JPWO2013187184A1 - Phosphorus-containing epoxy resin, composition containing epoxy resin as essential component, and cured product - Google Patents
Phosphorus-containing epoxy resin, composition containing epoxy resin as essential component, and cured product Download PDFInfo
- Publication number
- JPWO2013187184A1 JPWO2013187184A1 JP2014521221A JP2014521221A JPWO2013187184A1 JP WO2013187184 A1 JPWO2013187184 A1 JP WO2013187184A1 JP 2014521221 A JP2014521221 A JP 2014521221A JP 2014521221 A JP2014521221 A JP 2014521221A JP WO2013187184 A1 JPWO2013187184 A1 JP WO2013187184A1
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- phosphorus
- containing epoxy
- molecular weight
- content
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 184
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 184
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 84
- 239000011574 phosphorus Substances 0.000 title claims abstract description 81
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 59
- 239000000203 mixture Substances 0.000 title claims description 32
- -1 phosphorus compound Chemical class 0.000 claims abstract description 64
- 229920003986 novolac Polymers 0.000 claims abstract description 59
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000009826 distribution Methods 0.000 claims abstract description 23
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000011088 calibration curve Methods 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 14
- 230000001070 adhesive effect Effects 0.000 abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 36
- 238000001723 curing Methods 0.000 description 30
- 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 26
- 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 22
- 229910000831 Steel Inorganic materials 0.000 description 21
- 239000010959 steel Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 18
- 150000002989 phenols Chemical class 0.000 description 16
- 239000004593 Epoxy Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 12
- 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 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 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 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 229930003836 cresol Natural products 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 150000004780 naphthols Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- BXJGUBZTZWCMEX-UHFFFAOYSA-N dimethylhydroquinone Natural products CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- OVAZZMXASSWARN-UHFFFAOYSA-N naphthalen-1-ylmethanediol Chemical compound C1=CC=C2C(C(O)O)=CC=CC2=C1 OVAZZMXASSWARN-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- UHCXRMWHYLSPDJ-UHFFFAOYSA-N (2-aminophenyl) benzenesulfonate Chemical compound NC1=CC=CC=C1OS(=O)(=O)C1=CC=CC=C1 UHCXRMWHYLSPDJ-UHFFFAOYSA-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
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- BOJZPUPAXYETRK-UHFFFAOYSA-N 1,1-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)(CN)C1=CC=CC=C1 BOJZPUPAXYETRK-UHFFFAOYSA-N 0.000 description 1
- IEVIXDLZSRLUHW-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diol Chemical compound C=1C=CC=CC=1C(O)=C(O)C1=CC=CC=C1 IEVIXDLZSRLUHW-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- UQWJRHXJJRTQCX-UHFFFAOYSA-N 1-(ethoxymethyl)-4-[4-(ethoxymethyl)phenyl]benzene Chemical group C1=CC(COCC)=CC=C1C1=CC=C(COCC)C=C1 UQWJRHXJJRTQCX-UHFFFAOYSA-N 0.000 description 1
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RBAHPVZZUNVLLE-UHFFFAOYSA-N 1-phenoxy-1-phenylpropan-1-amine Chemical compound C=1C=CC=CC=1C(N)(CC)OC1=CC=CC=C1 RBAHPVZZUNVLLE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NWQWQKUXRJYXFH-UHFFFAOYSA-N 2,2-Dichloroacetaldehyde Chemical compound ClC(Cl)C=O NWQWQKUXRJYXFH-UHFFFAOYSA-N 0.000 description 1
- NKNIZOPLGAJLRV-UHFFFAOYSA-N 2,2-diphenylpropane-1,1-diamine Chemical compound C=1C=CC=CC=1C(C(N)N)(C)C1=CC=CC=C1 NKNIZOPLGAJLRV-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- LLNSYBHDHRWWME-UHFFFAOYSA-N 2,3,5,6-tetrabutyl-4-[2-(2,3,5,6-tetrabutyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound CCCCc1c(O)c(CCCC)c(CCCC)c(c1CCCC)C(C)(C)c1c(CCCC)c(CCCC)c(O)c(CCCC)c1CCCC LLNSYBHDHRWWME-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 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
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- LYXAQAXLWMRPOZ-UHFFFAOYSA-N 2-[1-(2-aminophenyl)-9h-fluoren-2-yl]aniline Chemical compound NC1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=CC=C1N LYXAQAXLWMRPOZ-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-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
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- OHPBKUJGDFXDRM-UHFFFAOYSA-N 3,4-diethyl-5-(2-phenylpropan-2-yl)benzene-1,2-diamine Chemical compound CCC1=C(N)C(N)=CC(C(C)(C)C=2C=CC=CC=2)=C1CC OHPBKUJGDFXDRM-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- DOJDHOJUHISJIT-UHFFFAOYSA-N 3-(3-amino-2-phenoxyphenoxy)-2-phenoxyaniline Chemical compound C=1C=CC=CC=1OC=1C(N)=CC=CC=1OC1=CC=CC(N)=C1OC1=CC=CC=C1 DOJDHOJUHISJIT-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- MCUFTLAXJMCWPZ-UHFFFAOYSA-N 3-butyl-2-methylphenol Chemical compound CCCCC1=CC=CC(O)=C1C MCUFTLAXJMCWPZ-UHFFFAOYSA-N 0.000 description 1
- FKSAYGREWVVCIZ-UHFFFAOYSA-N 3-methyl-1-phenylbut-3-en-1-one Chemical compound CC(=C)CC(=O)C1=CC=CC=C1 FKSAYGREWVVCIZ-UHFFFAOYSA-N 0.000 description 1
- BDBMKUGEVIQCGQ-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-dimethylaniline Chemical group C1=C(N)C(C)=C(C)C(C=2C=CC(N)=CC=2)=C1 BDBMKUGEVIQCGQ-UHFFFAOYSA-N 0.000 description 1
- VESRBMGDECAMNH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2,3,5,6-tetramethylphenol Chemical compound CC1=C(C(=C(C(=C1O)C)C)C(C)(C)C1=CC=C(C=C1)O)C VESRBMGDECAMNH-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- KSFAWAYSJUPRED-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetramine Chemical compound NC1=C(N)C(N)=CC(C=2C=CC=CC=2)=C1N KSFAWAYSJUPRED-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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- AXPZDYVDTMMLNB-UHFFFAOYSA-N Benzyl ethyl ether Chemical compound CCOCC1=CC=CC=C1 AXPZDYVDTMMLNB-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- AOAAAVXXAVTWSE-UHFFFAOYSA-N C1(=CC=CC=C1)O.C(C)(C)(C)C=1C(=C(O)C=CC1O)C(C)(C)C Chemical class C1(=CC=CC=C1)O.C(C)(C)(C)C=1C(=C(O)C=CC1O)C(C)(C)C AOAAAVXXAVTWSE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-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
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- SFHGONLFTNHXDX-UHFFFAOYSA-N [4-[4-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=C(CO)C=C1 SFHGONLFTNHXDX-UHFFFAOYSA-N 0.000 description 1
- KAPKGQYTDOPUJQ-UHFFFAOYSA-N [P].C1=CC=CC=2C3=CC=CC=C3OP(C12)=O Chemical compound [P].C1=CC=CC=2C3=CC=CC=C3OP(C12)=O KAPKGQYTDOPUJQ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JMCNGFNJWDJIIV-UHFFFAOYSA-N dibutyl(oxo)phosphanium Chemical compound CCCC[P+](=O)CCCC JMCNGFNJWDJIIV-UHFFFAOYSA-N 0.000 description 1
- YVXVNGVYXSQARS-UHFFFAOYSA-N diethyl(oxo)phosphanium Chemical compound CC[P+](=O)CC YVXVNGVYXSQARS-UHFFFAOYSA-N 0.000 description 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WQAWEUZTDVWTDB-UHFFFAOYSA-N dimethyl(oxo)phosphanium Chemical compound C[P+](C)=O WQAWEUZTDVWTDB-UHFFFAOYSA-N 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-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
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- NCIAGQNZQHYKGR-UHFFFAOYSA-N naphthalene-1,2,3-triol Chemical compound C1=CC=C2C(O)=C(O)C(O)=CC2=C1 NCIAGQNZQHYKGR-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-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
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
本発明は、従来の接着力を保持しつつ耐熱性の更なる向上した特性を有するエポキシ樹脂を提供するものであって、一般式(1)で示されるリン化合物とキノン化合物とエポキシ樹脂(a)を必須成分として反応して得られるリン含有エポキシ樹脂において、エポキシ樹脂(a)がゲルパーミエーションクロマトグラフィーにおける測定において、二核体含有率が15面積%以下、三核体含有率が15面積%〜60面積%であり、数平均分子量が350〜700である分子量分布を持つノボラック型エポキシ樹脂であることを特徴とするリン含有エポキシ樹脂(A)である。The present invention provides an epoxy resin having a further improved property of heat resistance while maintaining conventional adhesive strength, and comprises a phosphorus compound, a quinone compound and an epoxy resin (a) represented by the general formula (1). ) As an essential component, the epoxy resin (a) has a dinuclear content of 15 area% or less and a trinuclear content of 15 area in the measurement by gel permeation chromatography. It is a novolak type epoxy resin (A) characterized by being a novolak type epoxy resin having a molecular weight distribution of% to 60 area% and a number average molecular weight of 350 to 700.
Description
本発明は分子骨格にリン原子を含有するハロゲンフリー難燃性エポキシ樹脂及び、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物、更には該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に関し、電子回路基板に用いられるプリプレグ、銅張り積層板や電子部品に用いられるフィルム材・封止材・成形材・注型材・接着剤・電気絶縁塗料、難燃性の必要な複合材、粉体塗料などに適したエポキシ樹脂を提供する。 The present invention relates to a halogen-free flame-retardant epoxy resin containing a phosphorus atom in a molecular skeleton, an epoxy resin composition containing the epoxy resin as an essential component, and a cured epoxy resin obtained by curing the epoxy resin composition. , Prepregs used for electronic circuit boards, copper-clad laminates and film materials / sealing materials / molding materials / casting materials / adhesives / electric insulating paints used for electronic components, flame retardant composite materials, powders An epoxy resin suitable for paints is provided.
エポキシ樹脂の難燃化は従来テトラブロモビスフェノールAを原料とした臭素化エポキシ樹脂に代表されるようにハロゲン化により行われていた。しかし、ハロゲン化エポキシ樹脂を用いた場合、硬化物の燃焼時に熱分解反応により毒性の強いハロゲン化物の生成がみられるといった問題があった。これに対して近年リン化合物を利用したハロゲンフリー難燃技術が検討され、特許文献1〜特許文献7で開示されているようなリン含有エポキシ樹脂、リン含有フェノール樹脂が提案されている。
特許文献1、特許文献2で開示されているリン含有エポキシ樹脂は接着力が高いもののガラス転移温度に代表される耐熱性が十分では無く、特許文献3で開示されているリン含有エポキシ樹脂はガラス転移温度の改善はあるものの接着力との両立は困難であった。また、特許文献4で開示されているリン含有エポキシ樹脂はキノン化合物を使用することにより高接着力と高耐熱性の向上を図っている。更に、特許文献5では特定の2官能エポキシ樹脂を併用することで高接着力と高耐熱性を更に向上することを図っており、特許文献6で開示されているリン含有エポキシ樹脂に関しても接着力と高耐熱性との向上が検討されている。しかし、ガラス転移温度については更に高度な要求があり接着力を維持しつつ改良を求められていた。
リン化合物による難燃化手法により得られるリン含有エポキシ樹脂は、高耐熱性と高接着力の両立は難しく耐熱性を高めるため多官能化を行うと接着力が低下してしまい、接着力を高めるためリン化合物の2官能化を行うと耐熱性は低下してしまっていた。これに対して特許文献5では特定の2官能エポキシ樹脂を20%から45%の範囲で使用することによって高耐熱性と高接着力の更なる向上を提案している。Conventionally, flame retarding of epoxy resins has been performed by halogenation, as represented by brominated epoxy resins using tetrabromobisphenol A as a raw material. However, when a halogenated epoxy resin is used, there is a problem in that a highly toxic halide is generated due to a thermal decomposition reaction when the cured product is burned. On the other hand, in recent years, halogen-free flame retardant technology using phosphorus compounds has been studied, and phosphorus-containing epoxy resins and phosphorus-containing phenol resins as disclosed in
Although the phosphorus-containing epoxy resins disclosed in
Phosphorus-containing epoxy resin obtained by a flame-retarding technique using phosphorus compounds is difficult to achieve both high heat resistance and high adhesive strength. Therefore, when bifunctionalization of the phosphorus compound is performed, the heat resistance has been lowered. On the other hand, Patent Document 5 proposes further improvement of high heat resistance and high adhesive force by using a specific bifunctional epoxy resin in the range of 20% to 45%.
最近では電子回路基板等において、半田リフロー温度の上昇や長期信頼性確保の為、耐熱性、特にガラス転移温度は、更なる向上が要求されている。本発明は接着力を保持しつつ耐熱性の更なる向上した特性を有するエポキシ樹脂を提供することを課題とするものである。 Recently, in order to increase the solder reflow temperature and to ensure long-term reliability in electronic circuit boards and the like, further improvements in heat resistance, particularly the glass transition temperature, are required. An object of the present invention is to provide an epoxy resin having a further improved heat resistance while maintaining adhesive strength.
上記の課題を解決するために、本発明者はエポキシ樹脂の中でも特定の分子量分布を持つノボラック型エポキシ樹脂とリン化合物、キノン化合物を用いて得られるリン含有エポキシ樹脂は高い接着力を維持しつつ耐熱性を向上できることを見出し、更には難燃性において良好であることを見出し、本発明を完成した。
すなわち、本発明の要旨は、
(1)一般式(1)で示されるリン化合物とキノン化合物とエポキシ樹脂(a)を必須成分として反応して得られるリン含有エポキシ樹脂において、エポキシ樹脂(a)が下記にのべるゲルパーミエーションクロマトグラフィーにおける測定において二核体含有率が15面積%以下、三核体含有率が15面積%〜60面積%であり、数平均分子量が350〜700である分子量分布を持つノボラック型エポキシ樹脂であることを特徴とするリン含有エポキシ樹脂(A)である。
(ゲルパーミエーションクロマトグラフィー測定条件)
東ソー株式会社製 TSKgelG4000HXL、TSKgelG3000HXL、TSKgelG2000HXLを直列に備えたものを使用し、カラム温度は40℃にした。また、溶離液にはテトラヒドロフラン(THF)を用い、1ml/minの流速とし、検出器はRI(示差屈折計)検出器を用いた。測定用試料は、サンプル0.1gを10mlのTHFに溶解した。得られたクロマトグラムにより二核体含有率及び三核体含有率を算出し、標準ポリスチレンによる検量線により数平均分子量を測定する。
(2)上記(1)記載のリン含有エポキシ樹脂(A)と硬化剤を必須成分とし、リン含有エポキシ樹脂(A)のエポキシ基1当量に対して硬化剤の活性基を0.3当量〜1.5当量を配合してなるリン含有エポキシ樹脂組成物、
(3)上記(2)記載のリン含有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、
(4)上記(2)記載のリン含有エポキシ樹脂組成物を基材に含浸してなるプリプレグ、
(5)上記(2)記載のリン含有エポキシ樹脂組成物を硬化してなる積層板、
(6)上記(2)記載のリン含有エポキシ樹脂組成物を硬化してなる電子回路基板、である。In order to solve the above-mentioned problems, the present inventor has maintained a high adhesion of a phosphorus-containing epoxy resin obtained by using a novolak type epoxy resin having a specific molecular weight distribution, a phosphorus compound, and a quinone compound among epoxy resins. The inventors found that heat resistance can be improved, and further found that the flame retardancy is good, thereby completing the present invention.
That is, the gist of the present invention is as follows.
(1) In a phosphorus-containing epoxy resin obtained by reacting a phosphorus compound represented by the general formula (1), a quinone compound, and an epoxy resin (a) as essential components, the gel permeation chromatography described below is the epoxy resin (a). It is a novolak-type epoxy resin having a molecular weight distribution in which the dinuclear content is 15 area% or less, the trinuclear content is 15 area% to 60 area%, and the number average molecular weight is 350 to 700 in the measurement in the graphic. This is a phosphorus-containing epoxy resin (A).
(Gel permeation chromatography measurement conditions)
Tosoh Corporation TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL were used in series, and the column temperature was 40 ° C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector. As a measurement sample, 0.1 g of a sample was dissolved in 10 ml of THF. The binuclear content and trinuclear content are calculated from the obtained chromatogram, and the number average molecular weight is measured by a calibration curve using standard polystyrene.
(2) The phosphorus-containing epoxy resin (A) described in (1) above and a curing agent are essential components, and the active group of the curing agent is 0.3 equivalent to 1 equivalent of the epoxy group of the phosphorus-containing epoxy resin (A). A phosphorus-containing epoxy resin composition comprising 1.5 equivalents,
(3) An epoxy resin cured product obtained by curing the phosphorus-containing epoxy resin composition according to (2),
(4) A prepreg obtained by impregnating a base material with the phosphorus-containing epoxy resin composition described in (2) above,
(5) A laminate obtained by curing the phosphorus-containing epoxy resin composition described in (2) above,
(6) An electronic circuit board obtained by curing the phosphorus-containing epoxy resin composition described in (2) above.
本発明は、特定の分子量分布を持つノボラック型エポキシ樹脂とリン化合物とキノン化合物を必須として反応することによって得られるリン含有エポキシ樹脂であり、特定の分子量分布を持つノボラック型エポキシ樹脂を使用することにより、接着力を維持しつつガラス転移温度の高い硬化物物性を示すリン含有エポキシ樹脂が得られるものである。更にエポキシ樹脂の粘度が低く作業性及び基材に対する含浸性においても優れており、難燃性も良好である。 The present invention is a phosphorus-containing epoxy resin obtained by reacting a novolac type epoxy resin having a specific molecular weight distribution, a phosphorus compound and a quinone compound as essential, and uses a novolak type epoxy resin having a specific molecular weight distribution Thus, a phosphorus-containing epoxy resin exhibiting a cured product property having a high glass transition temperature while maintaining the adhesive force can be obtained. Furthermore, the viscosity of the epoxy resin is low, the workability and the impregnation with respect to the substrate are excellent, and the flame retardancy is also good.
図1は汎用型フェノールノボラック型エポキシ樹脂であるYDPN−638のゲルパーミエーションクロマトグラフィー(GPC)チャートを示す。横軸に溶出時間を示し、左縦軸に信号強度を示す。右縦軸に数平均分子量Mをlogで示す。用いた標準物質の数平均分子量の測定値を黒丸でプロットしており検量線としている。Aで示すピークが二核体、Bで示すピークが三核体を示す。
図2は合成例2のノボラック型エポキシ樹脂のGPCチャートを示す。Aで示すピークが二核体、Bで示すピークが三核体を示す。FIG. 1 shows a gel permeation chromatography (GPC) chart of YDPN-638, which is a general-purpose phenol novolac epoxy resin. The horizontal axis shows the elution time, and the left vertical axis shows the signal intensity. The number average molecular weight M is indicated by log on the right vertical axis. The measured value of the number average molecular weight of the standard substance used is plotted with a black circle, which is a calibration curve. The peak indicated by A indicates a dinuclear body, and the peak indicated by B indicates a trinuclear body.
FIG. 2 shows a GPC chart of the novolac type epoxy resin of Synthesis Example 2. The peak indicated by A indicates a dinuclear body, and the peak indicated by B indicates a trinuclear body.
以下、本発明の実施の形態について、詳細に説明する。
本発明に用いるエポキシ樹脂(a)は、フェノール類とアルデヒド類の反応生成物であって、特定の分子量分布を有するノボラック樹脂とエピハロヒドリンとを反応して得られる多官能のノボラック型エポキシ樹脂である。使用されるフェノール類としてはフェノール、クレゾール、エチルフェノール、ブチルフェノール、スチレン化フェノール、クミルフェノール、ナフトール、カテコール、レゾルシノール、ナフタレンジオール、ビスフェノールAなどが挙げられ、アルデヒド類としてはホルマリン、ホルムアルデヒド、ヒドロキシベンズアルデヒド、サリチルアルデヒドなどが挙げられる。また、アルデヒド類の代わりにキシリレンジメタノール、キシリレンジクロライド、ビスクロロメチルナフタレン、ビスクロロメチルビフェニルなどを用いたアラルキルフェノール樹脂も本発明ではノボラック樹脂に含む。前述のノボラック樹脂にエピハロヒドリンを用いてエポキシ化することでノボラック型エポキシ樹脂が得られる。
慣用されているノボラック型エポキシ樹脂の具体例としては、エポトートYDPN−638(新日鐵化学株式会社製 フェノールノボラック型エポキシ樹脂)、エピコート152、エピコート154(三菱化学株式会社製 フェノールノボラック型エポキシ樹脂)、エピクロンN−740、エピクロンN−770、エピクロンN−775(DIC株式会社製フェノールノボラック型エポキシ樹脂)、エポトートYDCN−700シリーズ(新日鐵化学株式会社製 クレゾールノボラック型エポキシ樹脂)、エピクロンN−660、エピクロンN−665、エピクロンN−670、エピクロンN−673、エピクロンN−695(DIC株式会社製 クレゾールノボラック型エポキシ樹脂)、EOCN−1020、EOCN−102S、EOCN−104S(日本化薬株式会社製 クレゾールノボラック型エポキシ樹脂)、エポトートZX−1071T、ZX−1270、ZX−1342(新日鐵化学株式会社製 アルキルノボラック型エポキシ樹脂)、エポトートZX−1247、GK−5855(新日鐵化学株式会社製 スチレン化フェノールノボラック型エポキシ樹脂)、エポトートZX−1142L(新日鐵化学株式会社製 ナフトールノボラック型エポキシ樹脂)、ESN−155、ESN−185V、ESN−175(新日鐵化学株式会社製 βナフトールアラルキル型エポキシ樹脂)、ESN−300シリーズのESN−355、ESN−375(新日鐵化学株式会社製 ジナフトールアラルキル型エポキシ樹脂)、ESN−400シリーズのESN−475V、ESN−485(新日鐵化学株式会社製 αナフトールアラルキル型エポキシ樹脂)ビスフェノールノボラック型エポキシ樹脂等が挙げられるが、これらのエポキシ樹脂は本発明における特定の分子量分布を持っていない。
本発明で用いる特定の分子量分布を持つエポキシ樹脂(a)を得るにはフェノール類とアルデヒド類のモル比を調整することと、得られたノボラック樹脂から低分子量成分を除去する方法によって得ることが出来る。また、特許文献8、特許文献9に示すような製造方法により得られるノボラック樹脂をエポキシ樹脂化しても良い。
The epoxy resin (a) used in the present invention is a reaction product of phenols and aldehydes, and is a polyfunctional novolac type epoxy resin obtained by reacting a novolak resin having a specific molecular weight distribution with an epihalohydrin. . Examples of phenols used include phenol, cresol, ethylphenol, butylphenol, styrenated phenol, cumylphenol, naphthol, catechol, resorcinol, naphthalenediol, and bisphenol A. Examples of aldehydes include formalin, formaldehyde, and hydroxybenzaldehyde. And salicylaldehyde. In the present invention, an aralkylphenol resin using xylylenediethanol, xylylenedichloride, bischloromethylnaphthalene, bischloromethylbiphenyl or the like instead of aldehydes is also included in the present invention. A novolac-type epoxy resin can be obtained by epoxidizing the above-mentioned novolak resin with epihalohydrin.
Specific examples of commonly used novolak type epoxy resins include Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epicoat 152, and Epicoat 154 (Phenol novolak type epoxy resin manufactured by Mitsubishi Chemical Corporation). , Epicron N-740, Epicron N-770, Epicron N-775 (phenol novolac type epoxy resin manufactured by DIC Corporation), Epotot YDCN-700 series (Cresol novolak type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epicron N- 660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-695 (a cresol novolac epoxy resin manufactured by DIC Corporation), EOCN-1020, EOCN-102S, EOCN-1 04S (Nippon Kayaku Co., Ltd. cresol novolak type epoxy resin), Epototo ZX-1071T, ZX-1270, ZX-1342 (Nippon Steel Chemical Co., Ltd. alkyl novolak type epoxy resin), Epototo ZX-1247, GK-5855 (Styrene phenolic novolac type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX-1142L (Naphthol novolak type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ESN-155, ESN-185V, ESN-175 (New Day) (Beta naphthol aralkyl epoxy resin manufactured by Sakai Chemical Co., Ltd.), ESN-300 series ESN-355, ESN-375 (Nippon Steel Chemical Co., Ltd. dinaphthol aralkyl epoxy resin), ESN-400 series ESN-475V, ESN-485 (new Steel Chemical Co., Ltd. α-naphthol aralkyl type epoxy resin) of bisphenol novolak epoxy resins, these epoxy resins does not have a particular molecular weight distribution in the present invention.
The epoxy resin (a) having a specific molecular weight distribution used in the present invention can be obtained by adjusting the molar ratio of phenols and aldehydes and removing low molecular weight components from the obtained novolak resin. I can do it. Further, a novolac resin obtained by a manufacturing method as shown in Patent Document 8 and Patent Document 9 may be converted to an epoxy resin.
フェノール類とアルデヒド類のモル比はアルデヒド類1モルに対するフェノール類のモル比で示され1以上の比率で製造されるが、モル比が大きい場合は二核体、三核体が多く生成され、モル比が小さい場合は高分子量体が多く生成し、二核体、三核体は少なくなる。
本発明で用いる特定の分子量分布を持つエポキシ樹脂(a)を得るには、得られたノボラック樹脂類から二核体を各種溶媒の溶解性差を利用して除去する方法、アルカリ水溶液に二核体を溶解して除去する方法などによって得ることが出来き、その他の公知の分離方法によっても良い。
分子量を制御したノボラック樹脂に公知のエポキシ化の手法を用いて特定の分子量分布を持つノボラック型エポキシ樹脂を得ることが出来る。あるいは市販のノボラック型エポキシ樹脂から二核体成分を各種方法により除去することによっても特定の分子量分布を持つノボラック型エポキシ樹脂を得ることが出来る。その他公知の分離方法によっても良い。
本発明で用いる特定の分子量分布を持つエポキシ樹脂(a)は、二核体含有率が15面積%以下が好ましく、5面積%〜12面積%がより好ましい。少量の二核体が含有することで、接着力などの物性を向上することが出来る。三核体含有率は、15面積%〜60面積%が好ましく、20面積%〜50面積%がより好ましい。三核体の含有率が15面積%未満では耐熱性に劣り易くなり、60面積%を超える場合には接着性に劣るものとなり易い。なお、四核体及び五核体以上の範囲に関しては特に規定するものではないが、三核体と四核体の含有率の合計が30面積%〜70面積%が好ましい。三核体と四核体の含有率の合計が30面積%〜70面積%の範囲でより難燃性が改善する。五核体以上の含有率は45面積%以下が好ましく、40面積%以下がより好ましい。五核体以上の含有率が45面積%以下ならばより接着力の高い硬化物を得ることができる。数平均分子量は350〜700が好ましく、380〜600がより好ましい。数平均分子量が700を超える場合は、得られるリン含有エポキシ樹脂(A)の粘度が高くなり、作業性や基材含浸性に悪影響を及ぼす恐れがある。これらの条件により得られるリン含有エポキシ樹脂(A)の難燃性が改善する理由については、得られる硬化物の弾性率が低くなることにより、燃焼時に生成するチャーがより強固となり、より高い断熱効果をもたらすためと考えられるが、検証はされていない。
本発明で用いる一般式(1)で示されるリン化合物は、具体的にはジメチルホスフィン、ジエチルホスフィン、ジフェニルホスフィン、9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド(HCA 三光株式会社製)、ジメチルホスフィンオキサイド、ジエチルホスフィンオキサイド、ジブチルホスフィンオキサイド、ジフェニルホスフィンオキサイド、1,4−シクロオクチレンホスフィンオキサイド、1,5−シクロオクチレンホスフィンオキサイド(CPHO 日本化学工業株式会社製)等が挙げられる。これらのリン化合物は単独でも2種類以上混合して使用しても良く、これらに限定されるものではない。
本発明におけるキノン化合物とはベンゾキノン、ナフトキノン、トルキノン、アントラキノン及びこれらの異性体、炭化水素基の置換基を持ったもの等が挙げられ、単独で使用しても2種類以上混合して使用しても良く、これらに限定されるものではない。一般式(1)で示されるリン化合物とキノン化合物とのモル比率は、リン化合物:キノン化合物=1:1以下が好ましく、1:0.99〜0.2がより好ましく、1:0.98〜0.40が望ましい。キノン化合物が過剰になると未反応成分としてリン含有エポキシ樹脂(A)に残存するために物性低下につながり易く、0.2より低い場合には耐熱性、難燃性に悪影響を及ぼす恐れがある。また、リン化合物とキノン化合物を反応後、精製により反応成分のみを取り出したものを使用しても良い。
本発明のリン含有エポキシ樹脂(A)は、一般式(1)で示されるリン化合物とキノン化合物と特定の分子量分布を持つエポキシ樹脂(a)を必須として反応して得られるが、本発明の作用効果に影響が無い範囲において更に、その他の公知慣用のエポキシ樹脂類や変性剤を使用することができる。
一般式(1)で示されるリン化合物とキノン化合物と特定の分子量分布を持つエポキシ樹脂(a)との反応は公知の方法で行われる。リン化合物とキノン化合物を反応後更にエポキシ樹脂(a)と反応する方法、リン化合物とキノン化合物をエポキシ樹脂(a)中で反応した後に、更にエポキシ樹脂(a)と反応する方法、あらかじめリン化合物とキノン化合物を反応したものを得ておき、エポキシ樹脂(a)と反応する方法等があるが本発明においては反応手順は特に限定されない。
反応温度は間接法エポキシ樹脂の合成に通常設定されている温度で良く、100℃〜250℃、好ましくは120℃〜200℃である。
反応には時間短縮や反応温度低減の為、触媒を使用しても良い。使用できる触媒は特に制限は無く、間接法エポキシ樹脂の合成に通常使用されているものが使用できる。例えば、ベンジルジメチルアミン等の第3級アミン類、テトラメチルアンモニウムクロライド等の第4級アンモニウム塩類、トリフェニルホスフィン、トリス(2,6−ジメトキシフェニル)ホスフィン等のホスフィン類、エチルトリフェニルホスホニウムブロマイド等のホスホニウム塩類、2メチルイミダゾール、2エチル4メチルイミダゾール等のイミダゾール類等各種触媒が使用可能であり、単独で用いても2種類以上併用してもよく、これらに限定されるものではない。また、分割して数回に分けて使用しても良い。
触媒量は特に限定されないが、エポキシ樹脂(a)や併用できるその他の公知慣用のエポキシ樹脂類の合計重量に対して5質量%以下、より好ましくは1質量%以下、更に好ましくは0.5質量%以下である。触媒量が多いと場合によってはエポキシ基の自己重合反応が進行するため、樹脂粘度が高くなり好ましくない。
一般式(1)で示されるリン化合物とキノン化合物と特定の分子量分布を持つエポキシ樹脂(a)を反応する際に、必要に応じて本発明の特性を損なわない範囲で各種エポキシ樹脂変性剤を併用しても良い。変性剤としてはビスフェノールA、ビスフェノールF、ビスフェノールAD、テトラブチルビスフェノールA、ハイドロキノン、メチルハイドロキノン、ジメチルハイドロキノン、ジブチルハイドロキノン、レゾルシン、メチルレゾルシン、ビフェノール、テトラメチルビフェノール、ジヒドロキシナフタレン、ジヒドロキシジフェニルエーテル、ジヒドロキシスチルベン類、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールAノボラック樹脂、ジシクロペンタジエンフェノール樹脂、フェノールアラルキル樹脂、ナフトールノボラック樹脂、テルペンフェノール樹脂、重質油変性フェノール樹脂、臭素化フェノールノボラック樹脂などの種々のフェノール類や、種々のフェノール類と、ヒドロキシベンズアルデヒド、クロトンアルデヒド、グリオキザールなどの種々のアルデヒド類との縮合反応で得られる多価フェノール樹脂や、アニリン、フェニレンジアミン、トルイジン、キシリジン、ジエチルトルエンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルエタン、ジアミノジフェニルプロパン、ジアミノジフェニルケトン、ジアミノジフェニルスルフィド、ジアミノジフェニルスルホン、ビス(アミノフェニル)フルオレン、ジアミノジエチルジメチルジフェニルメタン、ジアミノジフェニルエーテル、ジアミノベンズアニリド、ジアミノビフェニル、ジメチルジアミノビフェニル、ビフェニルテトラアミン、ビスアミノフェニルアントラセン、ビスアミノフェノキシベンゼン、ビスアミノフェノキシフェニルエーテル、ビスアミノフェノキシビフェニル、ビスアミノフェノキシフェニルスルホン、ビスアミノフェノキシフェニルプロパン、ジアミノナフタレン等のアミン化合物が挙げられるがこれらに限定されるものではなく2種類以上併用しても良い。
一般式(1)で示されるリン化合物とキノン化合物と特定の分子量分布を持つエポキシ樹脂(a)を反応する際に、必要に応じてその他の各種エポキシ樹脂類を本発明の特性を損なわない程度に併用することもできる。併用できるエポキシ樹脂類としては、具体的にはエポトート YDC−1312、ZX−1027(新日鐵化学株式会社製 ハイドロキノン型エポキシ樹脂)、YX−4000(三菱化学株式会社製)ZX−1251(新日鐵化学株式会社製 ビフェノール型エポキシ樹脂)、エポトート YD−127、エポトート YD−128、エポトート YD−8125、エポトート YD−825GS、エポトート YD−011、エポトート YD−900、エポトート YD−901(新日鐵化学株式会社製 BPA型エポキシ樹脂)、エポトート YDF−170、エポトート YDF−8170、エポトート YDF−870GS、エポトート YDF−2001(新日鐵化学株式会社製 BPF型エポキシ樹脂)、エポトート YDPN−638(新日鐵化学株式会社製 フェノールノボラック型エポキシ樹脂)、エポトート YDCN−701(新日鐵化学株式会社製 クレゾールノボラック型エポキシ樹脂)、ZX−1201(新日鐵化学株式会社製 ビスフェノールフルオレン型エポキシ樹脂)、NC−3000(日本化薬株式会社製 ビフェニルアラルキルフェノール型エポキシ樹脂)、EPPN−501H、EPPN−502H(日本化薬株式会社製 多官能エポキシ樹脂)ZX−1355(新日鐵化学株式会社製 ナフタレンジオール型エポキシ樹脂)、ESN−155、ESN−185V、ESN−175(新日鐵化学株式会社製 βナフトールアラルキル型エポキシ樹脂)、ESN−355、ESN−375(新日鐵化学株式会社製 ジナフトールアラルキル型エポキシ樹脂)、ESN−475V、ESN−485(新日鐵化学株式会社製 αナフトールアラルキル型エポキシ樹脂)等の多価フェノール樹脂等のフェノール化合物と、エピハロヒドリンとから製造されるエポキシ樹脂、エポトート YH−434、エポトート YH−434GS(新日鐵化学株式会社製 ジアミノジフェニルメタンテトラグリシジルエーテル)等のアミン化合物と、エピハロヒドリンとから製造されるエポキシ樹脂、YD−171(新日鐵化学株式会社製 ダイマー酸型エポキシ樹脂)等のカルボン酸類と、エピハロヒドリンとから製造されるエポキシ樹脂などが挙げられるがこれらに限定されるものではなく2種類以上併用しても良い。
一般式(1)で示されるリン化合物とキノン化合物と特定の分子量分布を持つエポキシ樹脂(a)を反応する際に、必要に応じて不活性溶媒を使用しても良い。具体的にはヘキサン、ヘプタン、オクタン、デカン、ジメチルブタン、ペンテン、シクロヘキサン、メチルシクロヘキサン、ベンゼン、トルエン、キシレン、エチルベンゼン等の各種炭化水素、エチルエーテル、イソプロピルエーテル、ブチルエーテル、ジイソアミルエーテル、メチルフェニルエーテル、エチルフェニルエーテル、アミルフェニルエーテル、エチルベンジルエーテル、ジオキサン、メチルフラン、テトラヒドロフラン等のエーテル類、メチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブ、セロソルブアセテート、エチレングリコールイソプロピルエーテル、ジエチレングリコールジメチルエーテル、メチルエチルカルビトール、プロピレングリコールモノメチルエーテル、ジメチルホルムアミド、ジメチルスルホキシド等が使用できるが、これらに限定されるものではなく、2種類以上混合して使用しても良い。
本発明のリン含有エポキシ樹脂(A)は硬化剤を配合することにより、硬化性のリン含有エポキシ樹脂組成物とすることが出来る。硬化剤としては各種フェノール樹脂類や酸無水物類、アミン類、ヒドラジッド類、酸性ポリエステル類等の通常使用されるエポキシ樹脂用硬化剤を使用することができ、これらの硬化剤は1種類だけ使用しても2種類以上使用しても良い。これらのうち、本発明の硬化性エポキシ樹脂組成物に含有する硬化剤としてはジシアンジアミドまたはフェノール系硬化剤が特に好ましい。本発明の硬化性エポキシ樹脂組成物において硬化剤の使用量は、エポキシ樹脂の官能基であるエポキシ基1当量に対して硬化剤の官能基0.4〜2.0当量が好ましく、0.5〜1.5当量がより好ましく、特に好ましくは0.5〜1.0当量である。エポキシ基1当量に対して硬化剤が0.4当量に満たない場合、あるいは2.0当量を超える場合は硬化が不完全になり良好な硬化物性が得られない恐れがある。
本発明の硬化性エポキシ樹脂組成物に用いることが出来るフェノール系硬化剤の具体例としては、ビスフェノールA、ビスフェノールF、ビスフェノールC、ビスフェノールK、ビスフェノールZ、ビスフェノールS、テトラメチルビスフェノールA、テトラメチルビスフェノールF、テトラメチルビスフェノールS、テトラメチルビスフェノールZ、ジヒドロキシジフェニルスルフィド、4,4’−チオビス(3−メチル−6−tert−ブチルフェノール)等のビスフェノール類、また、カテコール、レゾルシン、メチルレゾルシン、ハイドロキノン、モノメチルハイドロキノン、ジメチルハイドロキノン、トリメチルハイドロキノン、モノ−tert−ブチルハイドロキノン、ジ−tert−ブチルハイドロキノン等ジヒドロキシベンゼン類、ジヒドロキシナフタレン、ジヒドロキシメチルナフタレン、ジヒドロキシメチルナフタレン、トリヒドロキシナフタレン等ヒドロキシナフタレン類、フェノールノボラック樹脂、DC−5(新日鐵化学株式会社製 クレゾールノボラック樹脂)、ナフトールノボラック樹脂などのフェノール類及び/又はナフトール類とアルデヒド類との縮合物、SN−160、SN−395、SN−485(新日鐵化学株式会社製)等のフェノール類及び/又はナフトール類とキシリレングリコールとの縮合物、フェノール類及び/又はナフトール類とイソプロペニルアセトフェノンとの縮合物、フェノール類及び/又はナフトール類とジシクロペンタジエンとの反応物、フェノール類及び/又はナフトール類とビフェニル系縮合剤との縮合物等のフェノール化合物等が例示される。
上記の、フェノール類としては、フェノール、クレゾール、キシレノール、ブチルフェノール、アミルフェノール、ノニルフェノール、ブチルメチルフェノール、トリメチルフェノール、フェニルフェノール等が挙げられ、ナフトール類としては、1−ナフトール、2−ナフトール等が挙げられる。
アルデヒド類としては、ホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、バレルアルデヒド、カプロンアルデヒド、ベンズアルデヒド、クロルアルデヒド、ブロムアルデヒド、グリオキザール、マロンアルデヒド、スクシンアルデヒド、グルタルアルデヒド、アジピンアルデヒド、ピメリンアルデヒド、セバシンアルデヒド、アクロレイン、クロトンアルデヒド、サリチルアルデヒド、フタルアルデヒド、ヒドロキシベンズアルデヒド等が例示される。ビフェニル系縮合剤としてビス(メチロール)ビフェニル、ビス(メトキシメチル)ビフェニル、ビス(エトキシメチル)ビフェニル、ビス(クロロメチル)ビフェニル等が例示される。
本発明の硬化性エポキシ樹脂組成物に用いることが出来るその他の公知慣用の硬化剤としては、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、無水ピロメリット酸、無水フタル酸、無水トリメリット酸、メチルナジック酸等の酸無水物類、ジエチレントリアミン、トリエチレンテトラミン、メタキシレンジアミン、イソホロンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルフォン、ジアミノジフェニルエーテル、ジシアンジアミド、ダイマー酸等の酸類とポリアミン類との縮合物であるポリアミドアミン等のアミン系化合物等が挙げられる。
更には、エポキシ基の重合を引き起こして硬化せしめる硬化剤としてトリフェニルホスフィンなどのホスフィン化合物、テトラフェニルホスフォニウムブロマイド等のホスホニウム塩、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−ウンデシルイミダゾール、1−シアノエチル−2−メチルイミダゾール等のイミダゾール類及びそれらとトリメリット酸、イソシアヌル酸、硼素等との塩であるイミダゾール塩類、ベンジルジメチルアミン、2,4,6−トリス(ジメチルアミノメチル)フェノール等のアミン類、トリメチルアンモニウムクロライド等の4級アンモニウム塩類、ジアザビシクロ化合物及びそれらとフェノール類、フェノールノボラック樹脂類等との塩類3フッ化硼素とアミン類、エーテル化合物等との錯化合物、芳香族ホスホニウム又はヨードニウム塩などが例示できる。これら硬化剤は、単独でも良いし、2種類以上を併用しても良い。
本発明のエポキシ樹脂組成物に使用されるその他の公知慣用のエポキシ樹脂硬化剤の配合割合は、エポキシ基1当量当たり硬化剤の官能基が0.5〜1.5当量好ましくは0.8〜1.2当量の割合である。また、エポキシ基の重合を引き起こし硬化せしめる硬化剤の配合割合はエポキシ樹脂100質量部に対して0.1〜10質量部、より好ましくは、0.2〜5質量部である。
本発明のリン含有エポキシ樹脂(A)を含んでなる難燃性エポキシ樹脂組成物には、粘度調整用として有機溶剤も用いることができる。用いることが出来る有機溶剤としては、特に規定するものではないが、N,N−ジメチルホルムアミド等のアミド類、エチレングリコールモノメチルエーテル等のエーテル類、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール等のアルコール類、ベンゼン、トルエン等の芳香族炭化水素類等が挙げられ、これらの溶剤のうちの一又は複数種を混合したものを、エポキシ樹脂濃度として20〜90質量%の範囲で配合することができる。
本発明組成物には必要に応じて硬化促進剤を使用することができる。使用できる硬化促進剤の例としては2−メチルイミダゾール、2−エチルイミダゾール、2−エチル−4−メチルイミダゾールなどのイミダゾール類、2−(ジメチルアミノメチル)フェノール、1,8−ジアザ−ビシクロ(5,4,0)ウンデセン−7等の第3級アミン類、トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィントリフェニルボランなどのホスフィン類、オクチル酸スズ等の金属化合物が挙げられる。硬化促進剤は本発明のエポキシ樹脂組成物中のエポキシ樹脂成分100質量部に対して0.02〜5.0質量部が必要に応じて用いられる。硬化促進剤を用いることにより、硬化温度を下げたり、硬化時間を短縮することが出来る。
本発明組成物には必要に応じてフィラーを用いることが出来る。具体的には水酸化アルミニウム、水酸化マグネシウム、タルク、焼成タルク、クレー、カオリン、ベーマイト、酸化チタン、ガラス粉末、シリカバルーン等の無機フィラーが挙げられるが、顔料等を配合しても良い。一般的無機充填材を用いる理由として、耐衝撃性の向上が挙げられる。また、水酸化アルミ、水酸化マグネシウムなどの金属水酸化物を用いた場合、難燃助剤として作用し、リン含有率が少なくても難燃性を確保することが出来る。特に配合量が10質量%以上でないと、耐衝撃性の効果は少ない。しかしながら、配合量が150質量%を越えると積層板用途として必要な項目である接着性が低下する。また、ガラス繊維、パルプ繊維、合成繊維、セラミック繊維等の繊維質充填材や微粒子ゴム、熱可塑性エラストマーなどの有機充填材を上記樹脂組成物に含有することもできる。
本発明のエポキシ樹脂組成物を硬化することによってエポキシ樹脂硬化物を得ることが出来る。硬化の際には例えば樹脂シート、樹脂付き銅箔、プリプレグなどの形態とし、積層して加熱加圧硬化することで積層板としてのリン含有エポキシ樹脂硬化物を得ることが出来る。
本発明のリン含有エポキシ樹脂(A)を用いたリン含有エポキシ樹脂組成物を作成し、加熱硬化により積層板のリン含有エポキシ樹脂硬化物を評価した結果、リン化合物とキノン化合物と特定の分子量分布を持つエポキシ樹脂(a)を反応したリン含有エポキシ樹脂(A)は、従来公知のリン化合物とエポキシ樹脂類から得られるリン含有エポキシ樹脂と比較して低粘度で作業性が良いだけではなく、高い耐熱性と高い接着性を併せ持つことが可能であり、更には難燃性をも改良出来た。The molar ratio of phenols and aldehydes is indicated by the molar ratio of phenols to 1 mole of aldehydes, and is produced at a ratio of 1 or more. When the molar ratio is large, a large amount of dinuclear and trinuclear bodies are produced, When the molar ratio is small, a large amount of high molecular weight is formed, and dinuclear and trinuclear bodies are decreased.
In order to obtain the epoxy resin (a) having a specific molecular weight distribution used in the present invention, a method of removing dinuclear bodies from the obtained novolak resins by utilizing the difference in solubility of various solvents, dinuclear bodies in an aqueous alkali solution It can be obtained by a method of dissolving and removing, and other known separation methods may be used.
A novolak type epoxy resin having a specific molecular weight distribution can be obtained by using a known epoxidation technique for a novolak resin having a controlled molecular weight. Alternatively, a novolac type epoxy resin having a specific molecular weight distribution can also be obtained by removing dinuclear components from commercially available novolak type epoxy resins by various methods. Other known separation methods may also be used.
The epoxy resin (a) having a specific molecular weight distribution used in the present invention preferably has a dinuclear content of 15 area% or less, more preferably 5 area% to 12 area%. By containing a small amount of the binuclear body, physical properties such as adhesive strength can be improved. The trinuclear content is preferably 15 area% to 60 area%, more preferably 20 area% to 50 area%. If the trinuclear content is less than 15 area%, the heat resistance tends to be poor, and if it exceeds 60 area%, the adhesion tends to be poor. In addition, although it does not prescribe | regulate especially regarding the range more than a tetranuclear body and a pentanuclear body, 30 area%-70 area% of the sum total of the content rate of a trinuclear body and a tetranuclear body is preferable. Flame retardancy is further improved when the total content of trinuclear body and tetranuclear body is in the range of 30 area% to 70 area%. The content of pentanuclear or higher is preferably 45 area% or less, and more preferably 40 area% or less. If the content of pentanuclear or more is 45 area% or less, a cured product with higher adhesion can be obtained. The number average molecular weight is preferably 350 to 700, 380 to 600 is more preferable. When the number average molecular weight exceeds 700, the viscosity of the obtained phosphorus-containing epoxy resin (A) is increased, which may adversely affect workability and substrate impregnation properties. The reason why the flame retardancy of the phosphorus-containing epoxy resin (A) obtained under these conditions is improved is that the elastic modulus of the resulting cured product is lowered, so that the char generated at the time of combustion becomes stronger and higher heat insulation. It is thought to bring about an effect, but it has not been verified.
Specific examples of the phosphorus compound represented by the general formula (1) used in the present invention include dimethylphosphine, diethylphosphine, diphenylphosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA). Sanko Co., Ltd.), dimethyl phosphine oxide, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, 1,4-cyclooctylene phosphine oxide, 1,5-cyclooctylene phosphine oxide (manufactured by CPHO Nippon Chemical Industry Co., Ltd.) Etc. These phosphorus compounds may be used alone or in combination of two or more, and are not limited thereto.
Examples of the quinone compound in the present invention include benzoquinone, naphthoquinone, tolquinone, anthraquinone and isomers thereof, those having a substituent of a hydrocarbon group, and the like. However, it is not limited to these. The molar ratio of the phosphorus compound and quinone compound represented by the general formula (1) is preferably phosphorus compound: quinone compound = 1: 1 or less, more preferably 1: 0.99 to 0.2, and 1: 0.98. ~ 0.40 is desirable. If the quinone compound is excessive, it will remain in the phosphorus-containing epoxy resin (A) as an unreacted component, so that the physical properties are likely to be lowered. If it is lower than 0.2, the heat resistance and flame retardancy may be adversely affected. Moreover, after reacting a phosphorus compound and a quinone compound, you may use what extracted only the reaction component by refinement | purification.
The phosphorus-containing epoxy resin (A) of the present invention is obtained by reacting a phosphorus compound represented by the general formula (1), a quinone compound and an epoxy resin (a) having a specific molecular weight distribution as essential components. In addition, other known and commonly used epoxy resins and modifiers can be used as long as the effects are not affected.
The reaction of the phosphorus compound represented by the general formula (1), the quinone compound and the epoxy resin (a) having a specific molecular weight distribution is performed by a known method. A method of reacting with a phosphorus compound and a quinone compound and further reacting with an epoxy resin (a), a method of reacting a phosphorus compound and a quinone compound in an epoxy resin (a), and further reacting with an epoxy resin (a), a phosphorus compound in advance There is a method of reacting an epoxy resin (a) with a product obtained by reacting a quinone compound with a quinone compound, but the reaction procedure is not particularly limited in the present invention.
The reaction temperature may be a temperature usually set for the synthesis of the indirect epoxy resin, and is 100 ° C to 250 ° C, preferably 120 ° C to 200 ° C.
A catalyst may be used for the reaction to shorten the time and reduce the reaction temperature. The catalyst that can be used is not particularly limited, and those usually used for the synthesis of indirect epoxy resins can be used. For example, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium bromide, etc. Various catalysts such as phosphonium salts, imidazoles such as 2 methyl imidazole, 2 ethyl 4-methyl imidazole and the like can be used, and these may be used alone or in combination of two or more, but are not limited thereto. Further, it may be divided and used in several times.
The amount of the catalyst is not particularly limited, but is 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass based on the total weight of the epoxy resin (a) and other known and commonly used epoxy resins. % Or less. When the amount of the catalyst is large, the epoxy group self-polymerization reaction proceeds in some cases.
When reacting the phosphorus compound represented by the general formula (1), the quinone compound and the epoxy resin (a) having a specific molecular weight distribution, various epoxy resin modifiers are added within the range that does not impair the characteristics of the present invention. You may use together. Examples of the modifier include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, hydroquinone, methyl hydroquinone, dimethyl hydroquinone, dibutyl hydroquinone, resorcin, methyl resorcin, biphenol, tetramethyl biphenol, dihydroxy naphthalene, dihydroxy diphenyl ether, dihydroxy stilbene, Various phenols such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolak resin, terpene phenol resin, heavy oil modified phenol resin, brominated phenol novolak resin, , Various phenols and hydroxybenzaldehyde Polyhydric phenol resin obtained by condensation reaction with various aldehydes such as crotonaldehyde, glyoxal, aniline, phenylenediamine, toluidine, xylidine, diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone , Diaminodiphenyl sulfide, diaminodiphenyl sulfone, bis (aminophenyl) fluorene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bis Aminophenoxyphenyl ether, bisaminophenoxy Biphenyl, bis aminophenoxy phenyl sulfone, bis aminophenoxy phenyl propane, an amine compound such as diamino naphthalene may be used in combination of two or more kinds is not limited thereto.
When reacting the phosphorus compound represented by the general formula (1), the quinone compound and the epoxy resin (a) having a specific molecular weight distribution, the other epoxy resins are not impaired in the properties of the present invention as necessary. It can also be used together. Specific examples of epoxy resins that can be used in combination include Epototo YDC-1312, ZX-1027 (hydroquinone type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YX-4000 (manufactured by Mitsubishi Chemical Corporation) ZX-1251 (new day) Biphenol type epoxy resin manufactured by Sakai Chemical Co., Ltd.), Epototo YD-127, Epototo YD-128, Epotot YD-8125, Epotot YD-825GS, Epotot YD-011, Epotot YD-900, Epotot YD-901 BPA type epoxy resin manufactured by Co., Ltd.), Epototo YDF-170, Epototo YDF-8170, Epototo YDF-870GS, Epototo YDF-2001 (BPF type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo YDPN-638 (Nippon Steel) Chemistry (Phenol novolac type epoxy resin manufactured by a formula company), Epototo YDCN-701 (Cresol novolak type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000 (Nippon Kayaku Co., Ltd. biphenylaralkylphenol type epoxy resin), EPPN-501H, EPPN-502H (Nippon Kayaku Co., Ltd. polyfunctional epoxy resin) ZX-1355 (Nippon Chemical Co., Ltd. naphthalenediol type epoxy resin) ), ESN-155, ESN-185V, ESN-175 (manufactured by Nippon Steel Chemical Co., Ltd., β-naphthol aralkyl epoxy resin), ESN-355, ESN-375 (manufactured by Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl epoxy resin) ), ESN-475V Epoxy resin produced from a phenolic compound such as polyhydric phenol resin such as ESN-485 (manufactured by Nippon Steel Chemical Co., Ltd., α-naphthol aralkyl type epoxy resin) and epihalohydrin, Epototo YH-434, Epototo YH-434GS (New) Carboxylic acids such as epoxy resins manufactured from amine compounds such as diaminodiphenylmethane tetraglycidyl ether) manufactured by Nippon Steel Chemical Co., Ltd. and epihalohydrin, YD-171 (dimer acid type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) Examples include epoxy resins produced from epihalohydrin, but are not limited to these, and two or more types may be used in combination.
When reacting the phosphorus compound represented by the general formula (1), the quinone compound and the epoxy resin (a) having a specific molecular weight distribution, an inert solvent may be used as necessary. Specifically, various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methyl phenyl ether , Ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran and other ethers, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol, Propylene glycol monomethyl ether, dimethylformamide, dimethyl Although sulfoxide or the like can be used, is not limited thereto, it may be used by mixing 2 or more kinds.
The phosphorus-containing epoxy resin (A) of the present invention can be made into a curable phosphorus-containing epoxy resin composition by blending a curing agent. As the curing agent, various curing resins for epoxy resins such as various phenol resins, acid anhydrides, amines, hydrazides, and acidic polyesters can be used, and only one of these curing agents is used. Or you may use two or more types. Of these, dicyandiamide or a phenolic curing agent is particularly preferable as the curing agent contained in the curable epoxy resin composition of the present invention. In the curable epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.4 to 2.0 equivalents of the functional group of the curing agent with respect to 1 equivalent of the epoxy group that is the functional group of the epoxy resin. -1.5 equivalent is more preferable, Especially preferably, it is 0.5-1.0 equivalent. When the curing agent is less than 0.4 equivalent with respect to 1 equivalent of epoxy group, or when it exceeds 2.0 equivalent, curing may be incomplete and good cured properties may not be obtained.
Specific examples of the phenolic curing agent that can be used in the curable epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, and tetramethylbisphenol. Bisphenols such as F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4′-thiobis (3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcin, hydroquinone, monomethyl Dihydroxybenzes such as hydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone Phenols such as hydroxy, naphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene, phenol novolac resin, DC-5 (Cresol novolak resin manufactured by Nippon Steel Chemical Co., Ltd.), naphthol novolak resin, and the like // Condensates of naphthols and aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical Co., Ltd.) and / or condensates of naphthols and xylylene glycol, Condensates of phenols and / or naphthols with isopropenyl acetophenone, reactants of phenols and / or naphthols and dicyclopentadiene, condensates of phenols and / or naphthols and biphenyl condensing agents, etc. Fe Examples of the compound include a nor compound.
Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol. Examples of naphthols include 1-naphthol and 2-naphthol. It is done.
Aldehydes include formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelin aldehyde, sebacin aldehyde And acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. Examples of the biphenyl condensing agent include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, and bis (chloromethyl) biphenyl.
Other known and commonly used curing agents that can be used in the curable epoxy resin composition of the present invention include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methyl Acid anhydrides such as nadic acid, polyamidoamine that is a condensate of acids and polyamines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, dicyandiamide, and dimer acid And amine compounds such as
Furthermore, phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4methyl as curing agents that cause epoxy group polymerization and cure. Imidazoles such as imidazole, 2-undecyl imidazole, 1-cyanoethyl-2-methylimidazole and the like and salts thereof with trimellitic acid, isocyanuric acid, boron, etc., benzyldimethylamine, 2,4,6- Amines such as tris (dimethylaminomethyl) phenol, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds and salts thereof with phenols, phenol novolac resins, etc. Boron trifluoride and amines , Complex compounds of ether compounds, and aromatic phosphonium or iodonium salts can be exemplified. These curing agents may be used alone or in combination of two or more.
The blending ratio of other known and commonly used epoxy resin curing agents used in the epoxy resin composition of the present invention is such that the functional group of the curing agent is 0.5 to 1.5 equivalents, preferably 0.8 to 1 equivalent per epoxy group equivalent. The ratio is 1.2 equivalents. Moreover, the mixture ratio of the hardening | curing agent which causes superposition | polymerization of an epoxy group and is hardened is 0.1-10 mass parts with respect to 100 mass parts of epoxy resins, More preferably, it is 0.2-5 mass parts.
In the flame retardant epoxy resin composition comprising the phosphorus-containing epoxy resin (A) of the present invention, an organic solvent can also be used for viscosity adjustment. The organic solvent that can be used is not particularly specified, but amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, methanol, ethanol and the like. Examples include alcohols, aromatic hydrocarbons such as benzene and toluene, and a mixture of one or more of these solvents in an epoxy resin concentration range of 20 to 90% by mass. it can.
A hardening accelerator can be used for this invention composition as needed. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5 , 4, 0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, and metal compounds such as tin octylate. 0.02-5.0 mass parts is used for a hardening accelerator as needed with respect to 100 mass parts of epoxy resin components in the epoxy resin composition of the present invention. By using a curing accelerator, the curing temperature can be lowered or the curing time can be shortened.
A filler can be used for this invention composition as needed. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, boehmite, titanium oxide, glass powder, and silica balloon, but pigments may be blended. The reason for using a general inorganic filler is an improvement in impact resistance. Also, aluminum hydroxide, when a metal hydroxide such as magnesium hydroxide, acts as a flame retardant aid, even with a small phosphorus content can be secured flame retardancy. In particular, if the blending amount is not 10% by mass or more, the impact resistance effect is small. However, if the blending amount exceeds 150% by mass , the adhesiveness, which is an item necessary for the use of laminates, is lowered. Moreover, organic fillers, such as fiber fillers, such as glass fiber, a pulp fiber, a synthetic fiber, a ceramic fiber, fine particle rubber, and a thermoplastic elastomer, can also be contained in the said resin composition.
A cured epoxy resin can be obtained by curing the epoxy resin composition of the present invention. At the time of curing, for example, a resin sheet, a copper foil with a resin, a prepreg, and the like are formed and laminated and cured by heating and pressing to obtain a cured phosphorus-containing epoxy resin as a laminated board.
As a result of making a phosphorus-containing epoxy resin composition using the phosphorus-containing epoxy resin (A) of the present invention and evaluating the phosphorus-containing epoxy resin cured product of the laminate by heat curing, a phosphorus compound, a quinone compound, and a specific molecular weight distribution The phosphorus-containing epoxy resin (A) obtained by reacting the epoxy resin (a) having not only a low viscosity and good workability compared to a phosphorus-containing epoxy resin obtained from a conventionally known phosphorus compound and epoxy resins, It was possible to have both high heat resistance and high adhesiveness, and further improved flame retardancy.
実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。特に断りがない限り「部」は質量部を表し、「%」は質量%を表す。測定方法はそれぞれ以下の方法により測定した。
測定方法を以下に示す。
エポキシ当量:JIS K7236に準じた。
二核体含有率、三核体含有率、四核体含有率、五核体以上含有率、数平均分子量(Mn)、重量平均分子量(Mw)、及び分散度(Mw/Mn):ゲルパーミエーションクロマトグラフィーを用いて分子量分布を測定し、二核体含有率、三核体含有率、四核体含有率、五核体以上含有率はピークの面積%から、数平均分子量、重量平均分子量、分散度は標準の単分散ポリスチレン(東ソー株式会社製 A−500,A−1000,A−2500,A−5000,F−1,F−2,F−4,F−10,F−20,F−40)より求めた検量線より換算した。具体的には、本体(東ソー株式会社製 HLC−8220GPC)にカラム(東ソー株式会社製 TSKgelG4000HXL、TSKgelG3000HXL、TSKgelG2000HXL)を直列に備えたものを使用し、カラム温度は40℃にした。また、溶離液にはテトラヒドロフランを用い、1ml/minの流速とし、検出器はRI(示差屈折計)検出器を用いた。
リン含有率:試料に硫酸、塩酸、過塩素酸を加え、加熱して湿式灰化し、全てのリン原子をオルトリン酸とした。硫酸酸性溶液中でメタバナジン酸塩及びモリブデン酸塩を反応させ、生じたリンバナードモリブデン酸錯体の420nmにおける吸光度を測定し、予めリン酸二水素カリウムを用いて作成した検量線により、求めたリン原子含有率を%で表した。積層板のリン含有率は、積層板の樹脂成分に対する含有率として表した。
銅箔剥離強さ及び層間接着力:JIS C 6481に準じて測定し、層間接着力は7層めと8層めの間で引き剥がし測定した。
燃焼性:UL94(Underwriters Laboratories Inc.の安全認証規格)に準じた。5本の試験片について試験を行い、1回目と2回目の接炎(5本それぞれ2回ずつで計10回の接炎)後の有炎燃焼持続時間の合計時間を秒で表した。
ガラス転移温度DSC:示差走査熱量測定装置(エスアイアイ・ナノテクノロジー株式会社製 EXSTAR6000 DSC6200)にて10℃/分の昇温条件で測定を行った時のDSC外挿値の温度で表した。
ガラス転移温度TMA:熱機械分析装置(エスアイアイ・ナノテクノロジー株式会社製 EXSTAR6000 TMA/SS120U)にて5℃/分の昇温条件で測定を行った時のTMA外挿値の温度で表した。
実施例及び比較例に使用したエポキシ樹脂を次に示す。
エポトートYDPN−638(新日鐵化学株式会社製 汎用型フェノールノボラック型エポキシ樹脂、二核体含有率22面積%、三核体含有率15面積%、三核体及び四核体含有率の合計が25面積%、五核体以上含有率53面積%、数平均分子量528、重量平均分子量1127、分散度2.13、エポキシ当量176g/eq)(図1参照)
エポトートYDF−170(新日鐵化学株式会社製 ビスフェノールF型エポキシ樹脂 エポキシ当量170g/eq)
合成例1(フェノールノボラック樹脂の合成)
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた4つ口のガラス製セパラブルフラスコに、フェノール2500部、シュウ酸二水和物 7.5部を仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。37.4%ホルマリン 474.1部を80℃で滴下を開始し、30分で滴下を終了した。更に反応温度を92℃に保ち3時間反応を行った。昇温を行い反応生成水を系外に除去しながら110℃まで昇温した。残存フェノールを160℃にて減圧下回収を行い、フェノールノボラック樹脂を得た。更に温度を上げて二核体の一部を回収した。得られたフェノールノボラック樹脂の二核体含有率及び三核体含有率はゲルパーミエーションクロマトグラフィーによる測定でそれぞれ10面積%及び38面積%であった。
合成例2(フェノールノボラック型エポキシ樹脂の合成)
合成例1と同様な装置に、合成例1のフェノールノボラック樹脂 665.8部、エピクロロヒドリン 2110.8部、水 17部を仕込み、攪拌しながら50℃まで昇温した。49%水酸化ナトリウム水溶液 14.2部を仕込み3時間反応を行った。64℃まで昇温し、水の還流が起きる程度に減圧を引き、49%水酸化ナトリウム水溶液 457.7部を3時間かけて滴下し反応をおこなった。温度を70℃まで上げ脱水を行い、温度を135℃として残存するエピクロロヒドリンを回収した。常圧に戻し、MIBK 1232部を加えて溶解した。イオン交換水1200部を加え、攪拌静置して副生した食塩を水に溶解して除去した。次に49%水酸化ナトリウム水溶液 37.4部を仕込み80℃で90分間攪拌反応して精製反応を行った。MIBKを追加、水洗を数回行いイオン性不純物を除去した。溶剤を回収し、ノボラック型エポキシ樹脂を得た。二核体含有率9面積%、三核体含有率36面積%、三核体及び四核体含有率の合計が53面積%、五核体以上含有率38面積%、数平均分子量513、重量平均分子量713、分散度1.39、エポキシ当量174g/eqであった。(図2参照)
実施例1
合成例1と同様な装置にHCA(三光株式会社製 9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド リン含有率14.2%)127部、トルエン270部を仕込み、加熱して溶解した。次に1,4−ナフトキノン(東京化成工業株式会社製 純度98%以上)70部を発熱に注意しながら仕込み、90℃以下に温度を保ち、30分保持した。更に徐々に温度を上げて還流温度で2時間保持した。トルエンを一部回収後、合成例2のフェノールノボラック型エポキシ樹脂 804部を仕込み、窒素ガスを導入しながら攪拌を行い130℃まで昇温した。トリフェニルホスフィンを触媒として0.20部を添加して160℃で3時間反応を行った。得られたエポキシ樹脂のエポキシ当量は276g/eq、リン含有率は1.8%であった。結果を表1にまとめる。
実施例2
HCA 141部、1,4−ナフトキノン 77部、合成例2のフェノールノボラック型エポキシ樹脂 782部、トリフェニルホスフィン 0.22部とした以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は294g/eq、リン含有率は2.0%であった。結果を表1にまとめる。
実施例3
HCA 155部、1,4−ナフトキノン 85部、合成例2のフェノールノボラック型エポキシ樹脂 760部、トリフェニルホスフィン 0.24部とした以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は317g/eq、リン含有率は2.2%であった。結果を表1にまとめる。
実施例4
HCA 141部、1,4−ナフトキノン 83部、合成例2のフェノールノボラック型エポキシ樹脂 726部、トリフェニルホスフィン 0.22部とし、更にYDF−170B 50部をフェノールノボラック型エポキシ樹脂と同時に配合した以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は297g/eq、リン含有率は2.0%であった。結果を表1にまとめる。
実施例5
HCA 155部、1,4−ナフトキノン 57部、合成例2のフェノールノボラック型エポキシ樹脂 638部、トリフェニルホスフィン 0.21部とし、更にYDF−170 150部をフェノールノボラック型エポキシ樹脂と同時に配合した以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は286g/eq、リン含有率は2.2%であった。結果を表1にまとめる。
実施例6
HCA 155部、1,4−ナフトキノン 34部、合成例2のフェノールノボラック型エポキシ樹脂 777部、トリフェニルホスフィン 0.19部とし、更にBRG−555(昭和電工株式会社製フェノールノボラック樹脂)34部をフェノールノボラック型エポキシ樹脂と同時に配合した以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は310g/eq、リン含有率は2.2%であった。結果を表1にまとめる。
実施例7
HCA 155部、1,4−ナフトキノン 23部、合成例2のフェノールノボラック型エポキシ樹脂 779部、トリフェニルホスフィン 0.18部とし、更にBRG−555 43部をフェノールノボラック型エポキシ樹脂と同時に配合した以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は310g/eq、リン含有率は2.2%であった。結果を表1にまとめる。
合成例1と同様な装置にYDPN−638 824部、HCA 176部を仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。130℃にてトリフェニルホスフィンを触媒として0.18部を添加して160℃で3時間反応を行った。得られたエポキシ樹脂のエポキシ当量は263g/eq、リン含有率は2.5%であった。結果を表1にまとめる。
比較例2
合成例2のフェノールノボラック型エポキシ樹脂 824部、HCA 176部とした以外は比較例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は266g/eq、リン含有率は2.5%であった。結果を表1にまとめる。
比較例3
HCA 141部、1,4−ナフトキノン 77部、YDPN−638 782部、トリフェニルホスフィン 0.22部とした以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は303g/eq、リン含有率は2.0%であった。結果を表1にまとめる。
比較例4
HCA 155部、1,4−ナフトキノン 80部、YDPN−638 465部、トリフェニルホスフィン 0.23部とし、更にYDF−170を300部をフェノールノボラック型エポキシ樹脂と同時に配合した以外は実施例1と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は311g/eq、リン含有率は2.2%であった。結果を表1にまとめる。
実施例8〜実施例14及び比較例5〜比較例8
実施例1〜実施例7、比較例1〜比較例4のエポキシ樹脂と、硬化剤としてジシアンジアミドを表2の処方で配合し、メチルエチルケトン、プロピレングリコールモノメチルエーテル、N,N−ジメチルホルムアミドで調整した混合溶剤に溶解してエポキシ樹脂組成物ワニスを得た。
得られた樹脂組成物ワニスをガラスクロスWEA 7628 XS13(日東紡績株式会社製0.18mm厚)に含浸した。含浸したガラスクロスを150℃の熱風循環炉で乾燥を行い、プリプレグを得た。得られたプリプレグ8枚を重ね、上下に銅箔(三井金属鉱業株式会社製 3EC)を重ね、130℃×15分及び170℃×20kg/cm2×70分間加熱、加圧を行い積層板を得た。積層板のTMA、DSC、DMSによるガラス転移温度、銅箔剥離強さ、層間接着力、難燃性試験の結果を表2にまとめる。
The measuring method is shown below.
Epoxy equivalent: Conforms to JIS K7236.
Dinuclear content, trinuclear content, tetranuclear content, pentanuclear content, number average molecular weight (Mn), weight average molecular weight (Mw), and dispersity (Mw / Mn): gel perm The molecular weight distribution is measured using an association chromatography, and the binuclear content, trinuclear content, tetranuclear content, and pentanuclear content are the number average molecular weight and weight average molecular weight from the peak area%. The dispersion is standard monodisperse polystyrene (A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, manufactured by Tosoh Corporation). F-40) was converted from the calibration curve obtained. Specifically, a main body (HLC-8220GPC manufactured by Tosoh Corporation) and a column (TSKgel G4000HXL, TSKgel G3000HXL, TSKgelG2000HXL manufactured by Tosoh Corporation) were used in series, and the column temperature was set to 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector.
Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus atoms to orthophosphoric acid. Phosphorus atoms obtained by reacting metavanadate and molybdate in a sulfuric acid acidic solution, measuring the absorbance at 420 nm of the resulting phosphovanadomolybdate complex, and using a calibration curve prepared in advance using potassium dihydrogen phosphate representation of the content percent. Phosphorus content of the laminate was expressed as the content of the resin component of the laminate.
Copper foil peel strength and interlayer adhesion: measured according to JIS C 6481, and interlayer adhesion was measured by peeling between the seventh and eighth layers.
Flammability: Conforms to UL94 (Underwriters Laboratories Inc. safety certification standard). Five test pieces were tested, and the total time of the flammable combustion duration after the first and second flame contact (two flames each twice for a total of 10 flames) was expressed in seconds.
Glass transition temperature DSC: Expressed by the DSC extrapolated temperature when measured under a temperature rising condition of 10 ° C./min with a differential scanning calorimeter (EXSTAR DSC6200, manufactured by SII Nano Technology Co., Ltd.).
Glass transition temperature TMA: TMA extrapolated temperature when measured under a temperature rising condition of 5 ° C./min with a thermomechanical analyzer (EXSTAR6000 TMA / SS120U manufactured by SII Nano Technology Co., Ltd.).
The epoxy resins used in the examples and comparative examples are shown below.
Epototo YDPN-638 (manufactured by Nippon Steel Chemical Co., Ltd., general-purpose phenol novolac type epoxy resin,
Epototo YDF-170 (Nippon Steel Chemical Co., Ltd. bisphenol F type epoxy resin epoxy equivalent 170 g / eq)
Synthesis Example 1 (Synthesis of phenol novolac resin)
While introducing a nitrogen gas into a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction apparatus, charge 2500 parts of phenol and 7.5 parts of oxalic acid dihydrate. The mixture was stirred and heated to raise the temperature. Addition of 474.1 parts of 37.4% formalin was started at 80 ° C., and the addition was completed in 30 minutes. Further, the reaction was carried out for 3 hours while maintaining the reaction temperature at 92 ° C. The temperature was raised to 110 ° C. while removing the reaction product water out of the system. Residual phenol was collected at 160 ° C. under reduced pressure to obtain a phenol novolac resin. The temperature was further raised to recover a part of the binuclear body. The obtained phenol novolac resin had a dinuclear content and a trinuclear content of 10 area% and 38 area%, respectively, as measured by gel permeation chromatography.
Synthesis Example 2 (Synthesis of phenol novolac type epoxy resin)
In a device similar to Synthesis Example 1, 665.8 parts of the phenol novolak resin of Synthesis Example 1, 2110.8 parts of epichlorohydrin, and 17 parts of water were charged, and the temperature was raised to 50 ° C. with stirring. A 49% aqueous sodium hydroxide solution (14.2 parts) was charged and the reaction was carried out for 3 hours. The temperature was raised to 64 ° C., the pressure was reduced to such an extent that water was refluxed, and 457.7 parts of 49% aqueous sodium hydroxide solution was added dropwise over 3 hours to carry out the reaction. The temperature was raised to 70 ° C. to perform dehydration, and the remaining epichlorohydrin was recovered at a temperature of 135 ° C. The pressure was returned to normal pressure, and 1232 parts of MIBK was added and dissolved. 1200 parts of ion-exchanged water was added, and the mixture was left standing with stirring, and the salt produced as a by-product was dissolved in water and removed. Next, 37.4 parts of a 49% aqueous sodium hydroxide solution was added, and the mixture was stirred and reacted at 80 ° C. for 90 minutes to carry out a purification reaction. MIBK was added and washed with water several times to remove ionic impurities. The solvent was recovered to obtain a novolac type epoxy resin. Dinuclear content 9 area%, trinuclear content 36 area%, trinuclear and tetranuclear content total is 53 area%, pentanuclear or higher content 38 area%, number average molecular weight 513, weight The average molecular weight was 713, the degree of dispersion was 1.39, and the epoxy equivalent was 174 g / eq. (See Figure 2)
Example 1
127 parts of HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide phosphorus content 14.2% by Sanko Co., Ltd.) and 270 parts of toluene were charged in the same apparatus as in Synthesis Example 1. Dissolved by heating. Next, 70 parts of 1,4-naphthoquinone (purity 98% or more manufactured by Tokyo Chemical Industry Co., Ltd.) was charged while paying attention to heat generation, and the temperature was maintained at 90 ° C. or lower and held for 30 minutes. The temperature was gradually raised and maintained at the reflux temperature for 2 hours. After partially recovering toluene, 804 parts of the phenol novolac type epoxy resin of Synthesis Example 2 was added and stirred while introducing nitrogen gas, and the temperature was raised to 130 ° C. Using triphenylphosphine as a catalyst, 0.20 part was added and reacted at 160 ° C. for 3 hours. The epoxy equivalent of the obtained epoxy resin was 276 g / eq, and the phosphorus content was 1.8%. The results are summarized in Table 1.
Example 2
The same operation as in Example 1 was carried out except that 141 parts of HCA, 77 parts of 1,4-naphthoquinone, 782 parts of phenol novolac type epoxy resin of Synthesis Example 2 and 0.22 part of triphenylphosphine were used. The epoxy equivalent of the obtained epoxy resin was 294 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 1.
Example 3
The same operation as in Example 1 was carried out except that 155 parts of HCA, 85 parts of 1,4-naphthoquinone, 760 parts of phenol novolac type epoxy resin of Synthesis Example 2 and 0.24 part of triphenylphosphine were used. The epoxy equivalent of the obtained epoxy resin was 317 g / eq, and the phosphorus content was 2.2%. The results are summarized in Table 1.
Example 4
141 parts of HCA, 83 parts of 1,4-naphthoquinone, 726 parts of phenol novolac type epoxy resin of Synthesis Example 2, 0.22 part of triphenylphosphine, and 50 parts of YDF-170B were blended together with the phenol novolac type epoxy resin. The same operation as in Example 1 was performed. The epoxy equivalent of the obtained epoxy resin was 297 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 1.
Example 5
155 parts of HCA, 57 parts of 1,4-naphthoquinone, 638 parts of phenol novolac type epoxy resin of Synthesis Example 2, 0.21 part of triphenylphosphine, and 150 parts of YDF-170 were blended together with the phenol novolac type epoxy resin. The same operation as in Example 1 was performed. The epoxy equivalent of the obtained epoxy resin was 286 g / eq, and the phosphorus content was 2.2%. The results are summarized in Table 1.
Example 6
155 parts of HCA, 34 parts of 1,4-naphthoquinone, 777 parts of phenol novolac type epoxy resin of Synthesis Example 2, 0.19 part of triphenylphosphine, and 34 parts of BRG-555 (Phenol novolac resin manufactured by Showa Denko KK) The same operation as in Example 1 was performed except that it was blended simultaneously with the phenol novolac type epoxy resin. The epoxy equivalent of the obtained epoxy resin was 310 g / eq, and the phosphorus content was 2.2%. The results are summarized in Table 1.
Example 7
155 parts of HCA, 23 parts of 1,4-naphthoquinone, 779 parts of phenol novolac type epoxy resin of Synthesis Example 2 and 0.18 part of triphenylphosphine, and 43 parts of BRG-555 are blended together with the phenol novolac type epoxy resin. The same operation as in Example 1 was performed. The epoxy equivalent of the obtained epoxy resin was 310 g / eq, and the phosphorus content was 2.2%. The results are summarized in Table 1.
In the same apparatus as in Synthesis Example 1, 824 parts of YDPN-638 and 176 parts of HCA were charged, stirred while introducing nitrogen gas, heated and heated. At 130 ° C, 0.18 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 3 hours. The epoxy equivalent of the obtained epoxy resin was 263 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 1.
Comparative Example 2
The same operation as in Comparative Example 1 was performed except that 824 parts of the phenol novolac type epoxy resin of Synthesis Example 2 and 176 parts of HCA were used. The epoxy equivalent of the obtained epoxy resin was 266 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 1.
Comparative Example 3
The same operation as in Example 1 was carried out except that 141 parts of HCA, 77 parts of 1,4-naphthoquinone, 782 parts of YDPN-638, and 0.22 part of triphenylphosphine were used. The epoxy equivalent of the obtained epoxy resin was 303 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 1.
Comparative Example 4
Example 1 except that 155 parts of HCA, 80 parts of 1,4-naphthoquinone, 465 parts of YDPN-638, 0.23 part of triphenylphosphine, and 300 parts of YDF-170 were blended simultaneously with the phenol novolac epoxy resin. The same operation was performed. The epoxy equivalent of the obtained epoxy resin was 311 g / eq, and the phosphorus content was 2.2%. The results are summarized in Table 1.
Examples 8 to 14 and Comparative Examples 5 to 8
Example 1 to Example 7, Comparative Examples 1 to 4 and epoxy resin and dicyandiamide as a curing agent were blended according to the formulation shown in Table 2 and mixed with methyl ethyl ketone, propylene glycol monomethyl ether, and N, N-dimethylformamide. An epoxy resin composition varnish was obtained by dissolving in a solvent.
The obtained resin composition varnish was impregnated into glass cloth WEA 7628 XS13 (Nittobo Co., Ltd., 0.18 mm thickness). The impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C. to obtain a prepreg. 8 sheets of the obtained prepreg are stacked, and copper foil (3EC manufactured by Mitsui Mining & Smelting Co., Ltd.) is stacked on top and bottom, and heated and pressed at 130 ° C. × 15 minutes and 170 ° C. × 20 kg /
本発明は、特定のリン化合物とキノン化合物と特定の分子量分布を持つエポキシ樹脂(a)を必須として反応して得られるリン含有エポキシ樹脂(A)であって難燃性、耐熱性、接着性に優れた電子回路基板用のエポキシ樹脂として利用することが出来る。 The present invention is a phosphorus-containing epoxy resin (A) obtained by reacting a specific phosphorus compound, a quinone compound and an epoxy resin (a) having a specific molecular weight distribution as an essential component, and is flame retardant, heat resistant, and adhesive. It can be used as an epoxy resin for an electronic circuit board having excellent resistance.
Claims (6)
(ゲルパーミエーションクロマトグラフィー測定条件)
東ソー株式会社製 TSKgelG4000HXL、TSKgelG3000HXL、TSKgelG2000HXLを直列に備えたものを使用し、カラム温度は40℃にした。また、溶離液にはテトラヒドロフランを用い、1ml/minの流速とし、検出器はRI(示差屈折計)検出器を用いた。測定試料はサンプル0.1gを10mlのTHFに溶解した。得られたクロマトグラムにより二核体含有率及び三核体含有率を算出し、標準ポリスチレンによる検量線により数平均分子量を測定する。
(Gel permeation chromatography measurement conditions)
Tosoh Corporation TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL were used in series, and the column temperature was 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector. As a measurement sample, 0.1 g of a sample was dissolved in 10 ml of THF. The binuclear content and trinuclear content are calculated from the obtained chromatogram, and the number average molecular weight is measured by a calibration curve using standard polystyrene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014521221A JP6067699B2 (en) | 2012-06-15 | 2013-05-13 | Phosphorus-containing epoxy resin, composition containing epoxy resin as essential component, and cured product |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012135707 | 2012-06-15 | ||
JP2012135707 | 2012-06-15 | ||
PCT/JP2013/063865 WO2013187184A1 (en) | 2012-06-15 | 2013-05-13 | Phosphorus-containing epoxy resin, composition containing phosphorus-containing epoxy resin as essential component, and cured product |
JP2014521221A JP6067699B2 (en) | 2012-06-15 | 2013-05-13 | Phosphorus-containing epoxy resin, composition containing epoxy resin as essential component, and cured product |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2013187184A1 true JPWO2013187184A1 (en) | 2016-02-04 |
JP6067699B2 JP6067699B2 (en) | 2017-01-25 |
Family
ID=49758016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014521221A Active JP6067699B2 (en) | 2012-06-15 | 2013-05-13 | Phosphorus-containing epoxy resin, composition containing epoxy resin as essential component, and cured product |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP6067699B2 (en) |
KR (1) | KR102038173B1 (en) |
CN (3) | CN108314774B (en) |
SG (1) | SG11201408343TA (en) |
TW (1) | TWI598371B (en) |
WO (1) | WO2013187184A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6179446B2 (en) * | 2014-04-14 | 2017-08-16 | 株式会社オートネットワーク技術研究所 | Reactor |
JP6670045B2 (en) * | 2015-03-13 | 2020-03-18 | 日鉄ケミカル&マテリアル株式会社 | Oxazolidone ring-containing epoxy resin, production method thereof, epoxy resin composition and cured product |
JP6770793B2 (en) * | 2015-08-19 | 2020-10-21 | 日鉄ケミカル&マテリアル株式会社 | Flame-retardant epoxy resin composition and its cured product |
US11332608B2 (en) * | 2016-12-27 | 2022-05-17 | Nippon Steel Chemical & Material Co., Ltd. | Curable epoxy resin composition, and fiber-reinforced composite material using same |
JP2019104821A (en) * | 2017-12-12 | 2019-06-27 | 日鉄ケミカル&マテリアル株式会社 | Epoxy resin composition and cured product of the same |
KR20210047861A (en) * | 2018-08-27 | 2021-04-30 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Phosphorus-containing epoxy resin, epoxy resin composition, prepreg, laminate, circuit board material and cured product |
JP7211744B2 (en) * | 2018-09-19 | 2023-01-24 | 日鉄ケミカル&マテリアル株式会社 | Epoxy resin composition and cured product thereof |
JP7211829B2 (en) * | 2019-01-23 | 2023-01-24 | 日鉄ケミカル&マテリアル株式会社 | Epoxy resin composition and cured product thereof |
JP2020122034A (en) * | 2019-01-29 | 2020-08-13 | 日鉄ケミカル&マテリアル株式会社 | Epoxy resin composition, and cured product of the same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002012739A (en) * | 2000-06-29 | 2002-01-15 | Nippon Kayaku Co Ltd | Flame-retardant epoxy resin composition and use thereof |
JP2002194041A (en) * | 1999-12-16 | 2002-07-10 | Sumitomo Bakelite Co Ltd | Method for producing phenol resin |
JP2002249540A (en) * | 2001-02-23 | 2002-09-06 | Toto Kasei Co Ltd | Phosphorus-containing epoxy resin composition |
JP2007126683A (en) * | 2001-11-16 | 2007-05-24 | Asahi Organic Chem Ind Co Ltd | Novolak type phenolic resin and method for producing the same |
JP2010077263A (en) * | 2008-09-25 | 2010-04-08 | Panasonic Electric Works Co Ltd | Epoxy resin composition for prepreg, prepreg, and multilayer printed wiring board |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3268498B2 (en) | 1990-05-01 | 2002-03-25 | 東都化成株式会社 | Phosphorus-containing flame-retardant epoxy resin |
JP3092009B2 (en) | 1990-05-01 | 2000-09-25 | 東都化成株式会社 | Flame retardant and thermosetting flame-retardant resin composition containing the flame retardant |
JP2823057B2 (en) * | 1990-12-20 | 1998-11-11 | 日本化薬株式会社 | Manufacturing method of epoxy resin |
JP3613724B2 (en) | 1997-09-09 | 2005-01-26 | 東都化成株式会社 | Phosphorus-containing epoxy resin composition |
JP3533973B2 (en) | 1998-01-27 | 2004-06-07 | 東都化成株式会社 | Phosphorus-containing epoxy resin composition |
JP2001123049A (en) | 1999-10-28 | 2001-05-08 | Dainippon Ink & Chem Inc | Flame-retardant epoxy resin composition |
JP4588834B2 (en) | 2000-04-06 | 2010-12-01 | パナソニック電工株式会社 | Phosphorus-containing epoxy resin composition, flame-retardant resin sheet using the phosphorus-containing epoxy resin, metal foil with resin, prepreg and laminate, multilayer board |
JP4906020B2 (en) | 2001-07-26 | 2012-03-28 | 新日鐵化学株式会社 | Phosphorus-containing phenol resin and epoxy resin composition using the phenol resin |
CN100560631C (en) * | 2004-06-29 | 2009-11-18 | 旭化成电子材料株式会社 | Fire retarded epoxy resin composition |
WO2006006593A1 (en) * | 2004-07-13 | 2006-01-19 | Hitachi Chemical Co., Ltd. | Epoxy resin molding material for sealing and electronic component device |
JP5632163B2 (en) * | 2007-11-09 | 2014-11-26 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin and phosphorus-containing epoxy resin composition, production method thereof, curable resin composition and cured product using the resin, and resin composition |
JP5441477B2 (en) * | 2009-04-01 | 2014-03-12 | 新日鉄住金化学株式会社 | Flame retardant phosphorus-containing epoxy resin composition and cured product thereof |
JP5686512B2 (en) * | 2009-11-05 | 2015-03-18 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin, resin composition, and flame-retardant cured product thereof |
JP5544184B2 (en) * | 2010-02-08 | 2014-07-09 | 新日鉄住金化学株式会社 | Method for producing phosphorus-containing epoxy resin, epoxy resin composition and cured product thereof |
JP5579008B2 (en) * | 2010-09-29 | 2014-08-27 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin |
-
2013
- 2013-05-13 WO PCT/JP2013/063865 patent/WO2013187184A1/en active Application Filing
- 2013-05-13 CN CN201810193561.6A patent/CN108314774B/en active Active
- 2013-05-13 CN CN201811147674.9A patent/CN109293881B/en active Active
- 2013-05-13 CN CN201380030849.7A patent/CN104379626B/en active Active
- 2013-05-13 JP JP2014521221A patent/JP6067699B2/en active Active
- 2013-05-13 SG SG11201408343TA patent/SG11201408343TA/en unknown
- 2013-05-13 KR KR1020147034499A patent/KR102038173B1/en active IP Right Grant
- 2013-06-03 TW TW102119560A patent/TWI598371B/en active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002194041A (en) * | 1999-12-16 | 2002-07-10 | Sumitomo Bakelite Co Ltd | Method for producing phenol resin |
JP2002012739A (en) * | 2000-06-29 | 2002-01-15 | Nippon Kayaku Co Ltd | Flame-retardant epoxy resin composition and use thereof |
JP2002249540A (en) * | 2001-02-23 | 2002-09-06 | Toto Kasei Co Ltd | Phosphorus-containing epoxy resin composition |
JP2007126683A (en) * | 2001-11-16 | 2007-05-24 | Asahi Organic Chem Ind Co Ltd | Novolak type phenolic resin and method for producing the same |
JP2010077263A (en) * | 2008-09-25 | 2010-04-08 | Panasonic Electric Works Co Ltd | Epoxy resin composition for prepreg, prepreg, and multilayer printed wiring board |
Also Published As
Publication number | Publication date |
---|---|
JP6067699B2 (en) | 2017-01-25 |
CN109293881B (en) | 2021-04-13 |
CN104379626A (en) | 2015-02-25 |
WO2013187184A1 (en) | 2013-12-19 |
CN108314774B (en) | 2021-02-12 |
TW201402632A (en) | 2014-01-16 |
CN104379626B (en) | 2019-03-22 |
CN108314774A (en) | 2018-07-24 |
SG11201408343TA (en) | 2015-01-29 |
TWI598371B (en) | 2017-09-11 |
KR102038173B1 (en) | 2019-10-29 |
CN109293881A (en) | 2019-02-01 |
KR20150031237A (en) | 2015-03-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6067699B2 (en) | Phosphorus-containing epoxy resin, composition containing epoxy resin as essential component, and cured product | |
JP5911700B2 (en) | Flame retardant epoxy resin, composition containing epoxy resin as essential component, and cured product | |
US11884773B2 (en) | Phenolic resin, epoxy resin, epoxy resin composition and cured product of same | |
TWI823991B (en) | Method for manufacturing epoxy resin composition, prepreg, laminate, circuit board material, hardened product, and phosphorus-containing epoxy resin | |
JP7368551B2 (en) | Method for producing epoxy resin composition and method for using biphenylaralkyl phenolic resin | |
TW202330705A (en) | Polyvalent hydroxy resin, epoxy resin, method for producing the same, epoxy resin composition and cured product thereof | |
JP2020122034A (en) | Epoxy resin composition, and cured product of the same | |
CN102757547B (en) | The phosphorous epoxy resin with nitrogen | |
TW202130733A (en) | Epoxy resin composition, prepreg, laminate, printed circuit board, and cured product | |
JP5896693B2 (en) | Phosphorus and nitrogen containing epoxy resin | |
KR20200033205A (en) | Epoxy resin composition and cured product thereof | |
JP5591176B2 (en) | Phosphorus and nitrogen containing epoxy resin | |
JP6246126B2 (en) | Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product thereof | |
TW202208483A (en) | Epoxy resin composition and cured product thereof | |
TW202208486A (en) | 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: 20160418 |
|
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: 20161208 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161221 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6067699 Country of ref document: JP 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 |