, Furthermore, 0.1% to 10% is preferable.
本発明のエポキシ樹脂組成物は、特性を損ねない範囲で他の熱硬化性樹脂、熱可塑性樹脂を配合してもよい。例えばフェノール樹脂、アクリル樹脂、石油樹脂、インデン樹脂、クマロンインデン樹脂、フェノキシ樹脂、ポリウレタン、ポリエステル、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリフェニレンエーテル、変性ポリフェニレンエーテル、ポリエーテルスルホン、ポリスルホン、ポリエーテルエーテルケトン、ポリフェニレンスルフィド、ポリビニルホルマール等が挙げられるがこれらに限定されるものではない。 The epoxy resin composition of the present invention may be blended with other thermosetting resins and thermoplastic resins as long as the properties are not impaired. For example, phenol resin, acrylic resin, petroleum resin, indene resin, coumarone indene resin, phenoxy resin, polyurethane, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polyphenylene ether, modified polyphenylene ether, polyethersulfone, polysulfone, poly Examples include, but are not limited to, ether ether ketone, polyphenylene sulfide, and polyvinyl formal.
本発明のエポキシ樹脂組成物に配合される充填材としては、溶融シリカ、結晶シリカ、アルミナ、窒化ケイ素、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、タルク、マイカ、炭酸カルシウム、ケイ酸カルシウム、水酸化カルシウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、窒化ホウ素、炭素、炭素繊維、ガラス繊維、アルミナ繊維、シリカアルミナ繊維、炭化ケイ素繊維、ポリエステル繊維、セルロース繊維、アラミド繊維等が挙げられる。これら充填材は樹脂組成物全体に対し、１〜７０ｗｔ％が好ましい。 As fillers blended in the epoxy resin composition of the present invention, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, hydroxide Examples include calcium, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, and aramid fiber. These fillers are preferably 1 to 70 wt% with respect to the entire resin composition.
エポキシ樹脂組成物を板状基板等とする場合、その寸法安定性、曲げ強度等の点で繊維状のものが好ましい充填材として挙げられる。より好ましくはガラス繊維を網目状に編み上げたガラス繊維基板が挙げられる。 When the epoxy resin composition is used as a plate-like substrate or the like, a fibrous material is preferable in terms of dimensional stability, bending strength, and the like. More preferred is a glass fiber substrate in which glass fibers are knitted in a mesh shape.
本発明のエポキシ樹脂組成物は、さらに必要に応じてシランカップリング剤、酸化防止剤、離型剤、消泡剤、乳化剤、揺変性付与剤、平滑剤、難燃剤、顔料等の核種添加剤を配合することができる。これらの添加剤は樹脂組成物に対し、０．０１％から２０ｗｔ％の範囲が好ましい。 The epoxy resin composition of the present invention further includes a nuclide additive such as a silane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment as necessary. Can be blended. These additives are preferably in the range of 0.01% to 20% by weight with respect to the resin composition.
本発明のエポキシ樹脂組成物は、公知のエポキシ樹脂組成物と同様な方法により成型、硬化して硬化物とすることができる。成型方法、硬化方法は公知のエポキシ樹脂組成物と同様の方法をとることができ、例えば１３０℃〜２００℃で、１時間〜５時間程度で硬化することができる。また、ワニスとして使用することもできる。 The epoxy resin composition of the present invention can be molded and cured by the same method as known epoxy resin compositions to obtain a cured product. The molding method and the curing method can be the same as the known epoxy resin composition, and can be cured at 130 to 200 ° C. for about 1 to 5 hours, for example. It can also be used as a varnish.
本発明のエポキシ樹脂硬化物は、積層物、成型物、接着物、塗膜、フィルム等の形態をとることができる。 The cured epoxy resin of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film and the like.
次に本発明の実施例を示すが、本発明の範囲はこれら実施例に限定されるものではない。特に断りがない限り「部」は重量部を表す。また、分析方法、測定方法は以下の通りである。 Examples of the present invention are shown below, but the scope of the present invention is not limited to these examples. Unless otherwise specified, “parts” represents parts by weight. The analysis method and measurement method are as follows.
・エポキシ当量：ＪＩＳ Ｋ７２３６に準じた。
・フェノール性水酸基当量：試料に４％のメタノールを含むＴＨＦを加え、１０％テトラブチルアンモニウムヒドロキシドを加えて、紫外可視分光光度計を用いて波長４００ｎｍから２５０ｎｍ間の吸光度を測定した。同様の測定方法より求めた検量線より、フェノール性水酸基を水酸基１当量当たりの試料の重量として求めた。
・不揮発分：ＪＩＳ Ｋ７２３５−１９８６
・リン含有量：試料に硫酸、塩酸、過塩素酸を加え、加熱して湿式灰化し、全てのリン原子をオルトリン酸とした。硫酸酸性溶液中でメタバナジン酸塩及びモリブデン酸塩を反応させ、生じたリンバナードモリブデン酸錯体の４２０ｎｍにおける吸光度を測定し、予め作成した検量線により求めたリン原子含有量を重量％で表した。積層板のリン含有量は、積層板の樹脂分に対する含有量として表した。
溶融粘度：コーンプレート粘度計（東亜工業（株）製、ＡＳＰ−ＭＧ）を用いて、１５０℃にて測定した。
Epoxy equivalent: Conforms to JIS K7236.
Phenolic hydroxyl group equivalent: THF containing 4% methanol was added to the sample, 10% tetrabutylammonium hydroxide was added, and the absorbance between wavelengths 400 nm and 250 nm was measured using an ultraviolet-visible spectrophotometer. From the calibration curve obtained from the same measurement method, the phenolic hydroxyl group was determined as the weight of the sample per equivalent of hydroxyl group.
Nonvolatile content: JIS K7235-1986
Phosphorus content: sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus atoms to orthophosphoric acid. Metavanadate and molybdate were reacted in a sulfuric acid acidic solution, and the absorbance at 420 nm of the resulting phosphomadomolybdate complex was measured. The phosphorus atom content determined by a previously prepared calibration curve was expressed in wt%. The phosphorus content of the laminate was expressed as the content relative to the resin content of the laminate.
Melt viscosity: Measured at 150 ° C. using a cone plate viscometer (manufactured by Toa Kogyo Co., Ltd., ASP-MG).
・誘電率、誘電正接：マテリアルアナライザー／ＡＧＩＬＥＮＴ Ｔｅｃｈｎｏｌｏｇｉｅｓ 社製を用い、容量法により周波数１ＧＨｚにおける誘電率および誘電正接を求めることにより評価した。
・燃焼性：ＵＬ９４（Ｕｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．の安全認証規格）に準じた。５本の試験片について試験を行い、１回目と２回目の接炎（５本それぞれ２回ずつで計１０回の接炎）後の有炎燃焼持続時間の合計時間を秒で表した。
・層間剥離強さ（層間接着力）：ＪＩＳ Ｃ６４８１に準じた。
-Dielectric constant and dielectric loss tangent: It evaluated by calculating | requiring the dielectric constant and dielectric loss tangent in frequency 1GHz by the capacitance method using the material analyzer / AGILENT Technologies company make.
Combustibility: Conforms to UL94 (Underwriters Laboratories Inc. safety certification standard). Five test pieces were tested, and the total time of the flammable combustion duration after the first and second flame contact (two flames each twice for a total of 10 flames) was expressed in seconds.
-Interlaminar peel strength (interlayer adhesion): Conforms to JIS C6481.
合成例１
１Ｌの４口フラスコに、フェノールノボラック（昭和高分子製；ＢＲＧ−５５５、水酸基当量１０５ｇ／ｅｑ．、軟化点６７℃、１５０℃での溶融粘度０．０８Ｐａ・ｓ）１０５ｇを仕込み１４０℃に昇温した。次に、１４０℃にて攪拌しながら酸触媒としてｐ−トルエンスルホン酸０．０９９ｇ（フェノールノボラックとスチレンの合計に対して５００ｐｐｍ）を投入し、スチレン９３．６ｇ（０．９モル）を３時間かけて滴下し反応させた。さらに、１４０℃にて２時間反応後、３０％Ｎａ2ＣＯ3を０．１６３ｇ添加し中和を行った。次に、ＭＩＢＫ３３０ｇに溶解させ、８０℃にて５回水洗を行った。続いて、ＭＩＢＫを減圧留去した後、多価ヒドロキシ樹脂１９８ｇを得た。その水酸基当量は１９９ｇ／ｅｑ．、軟化点は７７℃、１５０℃での溶融粘度は０．２３Ｐａ・ｓであり、一般式（1）におけるｎは平均で３．３、ｐは０．９であった。この樹脂をＳｔＰＮ−Ａという。
Synthesis example 1
Into a 1 L 4-neck flask was charged 105 g of phenol novolac (manufactured by Showa Polymer; BRG-555, hydroxyl group equivalent 105 g / eq., Softening point 67 ° C., melt viscosity 0.08 Pa · s at 150 ° C.) and raised to 140 ° C. Warm up. Next, 0.099 g of p-toluenesulfonic acid (500 ppm based on the total of phenol novolac and styrene) was added as an acid catalyst while stirring at 140 ° C., and 93.6 g (0.9 mol) of styrene was added for 3 hours. The reaction was carried out by adding dropwise. Furthermore, after reacting at 140 ° C. for 2 hours, 0.163 g of 30% Na 2 CO 3 was added for neutralization. Next, it was dissolved in 330 g of MIBK and washed 5 times with water at 80 ° C. Subsequently, after MIBK was distilled off under reduced pressure, 198 g of a polyvalent hydroxy resin was obtained. Its hydroxyl equivalent is 199 g / eq. The softening point was 77 ° C., the melt viscosity at 150 ° C. was 0.23 Pa · s, n in the general formula (1) was 3.3 on average, and p was 0.9. This resin is referred to as StPN-A.
合成例２
１Ｌの４口フラスコに、フェノールノボラック（ＢＲＧ−５５５）１０５ｇを仕込み１４０℃に昇温した。次に、１４０℃にて攪拌しながら酸触媒としてｐ−トルエンスルホン酸０．１１５ｇ（フェノールノボラックとスチレンの合計に対して５００ｐｐｍ）を投入し、スチレン１３５．２ｇ（１．３モル）を３時間かけて滴下し反応させた。さらに、１４０℃にて２時間反応後、３０％Ｎａ2ＣＯ3を０．１８７ｇ添加し中和を行った。次に、ＭＩＢＫ３３０ｇに溶解させ、８０℃にて５回水洗を行った。続いて、ＭＩＢＫを減圧留去した後、多価ヒドロキシ樹脂２２９ｇを得た。その水酸基当量は２３５ｇ／ｅｑ．、軟化点は７８℃、１５０℃での溶融粘度は０．２６Ｐａ・ｓであり、ｎは平均で３．３、ｐは１．３であった。この樹脂をＳｔＰＮ−Ｂという。
Synthesis example 2
A 1 L 4-neck flask was charged with 105 g of phenol novolac (BRG-555) and heated to 140 ° C. Next, 0.115 g of p-toluenesulfonic acid (500 ppm based on the total of phenol novolac and styrene) was added as an acid catalyst while stirring at 140 ° C., and 135.2 g (1.3 mol) of styrene was added for 3 hours. The reaction was carried out by adding dropwise. Furthermore, after reacting at 140 ° C. for 2 hours, 0.187 g of 30% Na 2 CO 3 was added for neutralization. Next, it was dissolved in 330 g of MIBK and washed 5 times with water at 80 ° C. Subsequently, after MIBK was distilled off under reduced pressure, 229 g of a polyvalent hydroxy resin was obtained. Its hydroxyl equivalent is 235 g / eq. The softening point was 78 ° C., the melt viscosity at 150 ° C. was 0.26 Pa · s, n was 3.3 on average, and p was 1.3. This resin is referred to as StPN-B.
合成例３
攪拌装置、温度計、冷却管、窒素ガス導入管を備えた４つ口のガラス製セパラブルフラスコに、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（三光株式会社製 商品名ＨＣＡ、リン含有量１４．２重量％）４３２部及び１，４−ナフトキノン７９部、トルエン４９０部を入れ、７５℃で３０分間撹拌した後、系内の水分を除きながら１１０℃で９０分間反応させた後、トルエンを除いて１０−（１，４−ジオキシナフタレン）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（ＨＣＡ−ＮＱ）を得た。これにフェノールノボラック型エポキシ樹脂（新日鐵化学株式会社製 商品名ＹＤＰＮ−６３８、エポキシ当量１７５ｇ／ｅｑ．）１２４０部、触媒としてトリフェニルホスフィン（ＴＰＰ）０．５１部を加えて１６５℃で４．５時間反応を行った後、ＭＥＫで希釈した。得られたリン含有エポキシ樹脂溶液は濃褐色透明で、不揮発分７０％、溶液粘度１９００ｍＰａ・ｓ、エポキシ当量３９２ｇ／ｅｑ．、リン含有量３．５％であった。理論エポキシ当量は３８２ｇ／ｅｑ．、理論エポキシ当量に対する実測エポキシ当量の割合は１０３％であった。この樹脂をエポキシ樹脂Ａとする。
Synthesis example 3
To a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser tube, and a nitrogen gas inlet tube, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Co., Ltd.) Product name HCA, phosphorus content 14.2% by weight) 432 parts and 1,4-naphthoquinone 79 parts, toluene 490 parts, stirred at 75 ° C. for 30 minutes, and then at 110 ° C. while removing moisture in the system After reacting for 90 minutes, 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-NQ) was obtained by removing toluene. 1240 parts of phenol novolac type epoxy resin (trade name YDPN-638 manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent: 175 g / eq.) And 0.51 part of triphenylphosphine (TPP) as a catalyst were added at 4 ° C. at 165 ° C. After reacting for 5 hours, it was diluted with MEK. The resulting phosphorus-containing epoxy resin solution was dark brown and transparent, had a nonvolatile content of 70%, a solution viscosity of 1900 mPa · s, and an epoxy equivalent of 392 g / eq. The phosphorus content was 3.5%. The theoretical epoxy equivalent is 382 g / eq. The ratio of the actually measured epoxy equivalent to the theoretical epoxy equivalent was 103%. This resin is referred to as epoxy resin A.
合成例４
攪拌装置、温度計、冷却管、窒素ガス導入管を備えた４つ口のガラス製セパラブルフラスコに、ＨＣＡ ４３２部及び１，４−ナフトキノン７９部、トルエン４９０部を入れ、７５℃で３０分間撹拌した後、系内の水分を除きながら１１０℃で９０分間反応させた後、トルエンを除いてＨＣＡ−ＮＱを得た。これにＹＤＰＮ−６３８を１２４０部、ＴＰＰを０．１５部加えて１６５℃で４．５時間反応を行った後、ＭＥＫで希釈した。得られたリン含有エポキシ樹脂溶液は濃褐色透明で、不揮発分７０％、ワニス粘度３００ｍＰａ・ｓ、実測エポキシ当量２９２ｇ／ｅｑ．水酸基当量３６００ｇ／ｅｑ．、リン含有量３．５％であった。また、エポキシ樹脂類（ａ）のエポキシ基１当量に対する反応性官能基を有する化合物類（ｂ）の官能基は０．３０当量、理論エポキシ当量は３８２ｇ／ｅｑ．、理論エポキシ当量に対する実測エポキシ当量の割合は７６％であった。この樹脂をエポキシ樹脂Ｂとする。
Synthesis example 4
In a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser tube, and a nitrogen gas inlet tube, 432 parts of HCA, 79 parts of 1,4-naphthoquinone, and 490 parts of toluene were placed, and the mixture was heated at 75 ° C. for 30 minutes. After stirring, the reaction was carried out at 110 ° C. for 90 minutes while removing moisture in the system, and then toluene was removed to obtain HCA-NQ. 1240 parts of YDPN-638 and 0.15 parts of TPP were added thereto and reacted at 165 ° C. for 4.5 hours, and then diluted with MEK. The obtained phosphorus-containing epoxy resin solution was dark brown and transparent, had a nonvolatile content of 70%, a varnish viscosity of 300 mPa · s, an actually measured epoxy equivalent of 292 g / eq. Hydroxyl equivalent weight 3600 g / eq. The phosphorus content was 3.5%. Further, the functional group of the compound (b) having a reactive functional group with respect to 1 equivalent of the epoxy group of the epoxy resin (a) is 0.30 equivalent, and the theoretical epoxy equivalent is 382 g / eq. The ratio of the actually measured epoxy equivalent to the theoretical epoxy equivalent was 76%. This resin is referred to as epoxy resin B.
合成例５
四つ口セパラブルフラスコに合成例１で得たＳｔＰＮ−Ａ１５０ｇ、エピクロルヒドリン４１９ｇ、ジエチレングリコールジメチルエーテル６３ｇ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６２．９ｇ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１８０ｇを得た。得られた樹脂のエポキシ当量は２７０ｇ／ｅｑ．、軟化点は６１℃、１５０℃における溶融粘度は０．１３Ｐａ・ｓであった。このエポキシ樹脂をＳｔＰＮＥとする。
Synthesis example 5
In a four-necked separable flask, 150 g of StPN-A obtained in Synthesis Example 1, 419 g of epichlorohydrin, and 63 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, 62.9 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 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 generated by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 180 g of an epoxy resin. The epoxy equivalent of the obtained resin was 270 g / eq. The softening point was 61 ° C., and the melt viscosity at 150 ° C. was 0.13 Pa · s. This epoxy resin is referred to as StPNE.
実施例１〜６、比較例１〜４
上記の合成で得られた多価ヒドロキシ樹脂（ＳｔＰＮ−Ａ、ＳｔＰＮ−Ｂ）、エポキシ樹脂Ａ，エポキシ樹脂Ｂ、エポキシ樹脂ＳｔＰＮＥ、及び硬化促進剤として２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ）を溶剤（メチルエチルケトン、メトキシプロパノール）に溶解し、不揮発分を５０％とした。表１〜２に示す配合割合でエポキシ樹脂ワニスを調製した。表中の数値は配合における重量部を示す。PNはＢＲＧ−５５５であり、硬化剤成分である。ＦＸ−２８９Ｂは新日鐵化学株式会社製リン含有エポキシ樹脂である。リン含有率は樹脂組成物中のＰ含有率である。ＤＩＣＹはジシアンジアミド硬化剤である。なお、表１〜２において、Ｓｔ-ＰＮ−Ａ、Ｓｔ-ＰＮ−Ｂは、それぞれ上記ＳｔＰＮ−Ａ、ＳｔＰＮ−Ｂを意味する。
Examples 1-6, Comparative Examples 1-4
Polyhydric hydroxy resins (StPN-A, StPN-B) obtained by the above synthesis, epoxy resin A, epoxy resin B, epoxy resin StPNE, and 2-ethyl-4-methylimidazole (2E4MZ) as a curing accelerator. It was dissolved in a solvent (methyl ethyl ketone, methoxypropanol) to make the nonvolatile content 50%. Epoxy resin varnishes were prepared at the blending ratios shown in Tables 1-2. The numerical value in a table | surface shows the weight part in a mixing | blending. PN is BRG-555 and is a curing agent component. FX-289B is a phosphorus-containing epoxy resin manufactured by Nippon Steel Chemical Co., Ltd. The phosphorus content is the P content in the resin composition. DICY is a dicyandiamide curing agent. In Tables 1 and 2, St-PN-A and St-PN-B mean StPN-A and StPN-B, respectively.
実施例１〜６に示すように本発明のエポキシ樹脂組成物の硬化物は、誘電特性や難燃性に優れることが判った。従来技術でも比較例１の様にアミン系硬化剤を使用したり、比較例３に示す様に組成物リン含有率を高めることで難燃性は付与できるが、誘電特性は悪化してしまう。また、本発明のエポキシ樹脂組成物は接着性にも優れる硬化物を得ることができる。 As shown in Examples 1 to 6, the cured product of the epoxy resin composition of the present invention was found to be excellent in dielectric properties and flame retardancy. Even in the prior art, flame retardancy can be imparted by using an amine curing agent as in Comparative Example 1 or increasing the phosphorus content of the composition as shown in Comparative Example 3, but the dielectric properties deteriorate. Moreover, the epoxy resin composition of this invention can obtain the hardened | cured material which is excellent also in adhesiveness.
Claims (6)
Ｔ＝［（ａ1）+（ｂ1）］/（Ａ−Ｂ） （6）
ここで、（ａ1）はエポキシ樹脂（ａ）の量（ｇ）であり、（ｂ1）はリン化合物類（ｂ）の量（ｇ）である。Ａは式（７）で求められる値であり、Ｂは式（８）で求められる値である。
Ａ＝（ａ1）/エポキシ樹脂のエポキシ当量 （7）
Ｂ＝（ｂ1）/リン化合物類の水酸基当量 （8） The phosphorus-containing epoxy resin reacts with an epoxy resin (a) having two or more epoxy groups in one molecule and a phosphorus compound (b) represented by the general formula (3) and / or the general formula (5). and a phosphorus-containing epoxy resin obtained by an epoxy according to claim 2 in the range of 50% to 95% of the phosphorus-containing epoxy equivalent of the epoxy resin is represented by the following formula theoretical epoxy equivalent is obtained by (6) (T) Resin composition.
T = [(a1) + (b1)] / (AB) (6)
Here, (a1) is the amount (g) of the epoxy resin (a), and (b1) is the amount (g) of the phosphorus compounds (b). A is a value obtained by equation (7), and B is a value obtained by equation (8).
A = (a1) / Epoxy equivalent of epoxy resin (7)
B = (b1) / hydroxyl equivalent of phosphorus compounds (8)
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