JP5320130B2 - 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
- JP5320130B2 JP5320130B2 JP2009086384A JP2009086384A JP5320130B2 JP 5320130 B2 JP5320130 B2 JP 5320130B2 JP 2009086384 A JP2009086384 A JP 2009086384A JP 2009086384 A JP2009086384 A JP 2009086384A JP 5320130 B2 JP5320130 B2 JP 5320130B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- resin
- carbon atoms
- psn
- 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.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 103
- 229920000647 polyepoxide Polymers 0.000 title claims description 103
- 229920005989 resin Polymers 0.000 title claims description 63
- 239000011347 resin Substances 0.000 title claims description 63
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- -1 glycidyloxy group Chemical group 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 125000001424 substituent group Chemical group 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
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 35
- 150000002440 hydroxy compounds Chemical class 0.000 description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- 150000003440 styrenes Chemical class 0.000 description 22
- 150000002989 phenols Chemical class 0.000 description 19
- 229920003986 novolac Polymers 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 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
- 239000003566 sealing material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000000704 physical effect Effects 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
- 238000012360 testing method Methods 0.000 description 5
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 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
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 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 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000005504 styryl group Chemical group 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000004780 naphthols Chemical class 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 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
- 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
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 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
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000434 field desorption mass spectrometry Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 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
- 150000002576 ketones Chemical class 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
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007858 starting material 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
- 125000006839 xylylene group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
- 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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical class CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- AERZMMNNWVZSNB-UHFFFAOYSA-N 3-dodec-1-ynyloxolane-2,5-dione Chemical compound CCCCCCCCCCC#CC1CC(=O)OC1=O AERZMMNNWVZSNB-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000290594 Ficus sycomorus Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PBVKRVDQVCQUDK-UHFFFAOYSA-N naphthalene-1,6-diol;naphthalene-1,7-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21.C1=CC=C(O)C2=CC(O)=CC=C21 PBVKRVDQVCQUDK-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
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 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
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type 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
Images
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Description
本発明は、難燃性に優れるとともに、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 provides an epoxy resin that is excellent in flame retardancy and also provides a cured product excellent in moisture resistance and low elasticity, a polyvalent hydroxy resin suitable as an intermediate thereof, a production method thereof, an epoxy resin composition used in these, and It relates to the 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. However, 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。なお、特許文献７及び８にはナフトール系アラルキル型エポキシ樹脂及びこれを含有する半導体封止材料が開示されているが、難燃性に着目したものはない。
一方、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５及び６にはモノスチレン化フェノールノボラック樹脂及びそのエポキシ樹脂を用いるエポキシ樹脂組成物が開示されているが、これらは難燃性に着目したものではない。また、これらはモノスチレン化フェノールを出発原料として用いられていることから、原料物質であるモノスチレン化フェノールを製造する工程を余分に含む問題があった。また、ノボラック化反応後、残存する高沸点のモノスチレン化フェノールモノマーを除去する必要があり、該樹脂が煩雑な工程によって製造される問題があった。更には、予めモノスチレン化されたフェノール類を出発原料としてノボラック樹脂とした場合、溶融粘度が高くなることから流動性において問題があった。 On the other hand, as an example of an epoxy resin composition focused on improving moisture resistance and low stress properties, Patent Documents 5 and 6 disclose a monostyrenated phenol novolak resin and an epoxy resin composition using the epoxy resin. These do not focus on flame retardancy. In addition, since these use a monostyrenated phenol as a starting material, there is a problem that an extra step of producing a monostyrenated phenol as a raw material is included. Further, after the novolak reaction, it is necessary to remove the remaining high-boiling monostyrenated phenol monomer, and there is a problem that the resin is produced by a complicated process. Furthermore, when a novolak resin is used as a starting material from phenols that have been monostyrenated in advance, there is a problem in fluidity because the melt viscosity becomes high.
また、特許文献７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おり、耐熱性、耐湿性、耐クラック性等に優れることが記載されているが、難燃性に着目したものではなく、官能基濃度と難燃性の関係に着目したものもなかった。 Patent Document 7 discloses benzylated polyphenol and its epoxy resin, and describes that it is excellent in heat resistance, moisture resistance, crack resistance, etc., but it does not focus on flame retardancy. None of them focused on the relationship between functional group concentration and flame retardancy.
更に、特許文献８には、インデン構造含有のエポキシ樹脂硬化剤が示されており、誘電特性、耐熱性等に優れることが記載されているが、難燃性に着目したものではなかった。更には、剛直性の高いインデン構造を含むため耐熱性に優れるが接着性の点では性能が十分でなかった。 Furthermore, Patent Document 8 discloses an epoxy resin curing agent containing an indene structure and describes that it is excellent in dielectric properties, heat resistance, etc., but was not focused on flame retardancy. Furthermore, since the indene structure with high rigidity is included, the heat resistance is excellent, but the performance is not sufficient in terms of adhesiveness.
本発明の目的は、積層、成形、注型、接着等の用途において、難燃性に優れるとともに、耐湿性、低弾性等にも優れた性能を有する多価ヒドロキシ樹脂及びエポキシ樹脂を提供すること、優れた難燃性を有するとともに、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。 An object of the present invention is to provide a polyvalent hydroxy resin and an epoxy resin that have excellent performance in flame retardancy, moisture resistance, low elasticity, etc. in applications such as lamination, molding, casting, and adhesion. Providing an epoxy resin composition useful for sealing electrical and electronic parts, circuit board materials, etc., which has excellent flame retardancy, and gives a cured product excellent in moisture resistance, low elasticity, etc., and It is to provide the cured product.
本発明のエポキシ樹脂は、下記一般式（１）で表され、水酸基当量が２５０〜４００ｇ／ｅｑ．の範囲である多価ヒドロキシ樹脂から得ることができる。
The epoxy resin of the present invention is represented by the following general formula (1), and has a hydroxyl group equivalent of 250 to 400 g / eq. It can obtain from the polyhydric hydroxy resin which is the range.
上記多価ヒドロキシ樹脂は、１５０℃における溶融粘度が０．０１〜１０．０Ｐａ・ｓの範囲であることが好ましい。 The polyvalent hydroxy resin preferably has a melt viscosity at 150 ° C. in the range of 0.01 to 10.0 Pa · s.
そして、下記一般式（２）で表される多価ヒドロキシ化合物のヒドロキシ基１モルに対し、スチレン類０．１〜４．０モルを、酸触媒の存在下に反応させることにより、上記式（ａ）で表される置換基が多価ヒドロキシ化合物のベンゼン環又はナフタレン環に置換した構造を有する多価ヒドロキシ樹脂を製造することができる。
すなわち、本発明は、下記一般式（３）
上記エポキシ樹脂の１５０℃における溶融粘度が０．０１〜１０．０Ｐａ・ｓの範囲にあることが好ましい。 The epoxy resin preferably has a melt viscosity at 150 ° C. in the range of 0.01 to 10.0 Pa · s.
また、本発明は、上記の多価ヒドロキシ樹脂とエピクロルヒドリンを反応させることを特徴とするエポキシ樹脂の製造方法である。 Moreover, this invention is a manufacturing method of the epoxy resin characterized by making said polyhydric hydroxy resin and epichlorohydrin react.
更に、本発明は、エポキシ樹脂及び硬化剤よりなるエポキシ樹脂組成物において、上記の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である。また、本発明は上記のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物である。
Furthermore, this invention is an epoxy resin composition formed by mix | blending said epoxy resin as an essential component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent. Moreover, this invention is an epoxy resin hardened | cured material formed by hardening | curing said epoxy resin composition.
本発明のエポキシ樹脂及び多価ヒドロキシ樹脂は、エポキシ樹脂組成物に応用した場合、難燃性に優れるとともに、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、難燃性に優れ、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 flame retardancy and also in moisture resistance and low elasticity, and seals electrical and electronic parts It can be suitably used for applications such as circuit board materials. In particular, the use of a flame retardant having excellent flame retardancy and environmental impact is made unnecessary or reduced.
まず、本発明の多価ヒドロキシ樹脂（以下、ＰＳＮと略す）について説明する。本発明のＰＳＮは一般式（１）で表され、これは一般式（２）で表される多価ヒドロキシ化合物（ＰＳＮと区別する場合は、多価ヒドロキシ化合物（２）ともいう）とスチレン類を反応させることにより得ることができる。 First, the polyvalent hydroxy resin (hereinafter abbreviated as PSN) of the present invention will be described. The PSN of the present invention is represented by the general formula (1), which is a polyvalent hydroxy compound represented by the general formula (2) (also referred to as a polyvalent hydroxy compound (2) when distinguished from PSN) and styrenes. Can be obtained by reacting.
本発明のＰＳＮでは、先ず、多価ヒドロキシ化合物（２）の基本構造に対し、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（２）のベンゼン環又はナフタレン環の水素と式（a）で表わされる置換基（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、水酸基当量を高くすることで、エポキシ基由来の易燃成分の脂肪族炭素率は低くなり、高度な難燃性を発現させることができる。また、芳香族性に富んだスチレンを付加させることにより、芳香族性はより一層向上し、難燃性に加え耐湿性の向上にも効果的である。 In the PSN of the present invention, first, the hydroxyl group equivalent can be arbitrarily adjusted by adding styrenes to the basic structure of the polyvalent hydroxy compound (2). Here, the addition of styrenes refers to the replacement of hydrogen on the benzene ring or naphthalene ring of the polyvalent hydroxy compound (2) with the substituent represented by the formula (a) (also referred to as a styryl group). In other words, in the epoxy resin cured product, the hydroxypropyl group generated by the reaction between the epoxy group and the hydroxyl group is said to burn easily, but by increasing the hydroxyl equivalent, aliphatic carbon of the flammable component derived from the epoxy group The rate is low and a high degree of flame retardancy can be expressed. Moreover, by adding styrene rich in aromaticity, the aromaticity is further improved, and it is effective in improving moisture resistance in addition to flame retardancy.
よって、これらを用いて高難燃性のエポキシ樹脂組成物、特に半導体封止用エポキシ樹脂組成物が得られる。すなわち、それらの組成物における高難燃性とともに、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半導体装置が得られる。 Therefore, a highly flame-retardant epoxy resin composition, especially an epoxy resin composition for semiconductor encapsulation is obtained using these. That is, in addition to high flame retardancy in these compositions, physical properties excellent in moisture resistance and low elasticity are expressed, and a highly reliable semiconductor device can be obtained using this material.
次に、本発明のＰＳＮでは、スチレン類を付加することで、分子量は増加するが、半導体封止材等に適した溶融粘度範囲を維持できる。このことは半導体封止用材料として使用した場合、シリカ等の高充填化が可能であり、その結果、各種物性の向上、例えば、難燃性の向上や更なる低吸水化や熱膨張係数の減少等により信頼性に優れた材料が得られる。 Next, in the PSN of the present invention, the addition of styrenes increases the molecular weight, but can maintain a melt viscosity range suitable for a semiconductor encapsulant and the like. When this is used as a semiconductor sealing material, it is possible to increase the filling of silica or the like. As a result, various physical properties are improved, for example, improved flame retardancy, further lower water absorption and thermal expansion coefficient. A material having excellent reliability can be obtained due to reduction or the like.
本発明のＰＳＮは、一般式（２）で表される多価ヒドロキシ化合物（２）とスチレン類とを付加反応させることにより得られる。この際、多価ヒドロキシ化合物（２）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、フェノール成分（一般式（２）中のＡで表される基をいう）１モルに対するスチレン類の使用割合が０．１から４．０モルの範囲が好ましく、より好ましくは０．５〜３．０モルの範囲である。 The PSN of the present invention can be obtained by addition reaction of the polyvalent hydroxy compound (2) represented by the general formula (2) and styrenes. At this time, the proportion of the polyvalent hydroxy compound (2) and the styrenes is represented by a phenol component (A in the general formula (2), considering the balance between flame retardancy and curability of the obtained cured product. The ratio of the styrenes used per mole is preferably in the range of 0.1 to 4.0 moles, more preferably in the range of 0.5 to 3.0 moles.
この反応では、スチレン類が多価ヒドロキシ化合物（２）中のＯＨ基を有する芳香族環に付加して上記式（ａ）で表わされるスチレニル基が置換する。また、スチレン類の付加位置は、主として、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。 In this reaction, styrenes are added to the aromatic ring having an OH group in the polyvalent hydroxy compound (2) to substitute the styryl group represented by the above formula (a). Further, the addition position of styrenes is mainly the vacant ortho and / or para position of the polyvalent hydroxy compound.
また、本発明のＰＳＮの製造方法では、フェノール成分に対してスチレン類の使用割合を過剰とすれば、スチレンの付加反応割合が上昇し、分子量を容易に増大させることができる。 Further, in the method for producing PSN of the present invention, if the proportion of styrene used is excessive with respect to the phenol component, the proportion of addition reaction of styrene increases and the molecular weight can be easily increased.
このようにして得られる本発明のＰＳＮの水酸基当量は２５０〜４００ｇ／ｅｑ．の範囲にあり、より好ましくは２７０〜３５０ｇ／ｅｑ．の範囲である。水酸基当量がこの範囲より低いと高度な難燃性は得られ難く、この範囲より高いと高度な難燃性は得られるが、硬化性に劣り、同用途での使用が困難になる傾向がある。 The hydroxyl equivalent of the PSN of the present invention obtained in this way is 250 to 400 g / eq. More preferably, it is 270-350 g / eq. Range. If the hydroxyl equivalent is lower than this range, it is difficult to obtain high flame retardancy. .
また、本発明のＰＳＮの製造原料となる多価ヒドロキシ化合物（２）としては、汎用のフェノール樹脂、フェノールアラルキル樹脂、ナフトールアラルキル樹脂等が挙げられる。より高度な難燃性、耐湿性、接着性を得るためには、アラルキル構造を有する多価ヒドロキシ化合物を用いることが好ましい。すなわち、一般式（２）において、Ｘが式（ｃ）で表わされる構造を有する多価ヒドロキシ化合物が好ましい。 Moreover, general-purpose phenol resin, phenol aralkyl resin, naphthol aralkyl resin, etc. are mentioned as polyhydric hydroxy compound (2) used as the manufacturing raw material of PSN of this invention. In order to obtain higher flame retardancy, moisture resistance and adhesion, it is preferable to use a polyvalent hydroxy compound having an aralkyl structure. That is, in the general formula (2), a polyvalent hydroxy compound having a structure in which X is represented by the formula (c) is preferable.
また、本発明のＰＳＮ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 PSN of the present invention preferably has a melt viscosity at 150 ° C. 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.
一般式（１）、（２）及び（３）において、Ａを除き、共通の記号は同じ意味を有すると理解される。これらの式において、独立に、Ａは炭素数１〜８のアルキル基若しくは水酸基が置換してもよいベンゼン環又はナフタレン環からなる基を示す。ただし、一般式（３）においては、Ａは水酸基が置換することはなく、グリシジルオキシ基が置換する点で相違する。また、一般式（２）においては、Ａは式（a）で表わされる置換基を有しない点で相違する。なお、一般式（３）において、Ｇはグリシジル基を示す。一般式（１）、（２）及び（３）において、Ａにアルキル基が置換する場合、アルキル基としては炭素数１〜８のアルキル基が好ましい。水酸基が置換する場合、その数は１が好ましい。すなわち、Ａに置換する水酸基は合計して１又は２が好ましい。また、一般式（２）においては、Ａは式（a）で表わされる置換基と置換可能な水素を１以上、好ましくは３以上有する。 In general formulas (1), (2) and (3), it is understood that common symbols have the same meaning except A. In these formulas, A independently represents a group comprising a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 8 carbon atoms or a hydroxyl group. However, in the general formula (3), A is different in that a hydroxyl group is not substituted and a glycidyloxy group is substituted. In the general formula (2), A is different in that it does not have a substituent represented by the formula (a). In general formula (3), G represents a glycidyl group. In the general formulas (1), (2) and (3), when A is substituted with an alkyl group, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. When the hydroxyl group is substituted, the number is preferably 1. That is, the total number of hydroxyl groups substituted by A is preferably 1 or 2. In the general formula (2), A has 1 or more, preferably 3 or more, hydrogens that can be substituted with the substituent represented by the formula (a).
Ｒ1は上記式（ａ）で表されるスチレニル基を示す。ｐ及びｑは０〜２の数を示すが、ｐ＋ｑは１以上である。より好ましくは、ｐ＋ｑは２以上であり、更に好ましくは２.６〜４である。有利には１個のＡに対し、平均として０．２〜２個のスチレニル基が置換することが好まく、１．３〜２個が特に好ましい。式（ａ）において、Ｒ2は水素又は炭素数１〜６の炭化水素基を示すが、好ましくは水素又は炭素数１〜３のアルキル基であり、より好ましくは水素である。このＲ2は反応原料として使用するスチレン類によって定まる。ここで、ｑはｎが１以外の数である場合は、平均値である。また、ｐとｑの平均は全部のｐとｑの平均値を意味する。 R 1 represents a styryl group represented by the above formula (a). p and q represent a number of 0 to 2, but p + q is 1 or more. More preferably, p + q is 2 or more, and more preferably 2.6-4. It is preferred that an average of 0.2 to 2 styryl groups be substituted for one A, and 1.3 to 2 is particularly preferred. In the formula (a), R 2 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen. This R 2 is determined by the styrenes used as reaction raw materials. Here, q is an average value when n is a number other than 1. The average of p and q means the average value of all p and q.
Ｘは式（ｂ）又は式（ｃ）で表される架橋基であり、好ましくは式（ｃ）で表される架橋基である。Ｒ3、Ｒ4、Ｒ5及びＲ6は独立に、水素原子又は炭素数１〜６の炭化水素基を示すが、好ましくは、水素原子又は炭素数１〜３のアルキル基である。ｎは１〜２０の数を示すが、好ましくは、平均として１．５〜３．０の範囲である。更にｎ＝２以上である成分がゲルパーミエーションクロマトグラフィーチャートの面積百分率値において３０％以上であるものが好ましい。なお、ｎが異なる混合物である場合は、ｎは数平均である。 X is a crosslinking group represented by the formula (b) or the formula (c), preferably a crosslinking group represented by the formula (c). R 3 , R 4 , R 5 and R 6 independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Although n shows the number of 1-20, Preferably, it is the range of 1.5-3.0 as an average. Furthermore, it is preferable that the component in which n = 2 or more is 30% or more in the area percentage value of the gel permeation chromatography chart. In addition, when n is a different mixture, n is a number average.
次に、本発明のＰＳＮの製造方法について説明する。本発明のＰＳＮを製造する方法で用いる多価ヒドロキシ化合物（２）として、汎用のフェノール樹脂が挙げられる。具体的には一般式（２）における連結基Ｘがアルデヒド又はケトン類から誘導されたもの、例えば、一般式（５）で表されるものがある。 Next, the manufacturing method of PSN of this invention is demonstrated. As the polyvalent hydroxy compound (2) used in the method for producing PSN of the present invention, a general-purpose phenol resin can be mentioned. Specifically, there are those in which the linking group X in the general formula (2) is derived from aldehydes or ketones, for example, those represented by the general formula (5).
また、フェノールアラルキル樹脂も同様に挙げられる。具体的には一般式（２）における連結基Ｘがキシリレングリコール類、キシリレングリコールジメチルエーテル類、キシリレンジクロライド類、ジビニルベンゼン類、ジイソプロペニルベンゼン類等から誘導されたもの、例えば、一般式（６）で表されるものである。 Moreover, a phenol aralkyl resin is also mentioned similarly. Specifically, the linking group X in the general formula (2) is derived from xylylene glycols, xylylene glycol dimethyl ethers, xylylene dichlorides, divinylbenzenes, diisopropenylbenzenes, etc. It is represented by (6).
更には、ナフトールアラルキル樹脂も同様に挙げられる。具体的には一般式（２）におけるＡがナフタレン環を示し、連結基Ｘがキシリレングリコール類、キシリレングリコールジメチルエーテル類、キシリレンジクロライド類等から誘導されたもの、例えば、一般式（７）で表されるものである。 Furthermore, a naphthol aralkyl resin is mentioned similarly. Specifically, A in the general formula (2) represents a naphthalene ring, and the linking group X is derived from xylylene glycols, xylylene glycol dimethyl ethers, xylylene dichlorides, etc., for example, the general formula (7) It is represented by
これらの多価ヒドロキシ化合物（２）を得るために用いられるフェノール類又はナフトール類としては、例えば、フェノール、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単独でもよいし、２種以上を併用してもよい。
Examples of phenols or naphthols used to obtain these polyvalent hydroxy compounds (2) include phenol, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, and tertiary butylphenol. , Allylphenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-
反応に用いるスチレン類は、スチレン又は炭素数１〜６の炭化水素基若しくは水酸基が置換したスチレンである。このスチレン類は少量の他の反応成分を含んでもよい。他の反応成分として、α−メチルスチレン、ジビニルベンゼン、インデン、クマロン、ベンゾチオフェン、インドール、ビニルナフタレン等の不飽和結合含有成分を含む場合、得られる多価ヒドロキシ樹脂にはこれらから生ずる基が芳香環上に置換した化合物が含まれることになる。本発明の多価ヒドロキシ樹脂の製造方法で得られるフェノール樹脂は、このような置換基を有する多価ヒドロキシ樹脂を含み得る。同様に、本発明のエポキシ樹脂の製造方法で得られるエポキシ樹脂は、このような置換基を有するエポキシ樹脂を含み得る。 Styrenes used in the reaction are styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms or a hydroxyl group. The styrenes may contain small amounts of other reaction components. When other reactive components include unsaturated bond-containing components such as α-methylstyrene, divinylbenzene, indene, coumarone, benzothiophene, indole, and vinylnaphthalene, the resulting polyvalent hydroxy resin has aromatic groups. A substituted compound on the ring will be included. The phenol resin obtained by the method for producing a polyvalent hydroxy resin of the present invention may contain a polyvalent hydroxy resin having such a substituent. Similarly, the epoxy resin obtained by the method for producing an epoxy resin of the present invention can include an epoxy resin having such a substituent.
スチレン類を多価ヒドロキシ化合物（２）に反応させる本発明の方法において、スチレン類の使用量は、多価ヒドロキシ化合物のフェノール成分１モルに対し、０．１〜４モルの範囲が好ましい。より好ましくは、１.３〜３モルの範囲である。そして、一般式（１）におけるｐとｑが平均１.３〜２の範囲となることが好ましい。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。本発明では、これらスチレン類の使用量により、ＰＳＮの水酸基当量を２５０ｇ／ｅｑ〜４００ｇ／ｅｑ．に調整することが可能である。この結果、エポキシ樹脂組成物の難燃性、耐湿性、低弾性等の優れた物性を発現し、半導体封止材料等の用途で難燃性及び信頼性等に優れた組成物を与える。それ故、スチレン類の使用割合は、原料の多価ヒドロキシ化合物自身の水酸基当量により、変更される。すなわち、フェノールノボラック樹脂のような水酸基当量の小さいものは、比較的スチレン類の使用割合が多くなり、アルキル置換フェノールノボラック類、フェノールアラルキル樹脂類、ナフトールアラルキル樹脂類等では相対的に使用割合が少なくてもよい。 In the method of the present invention in which styrenes are reacted with the polyvalent hydroxy compound (2), the amount of styrene used is preferably in the range of 0.1 to 4 mol with respect to 1 mol of the phenol component of the polyvalent hydroxy compound. More preferably, it is the range of 1.3-3 mol. And it is preferable that p and q in General formula (1) become the range of 1.3-3 on average. 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. In the present invention, the hydroxyl group equivalent of PSN is 250 g / eq to 400 g / eq. It is possible to adjust to. As a result, the epoxy resin composition exhibits excellent physical properties such as flame retardancy, moisture resistance, and low elasticity, and gives a composition excellent in flame retardancy and reliability in applications such as semiconductor sealing materials. Therefore, the use ratio of styrenes is changed by the hydroxyl equivalent of the polyvalent hydroxy compound itself. That is, those having a small hydroxyl equivalent, such as phenol novolac resins, have a relatively high proportion of styrenes, and those having a relatively small proportion of alkyl-substituted phenol novolacs, phenol aralkyl resins, naphthol aralkyl resins, etc. May be.
この反応は酸触媒の存在下に行うことができる。この酸触媒としては、周知の無機酸、有機酸より適宜選択することができる。例えば、塩酸、硫酸、燐酸等の鉱酸や、ギ酸、シュウ酸、トリフルオロ酢酸、ｐ−トルエンスルホン酸、ジメチル硫酸、ジエチル硫酸等の有機酸や、塩化亜鉛、塩化アルミニウム、塩化鉄、三フッ化ホウ素等のルイス酸あるいはイオン交換樹脂、活性白土、シリカ−アルミナ、ゼオライト等の固体酸等が挙げられる。 This reaction can be carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride. Examples thereof include Lewis acids such as boron fluoride or ion exchange resins, activated clays, silica-alumina, solid acids such as zeolite, and the like.
また、この反応は通常、１０〜２５０℃で１〜２０時間行われる。更に、反応の際には、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、メチルセロソルブ、エチルセロソルブ等のアルコール類や、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、ジメチルエーテル、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、ベンゼン、トルエン、クロロベンゼン、ジクロロベンゼン等の芳香族化合物等を溶媒として使用することができる。 Moreover, this reaction is normally performed at 10-250 degreeC for 1 to 20 hours. Further, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, diisopropyl ether, Ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the solvent.
この反応を実施する具体的方法としては、全原料を一括装入し、そのまま所定の温度で反応させるか、又は、多価ヒドロキシ化合物と触媒を装入し、所定の温度に保ちつつ、スチレン類を滴下させながら反応させる方法が一般的である。この際、滴下時間は、５時間以下が好ましく、通常、１〜１０時間である。反応後、溶媒を使用した場合は、必要により、触媒成分を取り除いた後、溶媒を留去させて本発明の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. 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について述べる。
本発明のエポキシ樹脂(ＰＳＮＥと略す）は一般式（３）で表される。また、多価ヒドロキシ樹脂（ＰＳＮ）は一般式（１）で表される。ＰＳＮＥは、ＰＳＮをエポキシ化することにより得ることができる。
Next, the epoxy resin of the present invention will be described.
The epoxy resin (abbreviated as PSNE) of the present invention is represented by the general formula (3). The polyvalent hydroxy resin (PSN) is represented by the general formula (1). PSNE can be obtained by epoxidizing PSN.
一般式（３）において、一般式（１）と共通な記号及び式は、特に断らない限り同じ意味を有する。Gはグリシジル基を表すが、一般式（１）の水酸基が反応して生じる。Ｒ1は式（a）で表わされる置換基である。 In the general formula (3), symbols and formulas common to the general formula (1) have the same meanings unless otherwise specified. G represents a glycidyl group, which is generated by the reaction of the hydroxyl group of the general formula (1). R 1 is a substituent represented by the formula (a).
Ｘは式（ｂ）又は式（ｃ）で表される架橋基であるが、Ｒ3、Ｒ4、Ｒ5及びＲ6は独立に、水素原子又は炭素数１〜６の炭化水素基を示す。ＸはＡを架橋するが、Ｘの置換位置は、特に限定するものではない。
本発明のＰＳＮＥは、上記一般式（１）で表されるＰＳＮと、エピクロルヒドリンを反応させることより製造することが有利であるが、この反応に限らない。
X is a bridging group represented by formula (b) or formula (c), but R 3 , R 4 , R 5 and R 6 independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. . X crosslinks A, but the substitution position of X is not particularly limited.
The PSNE of the present invention is advantageously produced by reacting the PSN represented by the general formula (1) with epichlorohydrin, but is not limited to this reaction.
ＰＳＮをエピクロルヒドリンと反応させる反応の他、ＰＳＮとハロゲン化アリルを反応させ、アリルエーテル化合物とした後、過酸化物と反応させる方法をとることもできる。上記ＰＳＮをエピクロルヒドリンと反応させる反応は、通常のエポキシ化反応と同様に行うことができる。 In addition to the reaction of reacting PSN with epichlorohydrin, PSN and allyl halide can be reacted to form an allyl ether compound and then reacted with peroxide. The reaction of reacting the PSN with epichlorohydrin can be performed in the same manner as a normal epoxidation reaction.
例えば、上記ＰＳＮ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、ＰＳＮ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ＰＳＮ中の水酸基１モルに対して過剰に用いられるが、通常、ＰＳＮ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 PSN is dissolved in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, the temperature 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, per mol of the PSN hydroxyl group. Epichlorohydrin is used in excess with respect to 1 mol of the hydroxyl group in PSN, but is usually in the range of 1.5 to 30 mol, preferably 2 to 15 mol, with respect to 1 mol of the hydroxyl group in PSN. 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ＰＳＮＥを配合した組成物。
２）硬化剤の一部又は全部として前記ＰＳＮ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ＰＳＮＥとＰＳＮ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 PSNE as a part or all of an epoxy resin.
2) The composition which mix | blended the said PSN as a part or all of a hardening | curing agent.
3) The composition which mix | blended said PSNE and PSN as 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、ＰＳＮ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 compositions 2) and 3), the amount of PSN 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ＰＳＮを用いる場合、通常、ＰＳＮの配合量は、ＰＳＮ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 PSN is used as the total amount of the curing agent, the blending amount of PSN is usually blended in consideration of the equivalent balance of the OH group of PSN 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ＰＳＮ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、ＰＳＮ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。ＰＳＮ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。 A curing agent other than PSN 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 PSN 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 PSN is less than this, the effect of improving the low hygroscopicity, adhesion and flame retardancy is small, and when it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.
ＰＳＮ以外の硬化剤としては、一般にエポキシ樹脂の硬化剤として知られているものはすべて使用でき、ジシアンジアミド、酸無水物類、多価フェノール類、芳香族及び脂肪族アミン類等がある。これらの中でも、半導体封止材等の高い電気絶縁性が要求される分野においては、多価フェノール類を硬化剤として用いることが好ましい。以下に、硬化剤の具体例を示す。 As the curing agent other than PSN, all 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. Below, the specific example of a hardening | curing agent is shown.
酸無水物硬化剤としては、例えば、無水フタル酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチル無水ハイミック酸、無水ドデシニルコハク酸、無水ナジック酸、無水トリメリット酸等がある。 Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecynyl succinic anhydride, nadic anhydride, There are trimellitic anhydride and the like.
多価フェノール類としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４'−ビフェノール、２，２'−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類、あるいは、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、フェノールノボラック、ｏ-クレゾールノボラック、ナフトールノボラック、ポリビニルフェノール等に代表される３価以上のフェノール類がある。更には、フェノール類、ナフトール類、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４'−ビフェノール、２，２'−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類と、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｐ−キシリレンジクロライド、ビスクロロメチルビフェニル、ビスクロロメチルナフタレン等の縮合剤により合成される多価フェノール性化合物等がある。 Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol, or , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, There are phenols. Furthermore, divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, There are polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, bischloromethylnaphthalene, and the like.
アミン類としては、４，４'−ジアミノジフェニルメタン、４，４'−ジアミノジフェニルプロパン、４，４'−ジアミノジフェニルスルホン、ｍ−フェニレンジアミン、ｐ−キシリレンジアミン等の芳香族アミン類、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、リエチレンテトラミン等の脂肪族アミン類がある。
上記組成物には、これら硬化剤の１種又は２種以上を混合して用いることができる。
Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and reethylenetetramine.
One or more of these curing agents can be mixed and used in the composition.
上記組成物に使用されるエポキシ樹脂としては、１分子中にエポキシ基を２個以上有するもの中から選択される。例えば、ビスフェノールＡ、ビスフェノールＦ、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、テトラブロモビスフェノールＡ、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）エタンや、フェノール、クレゾール、ナフトール等のノボラック樹脂、フェノール、クレゾール、ナフトール等のアラルキル樹脂等の３価以上のフェノール性化合物の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。 The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, tetrabromobisphenol A, hydroquinone, resorcin, or tris- (4 -Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resins such as phenol, cresol and naphthol, and aralkyl resins such as phenol, cresol and naphthol There are glycidyl etherified compounds of the active compound. 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、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、ＰＳＮＥ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ＰＳＮＥを必須成分とする組成物の場合、ＰＳＮＥの配合量はエポキシ樹脂全体中、５〜１００％、好ましくは６０〜１００％の範囲であることがよい。 In the case of the compositions 1) and 3), another epoxy resin may be blended in addition to PSNE as an epoxy resin component in the epoxy resin composition. 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 PSNE of this invention as an essential component, the compounding quantity of PSNE is 5-100% in the whole epoxy resin, Preferably it is good to be the range of 60-100%.
本発明のエポキシ樹脂組成物中には、ポリエステル、ポリアミド、ポリイミド、ポリエーテル、ポリウレタン、石油樹脂、インデン樹脂、インデン・クマロン樹脂、フェノキシ樹脂等のオリゴマー又は高分子化合物を他の改質剤等として適宜配合してもよい。添加量は、通常、エポキシ樹脂１００重量部に対して、２〜３０重量部の範囲である。 In the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, etc. is used as another modifier. You may mix | blend suitably. The addition amount is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.
また、本発明のエポキシ樹脂組成物には、無機充填剤、顔料、難然剤、揺変性付与剤、カップリング剤、流動性向上剤等の添加剤を配合できる。無機充填剤としては、例えば、球状あるいは、破砕状の溶融シリカ、結晶シリカ等のシリカ粉末、アルミナ粉末、ガラス粉末、又はマイカ、タルク、炭酸カルシウム、アルミナ、水和アルミナ等が挙げられ、半導体封止材に用いる場合の好ましい配合量は７０重量％以上であり、更に好ましくは８０重量％以上である。 In addition, the epoxy resin composition of the present invention can contain additives such as inorganic fillers, pigments, refractory agents, thixotropic agents, coupling agents, fluidity improvers and the like. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a stopper is 70% by weight or more, 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、この硬化物は低吸湿性、高耐熱性、密着性、難燃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, and this cured product is excellent in terms of low hygroscopicity, high heat resistance, adhesion, flame retardancy, and the like. Become. 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。
ここで、粘度はＢ型粘度計を用い、軟化点はＪＩＳ−Ｋ−２２０７に従い環球法で測定した。また、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定条件は、装置；ＭＯＤＥＬ１５１（ウォーターズ（株）製）、カラム；ＴＳＫ−ＧＥＬ２０００×３本及びＴＳＫ−ＧＥＬ４００×１本（いずれも東ソー（株）製）、溶媒；テトラヒドロフラン、流量；１ ｍｌ／ｍｉｎ、温度；３８℃、検出器；ＲＩであり、検量線にはポリスチレン標準液を使用した。
なお、実施例1〜4及び9〜13は、参考例であると理解される。
Hereinafter, the present invention will be described more specifically with reference to examples.
Here, the viscosity was measured using a B-type viscometer, and the softening point was measured by the ring and ball method according to JIS-K-2207. The gel permeation chromatography (GPC) measurement conditions were as follows: apparatus; MODEL 151 (manufactured by Waters), column; TSK-
In addition, Examples 1-4 and 9-13 are understood as reference examples.
（多価ヒドロキシ樹脂の合成）
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、ＧＰＣ測定によるｎ＝１の成分（３８％）、ｎ＝２以上の成分（６２％））を１０５ｇ、酸触媒としてｐ−トルエンスルホン酸０．１３ｇを仕込み１５０℃に昇温した。次に、１５０℃にて攪拌しながら、スチレン類としてスチレン１５６ｇ（１．５モル）を３時間かけて滴下し反応させた。さらに１５０℃にて１時間反応後、ＭＩＢＫ５００ｇ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２５５ｇを得た。その軟化点は７５℃、１５０℃での溶融粘度は０．１６Ｐａ・ｓ、水酸基当量は２６１ｇ／ｅｑ．であり、ｐ、ｑの平均は１．５であった。この化合物をＰＳＮ−Ａという。ＰＳＮ−Ａの1Ｈ−ＮＭＲスペクトルを図１、赤外吸収スペクトルを図２、ＧＰＣチャートを図３、ＦＤ−ＭＳチャートを図４に示す。
(Synthesis of polyvalent hydroxy resin)
Example 1
Into a 1 L 4-neck flask, phenol novolac (manufactured by Showa Polymer; BRG-555, hydroxyl group equivalent 105 g / eq., Softening point 67 ° C., melt viscosity 0.080 Pa · s at 150 ° C., GPC as a polyvalent hydroxy compound component 105 g of n = 1 component (38%) and n = 2 or more component (62%)) and 0.13 g of p-toluenesulfonic acid as an acid catalyst were charged and heated to 150 ° C. Next, with stirring at 150 ° C., 156 g (1.5 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Furthermore, after reacting at 150 ° C. for 1 hour, it was dissolved in 500 g of MIBK and washed 5 times at 80 ° C. Subsequently, after MIBK was distilled off under reduced pressure, 255 g of a polyvalent hydroxy resin was obtained. Its softening point is 75 ° C., melt viscosity at 150 ° C. is 0.16 Pa · s, and hydroxyl equivalent is 261 g / eq. The average of p and q was 1.5. This compound is referred to as PSN-A. FIG. 1 shows the 1 H-NMR spectrum of PSN-A, FIG. 2 shows the infrared absorption spectrum, FIG. 3 shows the GPC chart, and FIG. 4 shows the FD-MS chart.
実施例２
多価ヒドロキシ化合物成分として、ビスフェノールＦ（本州化学製、４，４’体（３１％）、２，４’体（４９％）、２，２’体（２０％））を１００ｇ、酸触媒としてｐ−トルエンスルホン酸０．１３ｇを仕込み１５０℃に昇温した。次に、１５０℃にて攪拌しながら、スチレン類としてスチレン１５６ｇ（１．５モル）を３時間かけて滴下し反応させた。その後、実施例１と同様な処理を行った後、多価ヒドロキシ樹脂２５１ｇを得た。その軟化点は５０℃、１５０℃での溶融粘度は０．０２０Ｐａ・ｓ、水酸基当量は２５６ｇ／ｅｑ．であり、ｐ、ｑの平均は１．５であった。この化合物をＰＳＮ−Ｂという。
Example 2
As a polyvalent hydroxy compound component, 100 g of bisphenol F (4,4 ′ form (31%), 2,4 ′ form (49%), 2,2 ′ form (20%)) manufactured by Honshu Chemical Co., Ltd. as an acid catalyst 0.13 g of p-toluenesulfonic acid was charged and heated to 150 ° C. Next, with stirring at 150 ° C., 156 g (1.5 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Thereafter, the same treatment as in Example 1 was performed, and then 251 g of a polyvalent hydroxy resin was obtained. The softening point is 50 ° C., the melt viscosity at 150 ° C. is 0.020 Pa · s, and the hydroxyl equivalent is 256 g / eq. The average of p and q was 1.5. This compound is referred to as PSN-B.
実施例３
多価ヒドロキシ化合物成分として、フェノールアラルキル樹脂（明和化成株式会社製；ＭＥＨ−７８００ＳＳ、水酸基当量１７５ｇ／ｅｑ．、軟化点６６℃、１５０℃での溶融粘度０．０７Ｐａ・ｓ）を１７５ｇ、酸触媒としてｐ−トルエンスルホン酸０．１６ｇを仕込み１５０℃に昇温した。次に、１５０℃にて攪拌しながら、スチレン類としてスチレン１３５ｇ（１．３モル）を３時間かけて滴下し反応させた。その後、実施例１と同様な処理を行った後、多価ヒドロキシ樹脂３０５ｇを得た。その軟化点は８２℃、１５０℃での溶融粘度は０．４５Ｐａ・ｓ、水酸基当量は３１０ｇ／ｅｑ．であり、ｐ、ｑの平均は１．３であった。この化合物をＰＳＮ−Ｃという。
Example 3
As a polyvalent hydroxy compound component, 175 g of phenol aralkyl resin (Maywa Kasei Co., Ltd .; MEH-7800SS, hydroxyl equivalent 175 g / eq., Softening point 66 ° C., melt viscosity 0.050 Pa · s at 150 ° C.), acid catalyst P-toluenesulfonic acid 0.16g was prepared and heated to 150 ° C. Next, while stirring at 150 ° C., 135 g (1.3 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Then, after processing similar to Example 1, 305 g of polyvalent hydroxy resin was obtained. Its softening point is 82 ° C., melt viscosity at 150 ° C. is 0.45 Pa · s, and hydroxyl equivalent is 310 g / eq. The average of p and q was 1.3. This compound is referred to as PSN-C.
実施例４
多価ヒドロキシ化合物成分として、１−ナフトールアラルキル樹脂（東都化成株式会社製；ＳＮ−４７５、水酸基当量２１０ｇ／ｅｑ．、軟化点７７℃、１５０℃での溶融粘度０．０４Ｐａ・ｓ）を２１０ｇ、酸触媒としてｐ−トルエンスルホン酸０．１７ｇを仕込み１５０℃に昇温した。次に、１５０℃にて攪拌しながら、スチレン類としてスチレン１３５ｇ（１．３モル）を３時間かけて滴下し反応させた。その後、実施例１と同様な処理を行った後、多価ヒドロキシ樹脂３４０ｇを得た。その軟化点は８８℃、１５０℃での溶融粘度は０．４１Ｐａ・ｓ、水酸基当量は３４５ｇ／ｅｑ．であり、ｐ、ｑの平均は１．３であった。この化合物をＰＳＮ−Ｄという。
Example 4
As a polyvalent hydroxy compound component, 210 g of 1-naphthol aralkyl resin (manufactured by Toto Kasei Co., Ltd .; SN-475, hydroxyl group equivalent 210 g / eq., Softening point 77 ° C., melt viscosity 0.050 Pa · s at 150 ° C.), As an acid catalyst, 0.17 g of p-toluenesulfonic acid was charged and heated to 150 ° C. Next, while stirring at 150 ° C., 135 g (1.3 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Then, after processing similar to Example 1, 340 g of polyvalent hydroxy resin was obtained. Its softening point is 88 ° C., melt viscosity at 150 ° C. is 0.41 Pa · s, and hydroxyl equivalent is 345 g / eq. The average of p and q was 1.3. This compound is referred to as PSN-D.
ここで、ｐ、ｑの平均は、ｐとｑは実質的に等価であるので、1つのAに置換したR1の平均の数を意味する。なお、反応に使用したスチレンはほぼ全量が反応する。 Here, the average of p and q means the average number of R 1 substituted with one A because p and q are substantially equivalent. Note that almost all of the styrene used in the reaction reacts.
合成例１
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（昭和高分子製；ＢＲＧ−５５５、水酸基当量１０５ｇ／ｅｑ．、軟化点６７℃、１５０℃での溶融粘度０．０８Ｐａ・ｓ）を１０５ｇ、酸触媒としてｐ−トルエンスルホン酸０．１０ｇを仕込み１５０℃に昇温した。次に、１５０℃にて攪拌しながら、スチレン類としてスチレン７３ｇ（０．７モル）を２時間かけて滴下し反応させた。その後、実施例１と同様な処理を行った後、多価ヒドロキシ樹脂１７２ｇを得た。その軟化点は７２℃、１５０℃での溶融粘度は０．１１Ｐａ・ｓ、水酸基当量は１７８ｇ／ｅｑ．であり、ｐ、ｑの平均は０．７であった。
Synthesis example 1
105 g of phenol novolak (manufactured by Showa Polymer; BRG-555, hydroxyl group equivalent 105 g / eq., Softening point 67 ° C., melt viscosity 0.080 Pa · s at 150 ° C.) as the polyvalent hydroxy compound component, p as the acid catalyst -Toluenesulfonic acid 0.10g was prepared and it heated up at 150 degreeC. Next, while stirring at 150 ° C., 73 g (0.7 mol) of styrene as styrenes was dropped over 2 hours to be reacted. Thereafter, the same treatment as in Example 1 was performed, and then 172 g of a polyvalent hydroxy resin was obtained. Its softening point is 72 ° C., melt viscosity at 150 ° C. is 0.11 Pa · s, and hydroxyl equivalent is 178 g / eq. The average of p and q was 0.7.
合成例２
多価ヒドロキシ化合物成分として、ビスフェノールＦ（本州化学製、４，４’体（３１％）、２，４’体（４９％）、２，２’体（２０％））を２００ｇを仕込み１７５℃まで昇温させた。溶融後、撹拌しながらｐ−トルエンスルホン酸０．１３ｇを仕込み、１５０℃においてインデン１１６ｇ（１．０モル）を約３時間かけて滴下した。その後、実施例１と同様な処理を行った後、多価ヒドロキシ樹脂４１３ｇを得た。その軟化点は７８℃、１５０℃での溶融粘度は０．０６Ｐａ・ｓ、水酸基当量は２１６ｇ／ｅｑ．であり、ｐ、ｑの平均は１．０であった。
Synthesis example 2
200 g of bisphenol F (4,4 ′ form (31%), 2,4 ′ form (49%), 2,2 ′ form (20%)) manufactured by Honshu Chemical Co., Ltd. as a polyvalent hydroxy compound component was charged at 175 ° C. The temperature was raised to. After melting, 0.13 g of p-toluenesulfonic acid was charged with stirring, and 116 g (1.0 mol) of indene was added dropwise at 150 ° C. over about 3 hours. Then, after processing similar to Example 1, 413 g of polyvalent hydroxy resin was obtained. Its softening point is 78 ° C., melt viscosity at 150 ° C. is 0.06 Pa · s, and hydroxyl equivalent is 216 g / eq. The average of p and q was 1.0.
（エポキシ樹脂の合成）
実施例５
四つ口セパラブルフラスコに実施例１で得たＰＳＮ−Ａ１５０ｇ、エピクロルヒドリン３０６ｇ、ジエチレングリコールジメチルエーテル４６ｇ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４７．９ｇ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１７２ｇを得た（ＰＳＮＥ−Ａ）。得られた樹脂のエポキシ当量は３２９ｇ／ｅｑ．、軟化点は６２℃、１５０℃における溶融粘度は０．１８Ｐａ・ｓであった。ＰＳＮＥ−Ａの1Ｈ−ＮＭＲスペクトルを図５、赤外吸収スペクトルを図６、ＧＰＣチャートを図７に示す。
(Synthesis of epoxy resin)
Example 5
In a four-necked separable flask, 150 g of PSN-A obtained in Example 1, 306 g of epichlorohydrin and 46 g of diethylene glycol dimethyl ether were stirred and dissolved. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 47.9 g of 48% aqueous sodium hydroxide solution was dropped 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 produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 172 g of an epoxy resin (PSNE-A). The epoxy equivalent of the obtained resin was 329 g / eq. The softening point was 62 ° C. and the melt viscosity at 150 ° C. was 0.18 Pa · s. FIG. 5 shows the 1 H-NMR spectrum of PSNE-A, FIG. 6 shows the infrared absorption spectrum, and FIG. 7 shows the GPC chart.
実施例６
実施例２で得たＰＳＮ−Ｂ１５０ｇを用い、実施例５と同様に反応させエポキシ樹脂１７１ｇを得た（ＰＳＮＥ−Ｂ）。得られた樹脂のエポキシ当量は３２２ｇ／ｅｑ．、１５０℃における溶融粘度は０．０３Ｐａ・ｓであった。
Example 6
Using 150 g of PSN-B obtained in Example 2, the reaction was carried out in the same manner as in Example 5 to obtain 171 g of an epoxy resin (PSNE-B). The epoxy equivalent of the obtained resin was 322 g / eq. The melt viscosity at 150 ° C. was 0.03 Pa · s.
実施例７
実施例３で得たＰＳＮ−Ｃ１５０ｇを用い、実施例５と同様に反応させエポキシ樹脂１６５ｇを得た（ＰＳＮＥ−Ｃ）。得られた樹脂のエポキシ当量は３７８ｇ／ｅｑ．、軟化点は７１℃、１５０℃における溶融粘度は０．５７Ｐａ・ｓであった。
Example 7
Using 150 g of PSN-C obtained in Example 3, the reaction was carried out in the same manner as in Example 5 to obtain 165 g of epoxy resin (PSNE-C). The epoxy equivalent of the obtained resin was 378 g / eq. The softening point was 71 ° C. and the melt viscosity at 150 ° C. was 0.57 Pa · s.
実施例８
実施例４で得たＰＳＮ−Ｄ１５０ｇを用い、実施例５と同様に反応させエポキシ樹脂１６２ｇを得た（ＰＳＮＥ−Ｅ）。得られた樹脂のエポキシ当量は４１１ｇ／ｅｑ．、軟化点は８４℃、１５０℃における溶融粘度は０．６２Ｐａ・ｓであった。
Example 8
Using 150 g of PSN-D obtained in Example 4, the reaction was carried out in the same manner as in Example 5 to obtain 162 g of an epoxy resin (PSNE-E). The epoxy equivalent of the obtained resin was 411 g / eq. The softening point was 84 ° C. and the melt viscosity at 150 ° C. was 0.62 Pa · s.
合成例３
合成例１で得た樹脂を用い、実施例５と同様に反応させエポキシ樹脂１７１ｇを得た。得られた樹脂のエポキシ当量は２４６ｇ／ｅｑ．、軟化点は５７℃、１５０℃における溶融粘度は０．１４Ｐａ・ｓであった。
Synthesis example 3
The resin obtained in Synthesis Example 1 was reacted in the same manner as in Example 5 to obtain 171 g of an epoxy resin. The epoxy equivalent of the obtained resin was 246 g / eq. The softening point was 57 ° C. and the melt viscosity at 150 ° C. was 0.14 Pa · s.
合成例４
合成例２で得た樹脂を用い、実施例５と同様に反応させエポキシ樹脂１６９ｇを得た。得られた樹脂のエポキシ当量は２７８ｇ／ｅｑ．、軟化点は５８℃、１５０℃における溶融粘度は０．０５Ｐａ・ｓであった。
Synthesis example 4
The resin obtained in Synthesis Example 2 was used in the same manner as in Example 5 to obtain 169 g of epoxy resin. The epoxy equivalent of the obtained resin was 278 g / eq. The softening point was 58 ° C. and the melt viscosity at 150 ° C. was 0.05 Pa · s.
実施例９〜１３及び比較例１〜４
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、２、３、４で得たＰＳＮ−Ａ、ＰＳＮ−Ｂ、ＰＳＮ−Ｃ，ＰＳＮ−Ｄ、合成例１、２で得た樹脂の他、フェノールノボラック（硬化剤Ａ：群栄化学製、ＰＳＭ−４２６１；ＯＨ当量１０３、軟化点 ８２℃）又はフェノールアラルキル樹脂（硬化剤Ｂ；明和化成製、ＭＥＨ−７８００ＳＳ、ＯＨ当量１７５、軟化点６７℃）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及び表３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。
Examples 9-13 and Comparative Examples 1-4
An o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) was used as an epoxy resin component, and PSN-A and PSN-B obtained in Examples 1, 2, 3, and 4 were used as curing agents. In addition to the resins obtained in PSN-C, PSN-D and Synthesis Examples 1 and 2, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent 103, softening point 82 ° C.) or phenol aralkyl resin ( Curing agent B: Meiwa Kasei Co., Ltd., MEH-7800SS, OH equivalent 175, softening point 67 ° C.) was used. Silica (average particle diameter of 18 μm) as a filler and triphenylphosphine as a curing accelerator were kneaded with the formulations shown in Tables 1 and 3 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.
ガラス転移点（Ｔｇ）及び線膨張係数（ＣＴＥ）の測定は、熱機械測定装置を用いて１０℃／分の昇温速度で求めた。また吸水率は、直径５０mm、厚さ３mmの円形の試験片を用いて、８５℃、８５％ＲＨの条件で１００時間吸湿させた後の重量変化率とした。接着強度は、銅板２枚の間に２５ｍｍ×１２．５ｍｍ×０．５ｍｍの成形物を圧縮成形機により１７５℃で成形し、１８０℃にて１２時間ポストキュアを行った後、引張剪断強度を求めることにより評価した。難燃性は、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。結果を表２に示す。 The glass transition point (Tg) and linear expansion coefficient (CTE) were measured at a rate of temperature increase of 10 ° C./min using a thermomechanical measuring device. Further, the water absorption rate was defined as the rate of change in weight after absorbing moisture for 100 hours at 85 ° C. and 85% RH using a circular test piece having a diameter of 50 mm and a thickness of 3 mm. The adhesive strength was obtained by molding a molded product of 25 mm × 12.5 mm × 0.5 mm between two copper plates at 175 ° C. with a compression molding machine, post-curing at 180 ° C. for 12 hours, and then adjusting the tensile shear strength. Evaluated by seeking. Flame retardance was measured by molding a 1/16 inch thick test piece, evaluated according to the UL94V-0 standard, and expressed as the total burning time of 5 test pieces. The results are shown in Table 2.
実施例１４〜１９及び比較例５〜６
エポキシ樹脂成分として、実施例５、６、７、８で得たＰＳＮＥ−Ａ、ＰＳＮＥ−Ｂ、ＰＳＮＥ−Ｃ，ＰＳＮＥ−Ｄ、合成例３、４で得た樹脂の他、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、実施例１で合成したＰＳＮ−Ａ、フェノールノボラック（硬化剤Ａ：群栄化学製、ＰＳＭ−４２６１；ＯＨ当量１０３、軟化点 ８２℃）又はフェノールアラルキル樹脂（硬化剤Ｂ；明和化成製、ＭＥＨ−７８００ＳＳ、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 14-19 and Comparative Examples 5-6
As an epoxy resin component, PSNE-A, PSNE-B, PSNE-C, PSNE-D obtained in Examples 5, 6, 7 and 8; resins obtained in Synthesis Examples 3 and 4; and o-cresol novolak type Using an epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.), PSN-A synthesized in Example 1 as a curing agent component, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent) 103, softening point 82 ° C.) or phenol aralkyl resin (curing agent B; manufactured by Meiwa Kasei Co., Ltd., MEH-7800SS, OH equivalent 175, softening point 67 ° C.). Furthermore, spherical silica (average particle size 18 μm) was used as a filler, triphenylphosphine was used as a curing accelerator, and an epoxy resin composition was obtained with the formulation shown in Table 3. The numerical value in a table | surface shows the weight part in a mixing | blending.
このエポキシ樹脂組成物を用いて１７５℃で成形し、更に１７５℃にて１２時間ポストキュアを行い、硬化物試験片を得た後、各種物性測定に供した。結果を表４に示す。 This epoxy resin composition was molded at 175 ° C., and further post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. The results are shown in Table 4.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009086384A JP5320130B2 (en) | 2009-03-31 | 2009-03-31 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009086384A JP5320130B2 (en) | 2009-03-31 | 2009-03-31 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013034557A Division JP5548792B2 (en) | 2013-02-25 | 2013-02-25 | Polyvalent hydroxy resin, production method thereof, epoxy resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010235819A JP2010235819A (en) | 2010-10-21 |
| JP5320130B2 true JP5320130B2 (en) | 2013-10-23 |
Family
ID=43090452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009086384A Active JP5320130B2 (en) | 2009-03-31 | 2009-03-31 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5320130B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220306794A1 (en) * | 2021-03-29 | 2022-09-29 | Chang Chun Plastics Co. Ltd. | Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5548562B2 (en) * | 2010-09-10 | 2014-07-16 | 新日鉄住金化学株式会社 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
| SG188247A1 (en) * | 2010-09-27 | 2013-04-30 | Nippon Steel & Sumikin Chem Co | Polyhydric hydroxy resin, epoxy resin, production method therefor, epoxy resin composition and cured product thereof |
| JP5570380B2 (en) * | 2010-10-07 | 2014-08-13 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
| JP5570449B2 (en) * | 2011-01-31 | 2014-08-13 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
| JP2012167142A (en) * | 2011-02-10 | 2012-09-06 | Nippon Steel Chem Co Ltd | Epoxy resin composition and cured product |
| JP5570453B2 (en) * | 2011-02-10 | 2014-08-13 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
| JP5933954B2 (en) * | 2011-10-17 | 2016-06-15 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
| JP5914027B2 (en) * | 2012-02-16 | 2016-05-11 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
| SG11201405075SA (en) * | 2012-02-23 | 2014-10-30 | Nippon Steel & Sumikin Chem Co | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof |
| SG11201406632SA (en) * | 2012-04-16 | 2014-11-27 | Nippon Steel & Sumikin Chem Co | Epoxy resin composition and cured product |
| WO2013187185A1 (en) * | 2012-06-12 | 2013-12-19 | 新日鉄住金化学株式会社 | Polyhydroxy polyether resin, method for producing polyhydroxy polyether resin, resin composition containing polyhydroxy polyether resin, and cured product obtained therefrom |
| TWI631173B (en) * | 2012-10-11 | 2018-08-01 | 新日鐵住金化學股份有限公司 | Epoxy resin composition and hardened material |
| JP2014181326A (en) * | 2013-03-21 | 2014-09-29 | Nippon Steel & Sumikin Chemical Co Ltd | Epoxy acrylate resin, epoxy acrylate acid anhydride adduct, curable resin composition, alkali development type photosensitive resin composition, and cured product of the same |
| JP2014203964A (en) * | 2013-04-04 | 2014-10-27 | 日東電工株式会社 | Adhesive film for underfill, adhesive film for underfill integrated with tape for back grinding, adhesive film for underfill integrated with dicing tape, and semiconductor device |
| 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 |
| JP6758087B2 (en) | 2016-05-19 | 2020-09-23 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin curing agent composition, epoxy resin composition and cured product |
| JP6924000B2 (en) | 2016-05-20 | 2021-08-25 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin composition and its cured product |
| 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 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0656964A (en) * | 1991-09-30 | 1994-03-01 | Dainippon Ink & Chem Inc | Epoxy resin composition for electronic parts, epoxy resin and method for producing epoxy 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 |
| JP4031061B2 (en) * | 1995-05-01 | 2008-01-09 | 新日鐵化学株式会社 | NOVEL EPOXY RESIN, INTERMEDIATE AND PRODUCTION METHOD, AND EPOXY RESIN COMPOSITION USING THE SAME AND CURED PRODUCT THEREOF |
| JP2001302763A (en) * | 2000-04-26 | 2001-10-31 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2005187607A (en) * | 2003-12-25 | 2005-07-14 | Dainippon Ink & Chem Inc | Phenolic resin, epoxy resin, epoxy resin composition and cured product thereof |
| JP4962751B2 (en) * | 2004-10-20 | 2012-06-27 | Ｄｉｃ株式会社 | Epoxy resin composition, cured product thereof, novel dihydric phenol compound and production method thereof |
| JP5166096B2 (en) * | 2008-03-31 | 2013-03-21 | 新日鉄住金化学株式会社 | Polyvalent hydroxy compound, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
-
2009
- 2009-03-31 JP JP2009086384A patent/JP5320130B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220306794A1 (en) * | 2021-03-29 | 2022-09-29 | Chang Chun Plastics Co. Ltd. | Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof |
| US11629216B2 (en) * | 2021-03-29 | 2023-04-18 | Chang Chun Plastics Co., Ltd. | Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010235819A (en) | 2010-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5320130B2 (en) | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| JP5931234B2 (en) | Method for producing epoxy resin composition | |
| JP6406847B2 (en) | Modified polyvalent hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof | |
| JP5548562B2 (en) | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| JP6462295B2 (en) | Modified polyvalent hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof | |
| JP5000191B2 (en) | Carbazole skeleton-containing resin, carbazole skeleton-containing epoxy resin, epoxy resin composition and cured product thereof | |
| JP6124865B2 (en) | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| JP2017066268A (en) | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| JP5166096B2 (en) | Polyvalent hydroxy compound, epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| JP5570449B2 (en) | Epoxy resin composition and cured product | |
| JP5734603B2 (en) | Phenolic resin, epoxy resin, production method thereof, epoxy resin composition and cured product | |
| JP5548792B2 (en) | Polyvalent hydroxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| JPWO2003068837A1 (en) | Indole resins, epoxy resins and resin compositions containing these resins | |
| JP2007297538A (en) | Resin containing indole skeleton, epoxy resin containing indole skeleton, epoxy resin composition and cured product thereof | |
| WO2012043414A1 (en) | Epoxy resin composition and cured substance | |
| JP2008231071A (en) | New polyvalent hydroxy compound, and epoxy resin composition and its cured product | |
| JP4813201B2 (en) | Indole skeleton-containing epoxy resin, epoxy resin composition and cured product thereof | |
| JP2020105331A (en) | Polyhydric hydroxy resin, epoxy resin, epoxy resin composition, and cured material thereof | |
| JP2008222838A (en) | Epoxy resin and epoxy resin composition and its cured product | |
| JP2008239853A (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JP2008222837A (en) | New polyhydric hydroxy compound, method for producing the hydroxy compound, and thermosetting resin composition containing the hydroxy compound and its cured product | |
| WO2008117839A1 (en) | Novel polyvalent hydroxy compound, method for producing the same, epoxy resin using the compound, and epoxy resin composition and cured product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110922 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130109 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130115 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130225 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130709 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130712 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5320130 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |