JP7412939B2 - Method for manufacturing phenoxy resin - Google Patents
Method for manufacturing phenoxy resin Download PDFInfo
- Publication number
- JP7412939B2 JP7412939B2 JP2019172994A JP2019172994A JP7412939B2 JP 7412939 B2 JP7412939 B2 JP 7412939B2 JP 2019172994 A JP2019172994 A JP 2019172994A JP 2019172994 A JP2019172994 A JP 2019172994A JP 7412939 B2 JP7412939 B2 JP 7412939B2
- Authority
- JP
- Japan
- Prior art keywords
- phenoxy resin
- group
- producing
- bifunctional
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920006287 phenoxy resin Polymers 0.000 title claims description 65
- 239000013034 phenoxy resin Substances 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 15
- -1 phenol compound Chemical class 0.000 claims description 95
- 230000001588 bifunctional effect Effects 0.000 claims description 66
- 229920000647 polyepoxide Polymers 0.000 claims description 56
- 239000003822 epoxy resin Substances 0.000 claims description 55
- 229910052698 phosphorus Inorganic materials 0.000 claims description 27
- 239000011574 phosphorus Substances 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 28
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 21
- 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 20
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 229930185605 Bisphenol Natural products 0.000 description 13
- 239000002966 varnish Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 6
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 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
- 150000002989 phenols Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 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 3
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZKTFNWPPVIAFDC-UHFFFAOYSA-N OB(O)O.P.P.P Chemical class OB(O)O.P.P.P ZKTFNWPPVIAFDC-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- UTCOUOISVRSLSH-UHFFFAOYSA-N 1,2-Anthracenediol Chemical compound C1=CC=CC2=CC3=C(O)C(O)=CC=C3C=C21 UTCOUOISVRSLSH-UHFFFAOYSA-N 0.000 description 2
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 2
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 2
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 2
- BHMQYONSWBTGNV-UHFFFAOYSA-N 2-[[3-diphenylphosphoryl-4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C=1C=CC=CC=1P(C=1C(=CC=C(OCC2OC2)C=1)OCC1OC1)(=O)C1=CC=CC=C1 BHMQYONSWBTGNV-UHFFFAOYSA-N 0.000 description 2
- FSYPIGPPWAJCJG-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1OCC1CO1 FSYPIGPPWAJCJG-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- WQKILXGJWIEVHR-UHFFFAOYSA-N 1-(4-benzyl-6-oxobenzo[c][1,2]benzoxaphosphinin-6-yl)naphthalene-2,7-diol Chemical compound C12=CC(O)=CC=C2C=CC(O)=C1P(C1=CC=CC=C1C1=CC=C2)(=O)OC1=C2CC1=CC=CC=C1 WQKILXGJWIEVHR-UHFFFAOYSA-N 0.000 description 1
- WMPGCOIUVFJFMG-UHFFFAOYSA-N 1-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)naphthalene-2,7-diol Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=C(O)C=CC2=CC=C(O)C=C21 WMPGCOIUVFJFMG-UHFFFAOYSA-N 0.000 description 1
- HPHCUWNVOLOGRP-UHFFFAOYSA-N 1-[9-(2-hydroxynaphthalen-1-yl)fluoren-9-yl]naphthalen-2-ol Chemical class C1=CC=C2C(C3(C4=CC=CC=C4C4=CC=CC=C43)C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 HPHCUWNVOLOGRP-UHFFFAOYSA-N 0.000 description 1
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
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- VTQLZQMNJYFXIZ-UHFFFAOYSA-M benzyl(trimethyl)phosphanium;bromide Chemical compound [Br-].C[P+](C)(C)CC1=CC=CC=C1 VTQLZQMNJYFXIZ-UHFFFAOYSA-M 0.000 description 1
- TXXACRDXEHKXKD-UHFFFAOYSA-M benzyl(trimethyl)phosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)CC1=CC=CC=C1 TXXACRDXEHKXKD-UHFFFAOYSA-M 0.000 description 1
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- ROPYUGUXRIMKBU-UHFFFAOYSA-M cyclohexyl(trimethyl)phosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C1CCCCC1 ROPYUGUXRIMKBU-UHFFFAOYSA-M 0.000 description 1
- IJWRZPFPAQZLTK-UHFFFAOYSA-M cyclohexyl(trimethyl)phosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C1CCCCC1 IJWRZPFPAQZLTK-UHFFFAOYSA-M 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 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
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N methyl resorcinol Natural products COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical class CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 description 1
- TVVPMLFGPYQGTG-UHFFFAOYSA-M tetramethylphosphanium;iodide Chemical compound [I-].C[P+](C)(C)C TVVPMLFGPYQGTG-UHFFFAOYSA-M 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
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- IDXDWPWXHTXJMZ-UHFFFAOYSA-N tris(2,4,6-trimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(C)=C1P(C=1C(=CC(C)=CC=1C)C)C1=C(C)C=C(C)C=C1C IDXDWPWXHTXJMZ-UHFFFAOYSA-N 0.000 description 1
- XDHRVAHAGMMFMC-UHFFFAOYSA-N tris(2,4-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC=C1P(C=1C(=CC(C)=CC=1)C)C1=CC=C(C)C=C1C XDHRVAHAGMMFMC-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
- LQEKTSMTEYLBLJ-UHFFFAOYSA-N tris(4-ethoxyphenyl)phosphane Chemical compound C1=CC(OCC)=CC=C1P(C=1C=CC(OCC)=CC=1)C1=CC=C(OCC)C=C1 LQEKTSMTEYLBLJ-UHFFFAOYSA-N 0.000 description 1
- PKJSAOOUHLBNPB-UHFFFAOYSA-N tris(4-methoxy-2-propan-2-ylphenyl)phosphane Chemical compound CC(C)C1=CC(OC)=CC=C1P(C=1C(=CC(OC)=CC=1)C(C)C)C1=CC=C(OC)C=C1C(C)C PKJSAOOUHLBNPB-UHFFFAOYSA-N 0.000 description 1
- BDGUINGZRGNLPD-UHFFFAOYSA-N tris(4-methoxy-3,5-dimethylphenyl)phosphane Chemical compound C1=C(C)C(OC)=C(C)C=C1P(C=1C=C(C)C(OC)=C(C)C=1)C1=CC(C)=C(OC)C(C)=C1 BDGUINGZRGNLPD-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- UQHFPPSBVOIUFM-UHFFFAOYSA-N tris(4-tert-butylphenyl)phosphane Chemical compound C1=CC(C(C)(C)C)=CC=C1P(C=1C=CC(=CC=1)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1 UQHFPPSBVOIUFM-UHFFFAOYSA-N 0.000 description 1
- ADZJWYULTMTLQZ-UHFFFAOYSA-N tritylphosphane;hydrobromide Chemical compound [Br-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 ADZJWYULTMTLQZ-UHFFFAOYSA-N 0.000 description 1
- IZYFBZDLXRHRLF-UHFFFAOYSA-N tritylphosphane;hydroiodide Chemical compound [I-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 IZYFBZDLXRHRLF-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Description
本発明は、反応活性に優れ、得られるフェノキシ樹脂が他の成分、特に硬化剤と混合した際の貯蔵安定性に優れるフェノキシ樹脂の製造方法に関する。 The present invention relates to a method for producing a phenoxy resin which has excellent reaction activity and excellent storage stability when the resulting phenoxy resin is mixed with other components, particularly a curing agent.
エポキシ樹脂は耐熱性、接着性、耐薬品性、耐水性、機械的強度及び電気特性等に優れていることから、塗料、土木、接着、電気材料用途等の分野で広く使用されている。そして種々の方法で高分子量化することで製膜性が付与される。その高分子量化されたエポキシ樹脂は、フェノキシ樹脂と称される。特にビスフェノールＡ型のフェノキシ樹脂は、主に塗料用ワニスのベース樹脂、フィルム成形用のベース樹脂として使用され、或いはエポキシ樹脂ワニスに添加して流動性の調整や硬化物としたときの靭性改良、接着性改良の目的に使用される。また、リン原子や臭素原子を骨格中に有するものは、エポキシ樹脂組成物や熱可塑性樹脂に配合される難燃剤として使用されている。 Epoxy resins have excellent heat resistance, adhesiveness, chemical resistance, water resistance, mechanical strength, electrical properties, etc., and are therefore widely used in fields such as paints, civil engineering, adhesives, and electrical materials. Film-forming properties are imparted by increasing the molecular weight using various methods. The high molecular weight epoxy resin is called phenoxy resin. In particular, bisphenol A type phenoxy resins are mainly used as base resins for paint varnishes and film molding, or are added to epoxy resin varnishes to adjust fluidity and improve toughness when cured. Used for the purpose of improving adhesion. Moreover, those having a phosphorus atom or a bromine atom in their skeleton are used as flame retardants blended into epoxy resin compositions and thermoplastic resins.
フェノキシ樹脂の製造方法としては、一般的に、２官能フェノール化合物にアルカリの存在下、エピハロヒドリンを反応させる「一段法」や、２官能エポキシ樹脂と２官能フェノール化合物を触媒の存在下で反応させる「二段法」等が知られている。二段法は一段法に比べて食塩等の副生成物がほとんど生じないため、合成後に精製することが困難なフェノキシ樹脂の製造に適した方法であることが知られている。非特許文献１には二段法によりフェノキシ樹脂を製造する際の触媒として、アンモニウム塩類化合物、アルカリ性化合物類等が一般的に使用されることが記載されている。 Generally, methods for producing phenoxy resin include a "one-step method" in which a bifunctional phenol compound is reacted with epihalohydrin in the presence of an alkali, and a "one-step method" in which a bifunctional epoxy resin and a bifunctional phenol compound are reacted in the presence of a catalyst. Two-stage method" etc. are known. It is known that the two-stage method produces fewer by-products such as common salt than the one-stage method, and is therefore suitable for producing phenoxy resins that are difficult to purify after synthesis. Non-Patent Document 1 describes that ammonium salt compounds, alkaline compounds, etc. are generally used as catalysts when producing phenoxy resins by a two-step process.
フェノキシ樹脂を前述したような塗料、土木、接着、電気材料等の分野で用いる場合、主にベース樹脂として使用されるため、エポキシ樹脂や硬化剤を始めとする他材料との混合物として使用することが一般的である。本発明者らの詳細な検討によれば、二段法で製造する際に、上記非特許文献１に記載されているようなアンモニウム塩類化合物、アルカリ性化合物類を触媒として使用したフェノキシ樹脂は、他材料と混合した際の貯蔵安定性が不十分となる場合がある。また、リン系化合物としてトリフェニルホスフィンが触媒として使用されることも非特許文献１に記載されているが、ホスフィン類化合物は二段法の触媒としては活性が不十分であった。 When phenoxy resin is used in the aforementioned fields such as paints, civil engineering, adhesives, and electrical materials, it is mainly used as a base resin, so it must be used as a mixture with other materials such as epoxy resins and hardeners. is common. According to detailed studies by the present inventors, phenoxy resins using ammonium salt compounds and alkaline compounds as catalysts as described in the above non-patent document 1 when produced by a two-step process are Storage stability may be insufficient when mixed with other materials. Furthermore, Non-Patent Document 1 also describes that triphenylphosphine, which is a phosphorus compound, is used as a catalyst, but phosphine compounds have insufficient activity as catalysts for the two-step process.
本発明の課題は、２官能エポキシ樹脂と２官能フェノール化合物とを二段法で反応させる際に、反応が十分に進行し、かつ得られたフェノキシ樹脂が他材料との配合した際の貯蔵安定性に優れるフェノキシ樹脂の製造方法を提供することにある。 The object of the present invention is to ensure that the reaction proceeds sufficiently when a bifunctional epoxy resin and a bifunctional phenol compound are reacted in a two-step process, and that the obtained phenoxy resin has storage stability when blended with other materials. An object of the present invention is to provide a method for producing a phenoxy resin having excellent properties.
本発明者らは上記課題を解決するために鋭意検討した結果、２官能エポキシ樹脂と２官能フェノール化合物を原料として用いてフェノキシ樹脂を得る際に、特定のホスホニウムボレート化合物の存在下で反応させることにより、上記課題を解決し得ることを見出し、発明の完成に至った。 As a result of intensive studies to solve the above problems, the present inventors found that when obtaining a phenoxy resin using a bifunctional epoxy resin and a bifunctional phenol compound as raw materials, the reaction was carried out in the presence of a specific phosphonium borate compound. The inventors have discovered that the above-mentioned problems can be solved, and have completed the invention.
すなわち、本発明は、２官能エポキシ樹脂と２官能フェノール化合物とを触媒の存在下で反応させるフェノキシ樹脂の製造方法であって、該触媒が下記一般式（１）で表されるホスホニウムボレート化合物であることを特徴とするフェノキシ樹脂の製造方法である。
一般式（１）中、Ｐはリン原子、Ｒ１、Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、置換もしくは無置換のアリール基、アルキル基、アラルキル基、又は水素原子である。また、Ｂはホウ素原子、Ｘ１、Ｘ２、Ｘ３及びＸ４は、それぞれ独立して、置換もしくは無置換のアリール基、アルキル基、アラルキル基、水素原子、又はハロゲン原子である。
That is, the present invention is a method for producing a phenoxy resin in which a bifunctional epoxy resin and a bifunctional phenol compound are reacted in the presence of a catalyst, the catalyst being a phosphonium borate compound represented by the following general formula (1). This is a method for producing phenoxy resin characterized by the following.
In general formula (1), P is a phosphorus atom, and R 1 , R 2 , R 3 and R 4 are each independently a substituted or unsubstituted aryl group, alkyl group, aralkyl group, or hydrogen atom. Further, B is a boron atom, and X 1 , X 2 , X 3 and X 4 are each independently a substituted or unsubstituted aryl group, alkyl group, aralkyl group, hydrogen atom, or halogen atom.
上記ホスホニウムボレート化合物の配合量は、２官能エポキシ樹脂１００質量部に対して０．００５～５．０質量部であることが好ましく、上記２官能エポキシ樹脂１．０モルに対し、上記２官能フェノール化合物を０．９～１．０モル使用することが好ましい。 The blending amount of the phosphonium borate compound is preferably 0.005 to 5.0 parts by weight per 100 parts by weight of the bifunctional epoxy resin, and the amount of the above bifunctional phenol compound is preferably 0.005 to 5.0 parts by weight per 100 parts by weight of the bifunctional epoxy resin. Preferably, 0.9 to 1.0 mol of the compound is used.
上記２官能エポキシ樹脂の一部又は全部、及び／又は上記２官能フェノール化合物の一部又は全部は、フロオレン環含有化合物であることが好ましい。 It is preferable that a part or all of the bifunctional epoxy resin and/or a part or all of the bifunctional phenol compound are fluorene ring-containing compounds.
上記２官能エポキシ樹脂の一部又は全部、及び／又は上記２官能フェノール化合物の一部又は全部は、リン含有化合物であることが好ましく、得られるフェノキシ樹脂のリン含有率が１～６質量％であることが好ましい。 Part or all of the bifunctional epoxy resin and/or part or all of the bifunctional phenol compound are preferably phosphorus-containing compounds, and the resulting phenoxy resin has a phosphorus content of 1 to 6% by mass. It is preferable that there be.
得られるフェノキシ樹脂のエポキシ当量は、４０００～２０００００ｇ／ｅｑ．であることが好ましく、重量平均分子量（Ｍｗ）は、１００００～１５００００であることが好ましい。 The epoxy equivalent of the obtained phenoxy resin is 4000 to 200000 g/eq. The weight average molecular weight (Mw) is preferably 10,000 to 150,000.
本発明のフェノキシ樹脂の製造方法は、十分な反応速度を有する。また、本発明の製造方法により得られるフェノキシ樹脂は、他の成分、特に硬化剤を配合した際の貯蔵安定性に優れる。このことから、本発明の製造方法により得られるフェノキシ樹脂、及びそれを配合した樹脂組成物は、塗料、電気・電子材料、接着剤、炭素繊維強化樹脂（ＣＦＲＰ）等の分野において好適に用いることができる。 The method for producing a phenoxy resin of the present invention has a sufficient reaction rate. Furthermore, the phenoxy resin obtained by the production method of the present invention has excellent storage stability when other components, especially a curing agent, are added. Therefore, the phenoxy resin obtained by the production method of the present invention and the resin composition blended with the same can be suitably used in the fields of paints, electrical/electronic materials, adhesives, carbon fiber reinforced resins (CFRP), etc. I can do it.
本発明のフェノキシ樹脂の製造方法は、２官能エポキシ樹脂と２官能フェノール化合物を特定のホスホニウムボレート化合物の存在下で反応させる。なお、本明細書において、本発明のフェノキシ樹脂の製造方法を「本発明の製造方法」と、本発明の製造方法で得られるフェノキシ樹脂を「本発明のフェノキシ樹脂」と称することがある。 In the method for producing a phenoxy resin of the present invention, a bifunctional epoxy resin and a bifunctional phenol compound are reacted in the presence of a specific phosphonium borate compound. In addition, in this specification, the manufacturing method of the phenoxy resin of this invention may be called "the manufacturing method of this invention," and the phenoxy resin obtained by the manufacturing method of this invention may be called "the phenoxy resin of this invention."
本発明のフェノキシ樹脂は、他の成分、特に硬化剤と配合したときに、貯蔵安定性に顕著に優れるという効果を奏する。また、本発明において使用するホスホニウムボレート化合物は、ホスフィン化合物と比較して二段法での活性が高いため、反応時間が短くなる。 The phenoxy resin of the present invention exhibits the effect of significantly superior storage stability when blended with other components, particularly a curing agent. Furthermore, the phosphonium borate compound used in the present invention has higher activity in the two-step method than phosphine compounds, so the reaction time is shorter.
本発明の製造方法で使用する２官能エポキシ樹脂は、分子内に２個のエポキシ基を有するエポキシ樹脂であればよい。これらの２官能エポキシ樹脂は１種のみでも複数種を組み合わせて使用してもよい。 The bifunctional epoxy resin used in the production method of the present invention may be any epoxy resin having two epoxy groups in its molecule. These bifunctional epoxy resins may be used alone or in combination.
２官能エポキシ樹脂としては、例えば、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ビスフェノールＥジグリシジルエーテル、ビスフェノールＺジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、ビスフェノールアセトフェノンジグリシジルエーテル、ビスフェノールトリメチルシクロヘキサンジグリシジルエーテル、ビスフェノールフルオレンジグリシジルエーテル（例えば、ＺＸ－１２０１（日鉄ケミカル＆マテリアル株式会社製）等）、ビスクレゾールフルオレンジグリシジルエーテル、テトラメチルビスフェノールＡジグリシジルエーテル、テトラメチルビスフェノールＦジグリシジルエーテル、テトラ－ｔ－ブチルビスフェノールＡジグリシジルエーテル、テトラメチルビスフェノールＳジグリシジルエーテル、ジヒドロキシジフェニルエーテルジグリシジルエーテル、チオジフェノールジグリシジルエーテル、テトラブロムビスフェノールＡジグリシジルエーテル、等のビスフェノール型エポキシ樹脂や、ビフェノールジグリシジルエーテル、テトラメチルビフェノールジグリシジルエーテル、ジメチルビフェノールジグリシジルエーテル、テトラ－ｔ－ブチルビフェノールジグリシジルエーテル等のビフェノール型エポキシ樹脂や、ハイドロキノンジグリシジルエーテル、メチルハイドロキノンジグリシジルエーテル、ジブチルハイドロキノンジグリシジルエーテル、レゾルシンジグリシジルエーテル、メチルレゾルシンジグリシジルエーテル等のベンゼンジオール型エポキシ樹脂や、ジヒドロキシアントラセンジグリシジルエーテル、ヒドロアントラハイドロキノンジグリシジルエーテル、ジヒドロキシナフタレンジグリシジルエーテル、ビスナフトールフルオレンジグリシジルエーテル、ジフェニルジシクロペンタジエン型エポキシ樹脂等が挙げられる。 Examples of the bifunctional epoxy resin include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol S diglycidyl ether, bisphenol AD diglycidyl ether, and bisphenol acetophenone diglycidyl ether. , bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fluorene diglycidyl ether (for example, ZX-1201 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), etc.), biscresol fluorene glycidyl ether, tetramethylbisphenol A diglycidyl ether, tetramethylbisphenol Bisphenol-type epoxies such as F diglycidyl ether, tetra-t-butylbisphenol A diglycidyl ether, tetramethylbisphenol S diglycidyl ether, dihydroxydiphenyl ether diglycidyl ether, thiodiphenol diglycidyl ether, tetrabromobisphenol A diglycidyl ether, etc. Resins, biphenol type epoxy resins such as biphenol diglycidyl ether, tetramethylbiphenol diglycidyl ether, dimethylbiphenol diglycidyl ether, tetra-t-butylbiphenol diglycidyl ether, hydroquinone diglycidyl ether, methylhydroquinone diglycidyl ether, dibutyl Benzenediol-type epoxy resins such as hydroquinone diglycidyl ether, resorcin diglycidyl ether, methylresorcin diglycidyl ether, dihydroxyanthracene diglycidyl ether, hydroanthrahydroquinone diglycidyl ether, dihydroxynaphthalene diglycidyl ether, bisnaphthol fluorene glycidyl ether, Examples include diphenyldicyclopentadiene type epoxy resin.
２官能エポキシ樹脂としては、更に、上記２官能エポキシ樹脂の芳香環に水素を添加した２官能水素化エポキシ樹脂や、アジピン酸、コハク酸、フタル酸、テトラヒドロフタル酸、メチルヘキサヒドロフタル酸、テレフタル酸、イソフタル酸、オルソフタル酸、ビフェニルジカルボン酸、ダイマー酸等の種々のジカルボン酸類と、エピハロヒドリンとから製造されるグリシジルエステル型エポキシ樹脂や、アニリン等のアミン化合物と、エピハロヒドリンとから製造されるグリシジルアミン型エポキシ樹脂や、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、１，５－ペンタンジオールジグリシジルエーテル、ポリペンタメチレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ポリヘキサメチレングリコールジグリシジルエーテル、１，７－ヘプタンジオールジグリシジルエーテル、ポリヘプタメチレングリコールジグリシジルエーテル、１，８－オクタンジオールジグリシジルエーテル、１，１０－デカンジオールジグリシジルエーテル、２，２－ジメチル－１，３－プロパンジオールジグリシジルエーテル等の鎖状構造のみからなる（ポリ）アルキレングリコール型エポキシ樹脂や、１，４－シクロヘキサンジメタノールジグリシジルエーテル等の環状構造を有するアルキレングリコール型エポキシ樹脂や、脂肪族環状エポキシ樹脂や、リン含有２官能エポキシ樹脂（例えば、ＦＸ－３０５（日鉄ケミカル＆マテリアル株式会社製）、ジフェニルホスフィニルハイドロキノンジグリシジルエーテル等）等も挙げられる。
得られるフェノキシ樹脂の耐熱性の向上のためには、ジヒドロキシナフタレンジグリシジルエーテル、ビスフェノールフルオレンジグリシジルエーテル、ビスクレゾールフルオレンジグリシジルエーテル、ビスナフトールフルオレンジグリシジルエーテルが好ましく、ビスフェノールフルオレンジグリシジルエーテル、ビスクレゾールフルオレンジグリシジルエーテル、ビスナフトールフルオレンジグリシジルエーテル等のフルオレン環構造を有する２官能エポキシ樹脂がより好ましい。難燃性付与のためには、テトラブロムビスフェノールＡジグリシジルエーテル、リン含有２官能エポキシ樹脂が好ましく、リン含有２官能エポキシ樹脂がより好ましい。
Further examples of the bifunctional epoxy resin include bifunctional hydrogenated epoxy resins in which hydrogen is added to the aromatic ring of the above bifunctional epoxy resin, adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, and terephthalic acid. Glycidyl ester type epoxy resins manufactured from various dicarboxylic acids such as acids, isophthalic acid, orthophthalic acid, biphenyldicarboxylic acid, and dimer acid and epihalohydrin, and glycidyl amines manufactured from amine compounds such as aniline and epihalohydrin. type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,5 -Pentanediol diglycidyl ether, polypentamethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, 1,7-heptanediol diglycidyl ether, polyheptamethylene glycol diglycidyl ether , 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, etc. (poly)alkylene glycol type consisting only of a chain structure Epoxy resins, alkylene glycol type epoxy resins with a cyclic structure such as 1,4-cyclohexanedimethanol diglycidyl ether, aliphatic cyclic epoxy resins, and phosphorus-containing bifunctional epoxy resins (for example, FX-305 (Nippon Steel Chemical Co., Ltd.) & Material Co., Ltd.), diphenylphosphinyl hydroquinone diglycidyl ether, etc.).
In order to improve the heat resistance of the resulting phenoxy resin, dihydroxynaphthalene diglycidyl ether, bisphenol fluorene glycidyl ether, biscresol fluorene glycidyl ether, bisnaphthol fluorene glycidyl ether are preferred, and bisphenol fluorene glycidyl ether and biscresol are preferred. More preferred are bifunctional epoxy resins having a fluorene ring structure, such as fluorene glycidyl ether and bisnaphthol fluorene glycidyl ether. For imparting flame retardancy, tetrabromobisphenol A diglycidyl ether and phosphorus-containing bifunctional epoxy resin are preferred, and phosphorus-containing bifunctional epoxy resin is more preferred.
本発明の製造方法で使用する２官能フェノール化合物としては、芳香環に結合した水酸基を２個以上有する化合物であればよい。これらの２官能フェノール化合物は、１種のみでも複数種を組み合わせて使用してもよい。 The bifunctional phenol compound used in the production method of the present invention may be any compound having two or more hydroxyl groups bonded to an aromatic ring. These bifunctional phenol compounds may be used alone or in combination.
２官能フェノール化合物としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＥ、ビスフェノールＺ、ビスフェノールＳ、ビスフェノールＡＤ、ビスフェノールアセトフェノン、ビスフェノールトリメチルシクロヘキサン、ビスフェノールフルオレン、ビスクレゾールフルオレン、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－ｔ－ブチルビスフェノールＡ、テトラメチルビスフェノールＳ、ジヒドロキシジフェニルエーテル、ジヒドロキシジフェニルメタン、ビス（ヒドロキシフェノキシ）ベンゼン、チオジフェノール、ジヒドロキシスチルベン等のビスフェノール類や、ビフェノール、テトラメチルビフェノール、ジメチルビフェノール、テトラ－ｔ－ブチルビフェノール等のビフェノール類や、ハイドロキノン、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、メチルレゾルシン等のベンゼンジオール類や、ジヒドロキシアントラセン、ジヒドロキシナフタレン、ジヒドロアントラハイドロキノン類等が挙げられる。
得られるフェノキシ樹脂の耐熱性向上のためには、ジヒドロキシナフタレン、ビスフェノールフルオレン、ビスクレゾールフルオレンが好ましく、ビスフェノールフルオレン、ビスクレゾールフルオレンがより好ましい。
Examples of bifunctional phenol compounds include bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenolacetophenone, bisphenol trimethylcyclohexane, bisphenol fluorene, biscresol fluorene, tetramethylbisphenol A, and tetramethylbisphenol F. , tetra-t-butylbisphenol A, tetramethylbisphenol S, dihydroxydiphenyl ether, dihydroxydiphenylmethane, bis(hydroxyphenoxy)benzene, thiodiphenol, dihydroxystilbene and other bisphenols, biphenol, tetramethylbiphenol, dimethylbiphenol, tetra- Examples include biphenols such as t-butylbiphenol, benzenediols such as hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcinol, and methylresorcinol, and dihydroxyanthracene, dihydroxynaphthalene, and dihydroanthrahydroquinone.
In order to improve the heat resistance of the resulting phenoxy resin, dihydroxynaphthalene, bisphenol fluorene, and bis-cresol fluorene are preferred, and bisphenol fluorene and bis-cresol fluorene are more preferred.
２官能フェノール化合物の使用量は、２官能エポキシ樹脂１．００モルに対して、０．９～１．１モルが好ましく、０．９５～１．０５モルがより好ましく、０．９６～１．００モルが更に好ましく、０．９７～０．９９モルが特に好ましい。２官能フェノール化合物の配合量がこの範囲内であれば、得られるフェノキシ樹脂の分子量が十分伸長するので好ましい。また、反応性の点では末端基にエポキシ基を多く存在することが望ましいため、２官能フェノール化合物の配合量は１．００モル未満が好ましい。 The amount of the bifunctional phenol compound to be used is preferably 0.9 to 1.1 mol, more preferably 0.95 to 1.05 mol, and 0.96 to 1.0 mol per 1.00 mol of the bifunctional epoxy resin. 00 mol is more preferred, and 0.97 to 0.99 mol is particularly preferred. It is preferable that the amount of the bifunctional phenol compound is within this range because the molecular weight of the resulting phenoxy resin is sufficiently increased. Further, from the viewpoint of reactivity, it is desirable to have a large number of epoxy groups in the terminal groups, so the amount of the difunctional phenol compound to be blended is preferably less than 1.00 mol.
また、耐熱性を付与するためには、上記２官エポキシ樹脂の一部又は全部として、フルオレン環構造を有する２官能エポキシ樹脂や、上記２官能フェノール化合物の一部又は全部として、フルオレン環構造を有する２官能フェノール化合物を用いることが好ましい。
フルオレン環構造を有する２官能フェノール化合物としては、具体的には、９，９－ビス（４－ヒドロキシフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－２ーメチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３－エチルフェニル）フルオレン、９，９－ビス（３－ヒドロキシ－６－メチルフェニル）フルオレン、９，９－ビス（２－ヒドロキシ－４ーメチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３－ｔ－ブチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３，５－ジメチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－２，６－ジメチルフェニル）フルオレン、９，９－ビス（４－ヒド口キシ－３，５－ジ－ｔ－ブチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３－シク口ヘキシルフェニル）フルオレン。９，９－ビス（４－ヒドロキシ－３－フェニルフェニル）フルオレン等の９，９－ビス（ヒドロキシフェニル）フルオレン類や、９，９－ビス（２－ヒドロキシ－６－ナフチル）フルオレン、９，９－ビス（１－ヒドロキシ－５－ナフチル）フルオレン等の９，９－ビス（ヒドロキシナフチル）フルオレン類等が挙げられる。これらのフルオレン環構造含有フェノール化合物を１種類又は２種類以上併用してもよい。
フルオレン環構造を有する２官能エポキシ樹脂としては、上記フルオレン環構造を有する２官能フェノール化合物と、５～２０倍モルのエピクロルヒドリン等のエピハロヒドリンとを、水酸化ナトリウムや水酸化カリウム等のアルカリ触媒を用いて反応することで得られるジグリシジル化合物が挙げられる。具体的には、２官能エポキシ樹脂として例示したビスフェノールフルオレンジグリシジルエーテル、ビスクレゾールフルオレンジグリシジルエーテル、ビスナフトールフルオレンジグリシジルエーテル等が挙げられる。
In addition, in order to impart heat resistance, it is necessary to use a bifunctional epoxy resin having a fluorene ring structure as part or all of the above bifunctional epoxy resin, or a fluorene ring structure as part or all of the above bifunctional phenol compound. It is preferable to use a bifunctional phenol compound having the following.
Specific examples of the bifunctional phenol compound having a fluorene ring structure include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene, and 9,9-bis(4-hydroxyphenyl)fluorene. (4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(3-hydroxy-6-methylphenyl)fluorene, 9,9- Bis(2-hydroxy-4-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-t-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9 ,9-bis(4-hydroxy-2,6-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-di-t-butylphenyl)fluorene, 9,9-bis(4 -Hydroxy-3-cyclohexylphenyl)fluorene. 9,9-bis(hydroxyphenyl)fluorenes such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(2-hydroxy-6-naphthyl)fluorene, 9,9 Examples include 9,9-bis(hydroxynaphthyl)fluorenes such as -bis(1-hydroxy-5-naphthyl)fluorene. You may use one type or a combination of two or more types of these fluorene ring structure-containing phenol compounds.
The bifunctional epoxy resin having a fluorene ring structure is prepared by combining the above-mentioned bifunctional phenol compound having a fluorene ring structure and 5 to 20 times the mole of epihalohydrin such as epichlorohydrin using an alkali catalyst such as sodium hydroxide or potassium hydroxide. Examples include diglycidyl compounds obtained by reaction. Specific examples include bisphenol fluorene glycidyl ether, biscresol fluorene glycidyl ether, bisnaphthol fluorene glycidyl ether, and the like, which are exemplified as bifunctional epoxy resins.
また、難燃性を付与するために、上記２官能フェノール化合物の一部又は全部として、ハロゲンが付加した２官能のハロゲン化フェノール化合物（例えば、テトラブロムビスフェノールＡ等）や、２官能のリン含有フェノール化合物を用いてもよく、ハロゲンフリーの環境面からすると、２官能のリン含有フェノール化合物が好ましい。 In addition, in order to impart flame retardancy, a bifunctional halogenated phenol compound to which a halogen has been added (for example, tetrabromo bisphenol A, etc.) or a bifunctional phosphorus-containing compound may be used as part or all of the above bifunctional phenol compound. A phenol compound may be used, and a difunctional phosphorus-containing phenol compound is preferred from the viewpoint of halogen-free environment.
また、難燃性を付与するために、上記２官能エポキシ樹脂の一部又は全部として、リン含有化合物を使用することが好ましい。 Moreover, in order to impart flame retardancy, it is preferable to use a phosphorus-containing compound as part or all of the bifunctional epoxy resin.
２官能のリン含有フェノール化合物としては、例えば、１０－（２，５－ジヒドロキシフェニル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，７－ジヒドロキシ－１－ナフチル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（１，４－ジヒドロキシ－２－ナフチル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，５－ジヒドロキシフェニル）－８－ベンジル－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，７－ジヒドロキシ－１－ナフチル）－８－ベンジル－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、ジフェニルホスフィニルヒドロキノン、ジフェニルホスフェニル－１，４－ジオキシナフタリン、１，４－シクロオクチレンホスフィニル－１，４－フェニルジオール、１，５－シクロオクチレンホスフィニル－１，４－フェニルジオール等が挙げられる。これらのリン含有フェノール化合物を１種類又は２種類以上併用してもよい。
２官能エポキシ樹脂としてのリン含有化合物としては、上記リン含有フェノール化合物と、５～２０倍モルのエピハロヒドリンとを、アルカリ触媒を用いて反応することで得られるジグリシジル化合物が挙げられる。具体的にはリン含有２官能エポキシ樹脂として上述したＦＸ－３０５（日鉄ケミカル＆マテリアル社製）、ジフェニルホスフィニルハイドロキノンジグリシジルエーテル等が挙げられる。
Examples of the difunctional phosphorus-containing phenol compound include 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxy-1- naphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dihydroxy-2-naphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -(2,5-dihydroxyphenyl)-8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxy-1-naphthyl)-8- Benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl -1,4-phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol, and the like. One type or two or more types of these phosphorus-containing phenol compounds may be used in combination.
Examples of the phosphorus-containing compound as a bifunctional epoxy resin include diglycidyl compounds obtained by reacting the above-mentioned phosphorus-containing phenol compound with 5 to 20 times the mole of epihalohydrin using an alkali catalyst. Specific examples of the phosphorus-containing bifunctional epoxy resin include the above-mentioned FX-305 (manufactured by Nippon Steel Chemical & Materials), diphenylphosphinyl hydroquinone diglycidyl ether, and the like.
２官能のリン含有フェノール化合物を使用して得られたフェノキシ樹脂のリン含有率は、使用目的に応じて適宜調整すればよいが、１～６質量％が好ましく、２～５質量％がより好ましく、３～４．５質量％が更に好ましい。 The phosphorus content of the phenoxy resin obtained using a bifunctional phosphorus-containing phenol compound may be adjusted as appropriate depending on the purpose of use, but is preferably 1 to 6% by mass, more preferably 2 to 5% by mass. , 3 to 4.5% by mass is more preferable.
本発明の製造方法で使用する上記ホスホニウムボレート化合物は、２官能エポキシ樹脂と２官能フェノール化合物との反応の触媒として作用する。 The phosphonium borate compound used in the production method of the present invention acts as a catalyst for the reaction between the difunctional epoxy resin and the difunctional phenol compound.
本発明の製造方法において触媒として使用するホスホニウムボレート化合物は、上記一般式（１）で表される。 The phosphonium borate compound used as a catalyst in the production method of the present invention is represented by the above general formula (1).
上記一般式（１）において、Ｐはリン原子であり、Ｒ１、Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、置換もしくは無置換のアリール基、アルキル基、アラルキル基、又は水素原子である。また、Ｂはホウ素原子であり、Ｘ１、Ｘ２、Ｘ３及びＸ４は、それぞれ独立して、置換もしくは無置換のアリール基、アルキル基、アラルキル基、水素原子、又はハロゲン原子である。 In the above general formula (1), P is a phosphorus atom, and R 1 , R 2 , R 3 and R 4 are each independently a substituted or unsubstituted aryl group, alkyl group, aralkyl group, or a hydrogen atom. It is. Further, B is a boron atom, and X 1 , X 2 , X 3 and X 4 are each independently a substituted or unsubstituted aryl group, alkyl group, aralkyl group, hydrogen atom, or halogen atom.
上記一般式（１）中のＲ１～Ｒ４及び上記Ｘ１～Ｘ４のアリール基としては、置換されていても無置換でもよく、例えば、フェニル基、１－ナフチル基、２－ナフチル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、キシリル基（ジメチルフェニル基）等が挙げられる。
アリール基の炭素数（置換基の炭素数は含まない）は、好ましくは６～１２である。
The aryl groups of R 1 to R 4 and X 1 to , o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group), and the like.
The number of carbon atoms in the aryl group (excluding the number of carbon atoms in substituents) is preferably 6 to 12.
上記一般式（１）中のＲ１～Ｒ４及び上記Ｘ１～Ｘ４のアルキル基としては、直鎖状、分岐状のいずれでもよく、更に不飽和基でもよく、また、アリール基を置換基として有するアラルキル基でもよい。例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｔ－ペンチル基、１－メチルブチル基、ｎ－ヘキシル基、２－メチルペンチル基、３－メチルペンチル基、２，２－ジメチルブチル基、２，３－ジメチルブチル基、ｎ－ヘプチル基、２－メチルヘキシル基、３－メチルヘキシル基、２，２－ジメチルペンチル基、２，３－ジメチルペンチル基、２，４－ジメチルペンチル基、３，３－ジメチルペンチル基、３－エチルペンチル基、２，２，３－トリメチルブチル基、ｎ－オクチル基、イソオクチル基、２－エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基や、ビニル基、アリル基、メタリル基や、ベンジル基（フェニルメチル基）、о－メチルベンジル基（о－メチルフェニルメチル基）、ｍ－メチルベンジル基（ｍ－メチルフェニルメチル基）、ｐ－メチルベンジル基（ｐ－メチルフェニルメチル基）、フェニルエチル基、ナフチルメチル基、ナフチルエチル基等が挙げられる。
アルキル基の炭素数（置換基の炭素数は含まない）は、好ましくは１～６である。
The alkyl groups of R 1 to R 4 and X 1 to It may also be an aralkyl group as a group. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1 -Methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3- Methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, vinyl group, allyl group, methallyl group, benzyl group (phenylmethyl group), о-methylbenzyl group group (о-methylphenylmethyl group), m-methylbenzyl group (m-methylphenylmethyl group), p-methylbenzyl group (p-methylphenylmethyl group), phenylethyl group, naphthylmethyl group, naphthylethyl group, etc. can be mentioned.
The number of carbon atoms in the alkyl group (not including the number of carbon atoms in substituents) is preferably 1 to 6.
上記一般式（１）中のＸ１～Ｘ４のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。中でも、フッ素原子が好ましい。 Examples of the halogen atoms represented by X 1 to X 4 in the above general formula (1) include fluorine atom, chlorine atom, bromine atom, and iodine atom. Among these, fluorine atoms are preferred.
上記一般式（１）で表されるホスホニウムボレート化合物としては、例えば、テトラブチルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラ－ｐ－トリルボレート、トリ－ｔ－ブチルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラフルオロボレート等が挙げられる。特に、テトラブチルホスホニウムテトラフェニルボレート及びテトラフェニルホスホニウムテトラフェニルボレートが好ましい。これらのホスホニウムボレート化合物は、１種のみでも複数種を組み合わせて使用してもよい。 Examples of the phosphonium borate compound represented by the above general formula (1) include tetrabutylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tri-t-butylphosphoniumtetraphenyl Examples include borate, tetraphenylphosphonium tetrafluoroborate, and the like. Particularly preferred are tetrabutylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate. These phosphonium borate compounds may be used alone or in combination.
上記ホスホニウムボレート化合物の配合量は、２官能エポキシ樹脂１００質量部に対して、０．００５～５．０質量部が好ましく、０．００６～１．０質量部がより好ましく、０．００７～０．１５質量部が更に好ましく、０．０１～０．１質量部が特に好ましい。ホスホニウムボレート化合物の配合量が少ないとフェノキシ樹脂の分子量が十分大きくならない恐れがある。また、配合量が多いと貯蔵安定性が悪化しやすく、反応後に除去する必要性がある。ホスホニウムボレート化合物は、反応開始時に一括して仕込んでもよいし、反応の経時に従って適時分割して仕込んでもよい。 The blending amount of the phosphonium borate compound is preferably 0.005 to 5.0 parts by mass, more preferably 0.006 to 1.0 parts by mass, and 0.007 to 0 parts by mass, based on 100 parts by mass of the bifunctional epoxy resin. .15 parts by weight is more preferred, and 0.01 to 0.1 parts by weight is particularly preferred. If the blending amount of the phosphonium borate compound is small, the molecular weight of the phenoxy resin may not be sufficiently large. Furthermore, if the amount is too large, storage stability tends to deteriorate, and it is necessary to remove the compound after the reaction. The phosphonium borate compound may be charged all at once at the start of the reaction, or may be charged in portions as appropriate over time of the reaction.
上記ホスホニウムボレート化合物は、有機溶媒又は水で希釈してから用いることができる。有機溶媒としては、ホスホニウムボレート化合物などの原料を溶解するものであれば、どのようなものでもよい。具体的には、後述する本発明のフェノキシ樹脂の反応時に使用できる有機溶媒と同様のものが挙げられる。 The above phosphonium borate compound can be used after being diluted with an organic solvent or water. Any organic solvent may be used as long as it dissolves the raw material such as the phosphonium borate compound. Specifically, the same organic solvents as those that can be used in the reaction of the phenoxy resin of the present invention, which will be described later, may be mentioned.
本発明の上記２官能エポキシ樹脂と上記２官能フェノール化合物との反応は、常圧、加圧、減圧いずれの条件で行うこともできる。また、使用する触媒が分解しない程度の温度範囲で行う。
反応温度が高すぎると生成するフェノキシ樹脂が劣化する恐れがあり、低すぎると反応が進まずに目的の分子量にならない恐れがある。そのため反応温度は、８０～２４０℃が好ましく、１００～２２０℃がより好ましく、１２０～２００℃が更に好ましく、１４０～１８０℃が特に好ましい。
反応時間は特に限定されないが、０．５～２４時間が好ましく、１～２０時間がより好ましく、２～１２時間が更に好ましく、３～１０時間が特に好ましい。反応時間が好ましい範囲内であれば、生産効率向上の点でも、未反応成分を削減できる点でも好ましい。
また、アセトンやメチルエチルケトンのような低沸点溶媒を使用する場合には、オートクレーブを使用して高圧下で反応を行うことで、反応温度を確保することができる。なお、反応熱の除去が必要な場合は、通常、反応熱による使用溶媒の蒸発・凝縮・還流法、間接冷却法、又はこれらの併用により行われる。
The reaction between the bifunctional epoxy resin of the present invention and the bifunctional phenol compound can be carried out under normal pressure, increased pressure, or reduced pressure. Further, the temperature range is such that the catalyst used does not decompose.
If the reaction temperature is too high, the phenoxy resin produced may deteriorate; if the reaction temperature is too low, the reaction may not proceed and the desired molecular weight may not be achieved. Therefore, the reaction temperature is preferably 80 to 240°C, more preferably 100 to 220°C, even more preferably 120 to 200°C, and particularly preferably 140 to 180°C.
The reaction time is not particularly limited, but preferably 0.5 to 24 hours, more preferably 1 to 20 hours, even more preferably 2 to 12 hours, and particularly preferably 3 to 10 hours. If the reaction time is within a preferable range, it is preferable from the viewpoint of improving production efficiency and reducing unreacted components.
Furthermore, when using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave. In addition, when it is necessary to remove the reaction heat, it is usually carried out by evaporation, condensation, and reflux of the solvent used by the reaction heat, an indirect cooling method, or a combination thereof.
本発明の製造方法において溶媒を用いてもよい。溶媒としては、原料や反応生成物（フェノキシ樹脂）を溶解し、反応に悪影響のないものであれば、どのようなものでもよいが、通常は有機溶媒である。有機溶媒としては、例えば、芳香族系溶媒、ケトン系溶媒、エステル系溶媒、エーテル系溶媒、アミド系溶媒、グリコールエーテル系溶媒等が挙げられる。これらの溶媒は単独で用いても、２種以上を混合して使用してもよい。使用する溶媒の量は、反応条件に応じて適宜選択することができるが、固形分濃度として３５～９５質量％が好ましい。また、反応中に高粘性生成物が生じた場合は反応途中で溶媒を更に加えて反応を継続してもよい。 A solvent may be used in the production method of the present invention. The solvent may be any solvent as long as it dissolves the raw materials and the reaction product (phenoxy resin) and does not adversely affect the reaction, but is usually an organic solvent. Examples of the organic solvent include aromatic solvents, ketone solvents, ester solvents, ether solvents, amide solvents, and glycol ether solvents. These solvents may be used alone or in combination of two or more. The amount of solvent used can be appropriately selected depending on the reaction conditions, but the solid content concentration is preferably 35 to 95% by mass. Further, if a highly viscous product is generated during the reaction, a solvent may be further added during the reaction to continue the reaction.
芳香族系溶媒としては、例えば、ベンゼン、トルエン、キシレン等が挙げられる。ケトン系溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、２－ヘプタノン、４－ヘプタノン、２－オクタノン、シクロペンタノン、シクロヘキサノン、アセチルアセトン等が挙げられる。エステル系溶媒としては、例えば、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸ベンジル、プロピオン酸エチル、酪酸エチル、酪酸ブチル、バレロラクトン、ブチロラクトン等が挙げられる。エーテル系溶媒としては、例えば、ジエチルエーテル、ジブチルエーテル、ｔ－ブチルメチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジオキサン等が挙げられる。アミド系溶媒としては、例えば、ホルムアミド、Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、アセトアミド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、２－ピロリドン、Ｎ－メチルピロリドン等が挙げられる。グリコールエーテル系溶媒としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ－ｎ－ブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールジメチルエーテル等が挙げられる。 Examples of aromatic solvents include benzene, toluene, and xylene. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, and acetylacetone. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, butyrolactone, and the like. Examples of the ether solvent include diethyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran (THF), and dioxane. Examples of amide solvents include formamide, N-methylformamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, and the like. It will be done. Examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoethyl ether. -n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, and the like.
反応終了後、溶媒は必要に応じて蒸留等により除去することもできるし、更に追加して固形分濃度を調整してもよい。その溶媒としては、フェノキシ樹脂を溶解するものであれば、どのようなものでもよいが、通常は有機溶媒である。有機溶媒としては、上記有機溶媒と同様のものが挙げられる。 After the reaction is completed, the solvent can be removed by distillation or the like, if necessary, or may be added to adjust the solid content concentration. The solvent may be any solvent as long as it dissolves the phenoxy resin, but it is usually an organic solvent. Examples of the organic solvent include those similar to the above organic solvents.
本発明の製造方法において、貯蔵安定性が悪化しない範囲で、上記ホスホニウムボレート化合物と共に、その他の触媒を併用してもよい。その他の触媒としては、通常、二段法の触媒として用いられるものであれば特に制限されない。例えば、アルカリ金属化合物、上記ホスホニウムボレート化合物以外の有機リン化合物、第３級アミン類、第４級アンモニウム塩、環状アミン類、イミダゾール類等が挙げられる。これらその他の触媒は、１種のみでも２種以上を組み合わせて用いてもよい。なお、貯蔵安定性の観点からは、樹脂組成物を保管する際等にはその他の触媒を含まないか、上記ホスホニウムボレート化合物よりも少量の配合量としておくことが好ましい。 In the production method of the present invention, other catalysts may be used in combination with the phosphonium borate compound as long as storage stability is not deteriorated. Other catalysts are not particularly limited as long as they are normally used as catalysts in a two-stage process. Examples include alkali metal compounds, organic phosphorus compounds other than the above-mentioned phosphonium borate compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles, and the like. These other catalysts may be used alone or in combination of two or more. In addition, from the viewpoint of storage stability, when storing the resin composition, it is preferable that other catalysts are not included or that the amount of other catalysts is smaller than that of the above-mentioned phosphonium borate compound.
アルカリ金属化合物としては、例えば、水酸化ナトリウム、水酸化リチウム、水酸化カリウム等のアルカリ金属水酸化物や、炭酸ナトリウム、重炭酸ナトリウム、塩化ナトリウム、塩化リチウム、塩化カリウム等のアルカリ金属塩や、ナトリウムメトキシド、ナトリウムエトキシド等のアルカリ金属アルコキシドや、アルカリ金属フェノキシド、水素化ナトリウム、水素化リチウム等のアルカリ金属の水素化物や、酢酸ナトリウム、ステアリン酸ナトリウム等の有機酸のアルカリ金属塩等が挙げられる。
上記ホスホニウムボレート化合物以外の有機リン化合物としては、例えば、テトラメチルホスホニウムブロマイド、テトラメチルホスホニウムアイオダイド、テトラメチルホスホニウムハイドロオキサイド、トリメチルシクロヘキシルホスホニウムクロライド、トリメチルシクロヘキシルホスホニウムブロマイド、トリメチルベンジルホスホニウムクロライド、トリメチルベンジルホスホニウムブロマイド、テトラフェニルホスホニウムブロマイド、トリフェニルメチルホスホニウムブロマイド、トリフェニルメチルホスホニウムアイオダイド、トリフェニルエチルホスホニウムクロライド、トリフェニルエチルホスホニウムブロマイド、トリフェニルエチルホスホニウムアイオダイド、トリフェニルベンジルホスホニウムクロライド、トリフェニルベンジルホスホニウムブロマイド等のホスホニウム塩類や、トリフェニルホスフィン、トリス（４－メチルフェニル）ホスフィン、トリス（２，４－キシリル）ホスフィン、トリメシチルホスフィン、トリス（４－ｔ－ブチルフェニル）ホスフィン、トリス（４－メトキシフェニル）ホスフィン、トリス（４－エトキシフェニル）ホスフィン、トリス（２－イソプロピル－４－メトキシフェニル）ホスフィン、トリス（４－メトキシ－３，５－ジメチルフェニル）ホスフィン等のホスフィン類が挙げられる。
第３級アミン類としては、例えば、トリエチルアミン、トリ－ｎ－プロピルアミン、トリ－ｎ－ブチルアミン、トリエタノールアミン、ベンジルジメチルアミン等が挙げられる。
第４級アンモニウム塩としては、例えば、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、テトラメチルアンモニウムハイドロオキサイド、トリエチルメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、テトラエチルアンモニウムアイオダイド、テトラプロピルアンモニウムブロマイド、テトラプロピルアンモニウムハイドロオキサイド、テトラブチルアンモニウムクロライド、テトラブチルアンモニウムブロマイド、テトラブチルアンモニウムアイオダイド、ベンジルトリメチルアンモニウムクロライド、ベンジルトリメチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムハイドロオキサイド、ベンジルトリブチルアンモニウムクロライド、フェニルトリメチルアンモニウムクロライド等が挙げられる。
環状アミン類としては、例えば、１，８－ジアザビシクロ（５，４，０）－７－ウンデセン、１，５ジアザビシクロ（４，３，０）－５－ノネン等が挙げられる。
イミダゾール類としては、例えば、２－メチルイミダゾール、２－エチルイミダゾール、２－フェニルイミダゾール、２－ウンデシルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－メチルイミダゾール等が挙げられる。
Examples of alkali metal compounds include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Alkali metal alkoxides such as sodium methoxide and sodium ethoxide, alkali metal hydrides such as alkali metal phenoxides, sodium hydride and lithium hydride, and alkali metal salts of organic acids such as sodium acetate and sodium stearate, etc. Can be mentioned.
Examples of organic phosphorus compounds other than the above-mentioned phosphonium borate compounds include tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, and trimethylbenzylphosphonium bromide. , tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, etc. Phosphonium salts of, triphenylphosphine, tris(4-methylphenyl)phosphine, tris(2,4-xylyl)phosphine, trimesitylphosphine, tris(4-t-butylphenyl)phosphine, tris(4-methoxyphenyl) Examples include phosphines such as phosphine, tris(4-ethoxyphenyl)phosphine, tris(2-isopropyl-4-methoxyphenyl)phosphine, and tris(4-methoxy-3,5-dimethylphenyl)phosphine.
Examples of tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, and benzyldimethylamine.
Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, and tetramethylammonium bromide. Propylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride, etc. .
Examples of the cyclic amines include 1,8-diazabicyclo(5,4,0)-7-undecene and 1,5diazabicyclo(4,3,0)-5-nonene.
Examples of imidazoles include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-methylimidazole.
本発明の製造方法で得られるフェノキシ樹脂の重量平均分子量（Ｍｗ）は、１００００～１５００００が好ましく、２００００～１０００００がより好ましく、２５０００～８００００が更に好ましく、３００００～６００００が特に好ましい。Ｍｗが低いものではフィルム製膜性や伸び性が劣り、Ｍｗが高すぎると樹脂の取り扱い性が著しく悪化する。ここで、ＭｗはＧＰＣの測定によって決定され、ＧＰＣの測定方法は、実施例に記載の条件に従う。 The weight average molecular weight (Mw) of the phenoxy resin obtained by the production method of the present invention is preferably 10,000 to 150,000, more preferably 20,000 to 100,000, even more preferably 25,000 to 80,000, and particularly preferably 30,000 to 60,000. If the Mw is low, the film formability and elongation properties will be poor, and if the Mw is too high, the handling properties of the resin will deteriorate significantly. Here, Mw is determined by GPC measurement, and the GPC measurement method follows the conditions described in Examples.
このフェノキシ樹脂のエポキシ当量（ｇ／ｅｑ．）は、４０００～２０００００が好ましく、６０００～１５００００がより好ましく、７０００～１０００００が更に好ましく、８０００～５００００が特に好ましい。エポキシ当量が好ましい範囲内であるとフェノキシ樹脂の分子量が十分大きいことであり、可撓性の観点で好ましい。 The epoxy equivalent (g/eq.) of this phenoxy resin is preferably 4,000 to 200,000, more preferably 6,000 to 150,000, even more preferably 7,000 to 100,000, and particularly preferably 8,000 to 50,000. When the epoxy equivalent is within a preferable range, the molecular weight of the phenoxy resin is sufficiently large, which is preferable from the viewpoint of flexibility.
本発明のフェノキシ樹脂は、他の成分、特に硬化成分例えばイソシアネート系硬化剤又は酸無水物系硬化剤を配合した樹脂組成物として貯蔵安定性に優れる。そのため本発明のフェノキシ樹脂は、塗料、電気・電子材料、封止材料、注型材料、炭素繊維強化樹脂や、導電ペースト、接着剤、絶縁材料等の様々な分野に適用可能であり、特に、電気・電子分野における絶縁注型、積層材料、封止材料等として有用である。 The phenoxy resin of the present invention has excellent storage stability as a resin composition blended with other components, particularly a curing component such as an isocyanate curing agent or an acid anhydride curing agent. Therefore, the phenoxy resin of the present invention can be applied to various fields such as paints, electrical and electronic materials, sealing materials, casting materials, carbon fiber reinforced resins, conductive pastes, adhesives, and insulating materials. It is useful as insulation casting, laminated material, sealing material, etc. in the electrical and electronic fields.
以下、本発明を実施例及び比較例に基づいてより具体的に説明するが、本発明はその要旨を超えない限り、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」は質量部を表す。 Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples, but the present invention is not limited thereto unless it exceeds the gist thereof. Unless otherwise specified, "parts" represent parts by mass.
（１）エポキシ当量：ＪＩＳ Ｋ ７２３６規格に準拠して測定を行い、単位は「ｇ／ｅｑ．」で表した。具体的には、電位差滴定装置を用い、溶媒としてシクロヘキサノンを使用し、臭素化テトラエチルアンモニウム酢酸溶液を加え、０．１ｍｏｌ／Ｌ過塩素酸－酢酸溶液を用いた。なお、溶媒希釈品（樹脂ワニス）は、不揮発分から固形分換算値としての数値を算出した。 (1) Epoxy equivalent: Measured in accordance with the JIS K 7236 standard, and expressed in units of "g/eq." Specifically, a potentiometric titration device was used, cyclohexanone was used as a solvent, a brominated tetraethylammonium acetic acid solution was added, and a 0.1 mol/L perchloric acid-acetic acid solution was used. In addition, for the solvent diluted product (resin varnish), the numerical value was calculated as a solid content conversion value from the nonvolatile content.
（２）不揮発分：ＪＩＳ Ｋ ７２３５規格に準拠して測定した。乾燥温度は２００℃で、乾燥時間は６０分とした。 (2) Nonvolatile content: Measured according to JIS K 7235 standard. The drying temperature was 200°C and the drying time was 60 minutes.
（３）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、生じたリンバナドモリブデン酸錯体の４２０ｎｍにおける吸光度を測定し、予め作成した検量線により求めたリン含有率を％で表した。 (3) Phosphorus content: Sulfuric acid, hydrochloric acid, and perchloric acid were added to the sample and wet ashing was performed by heating to convert all phosphorus atoms into orthophosphoric acid. Metavanadate and molybdate were reacted in an acidic sulfuric acid solution, and the absorbance at 420 nm of the resulting phosphovanadomolybdate complex was measured, and the phosphorus content determined from a calibration curve prepared in advance was expressed in %.
（４．１）重量平均分子量（Ｍｗ）：ＧＰＣ測定により求めた。具体的には、本体（東ソー株式会社製、ＨＬＣ８２２０ＧＰＣ）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ＴＨＦを用い、１ｍＬ／分の流速とし、検出器は示差屈折率検出器を用いた。測定試料は固形分で０．０５ｇを１０ｍＬのＴＨＦに溶解し、０．４５μｍのマイクロフィルターでろ過したものを５０μＬ使用した。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、Ｆ－８０、Ｆ－１２８）より求めた検量線より換算して、Ｍｗを求めた。なお、データ処理は、東ソー株式会社製ＧＰＣ８０２０モデルＩＩバージョン６．００を使用した。なお、リン含有フェノキシ樹脂の場合は、（３．２）の測定方法を用いた。 (4.1) Weight average molecular weight (Mw): Determined by GPC measurement. Specifically, a main body (manufactured by Tosoh Corporation, HLC8220GPC) equipped with a column (manufactured by Tosoh Corporation, TSKgelG4000H XL , TSKgelG3000H XL , TSKgelG2000H XL ) in series was used, and the column temperature was set at 40°C. Further, THF was used as the eluent at a flow rate of 1 mL/min, and a differential refractive index detector was used as the detector. As for the measurement sample, 0.05 g of solid content was dissolved in 10 mL of THF, and 50 μL of the solution was filtered through a 0.45 μm microfilter. Standard monodisperse polystyrene (manufactured by Tosoh Corporation, A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40 , F-80, F-128), and calculated the Mw. Note that GPC8020 Model II version 6.00 manufactured by Tosoh Corporation was used for data processing. In addition, in the case of phosphorus-containing phenoxy resin, the measurement method (3.2) was used.
（４．２）重量平均分子量（Ｍｗ）：ＧＰＣ測定により求めた。具体的には、本体（東ソー株式会社製、ＨＬＣ８３２０ＧＰＣ）にカラム（東ソー株式会社製、ＴＳＫｇｅｌ ＳｕｐｅｒＨ－Ｈ、ＳｕｐｅｒＨ２０００、ＳｕｐｅｒＨＭ－Ｈ、ＳｕｐｅｒＨＭ－Ｈ）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、溶離液はＤＭＦ（２０ｍＭ臭化リチウム含有品）を使用し、０．３ｍＬ／分の流速とし、検出器は示差屈折率検出器を使用した。測定試料は固形分で０．１ｇを１０ｍＬのＤＭＦに溶解し、０．４５μｍのマイクロフィルターでろ過したものを２０μＬ使用した。標準ポリエチレンオキシド（東ソー株式会社製、ＳＥ－２、ＳＥ－５、ＳＥ－８、ＳＥ－１５、ＳＥ－３０、ＳＥ－７０、ＳＥ－１５０）より求めた検量線より換算して、Ｍｗを求めた。なお、データ処理は東ソー株式会社製ＧＰＣ８０２０モデルＩＩバージョン６．００を使用した。 (4.2) Weight average molecular weight (Mw): Determined by GPC measurement. Specifically, we used a main body (manufactured by Tosoh Corporation, HLC8320GPC) equipped with a column (manufactured by Tosoh Corporation, TSKgel SuperHH, SuperH2000, SuperHM-H, SuperHM-H) in series, and the column temperature was The temperature was set to 40°C. Furthermore, DMF (containing 20 mM lithium bromide) was used as the eluent, with a flow rate of 0.3 mL/min, and a differential refractive index detector was used as the detector. As for the measurement sample, 0.1 g of solid content was dissolved in 10 mL of DMF, and 20 μL of the solution was filtered through a 0.45 μm microfilter. Calculate Mw by converting from the calibration curve obtained from standard polyethylene oxide (manufactured by Tosoh Corporation, SE-2, SE-5, SE-8, SE-15, SE-30, SE-70, SE-150). Ta. Note that GPC8020 Model II version 6.00 manufactured by Tosoh Corporation was used for data processing.
（５）ガラス転移温度（Ｔｇ）： ＩＰＣＴＭ－６５０ ２．４．２５．ｃ規格に準拠して測定した。具体的には、示差走査熱量測定の２サイクル目に得られたＤＳＣチャートの補外ガラス転移開始温度（Ｔｉｇ）で表した。示差走査熱量測定装置は、エスアイアイ・ナノテクノロジー株式会社製のＥＸＳＴＡＲ６０００ ＤＳＣ６２００を使用した。測定試料は、樹脂フィルムをパンチングし、積層、アルミニウム製カプセルにパッキングして使用した。測定は、１０℃／分の昇温速度で室温から２８０℃までを２サイクル行った。 (5) Glass transition temperature (Tg): IPCTM-650 2.4.25. Measured in accordance with c standard. Specifically, it was expressed as the extrapolated glass transition initiation temperature (Tig) of the DSC chart obtained in the second cycle of differential scanning calorimetry. EXSTAR6000 DSC6200 manufactured by SII Nanotechnology Co., Ltd. was used as a differential scanning calorimeter. The measurement sample was used by punching a resin film, laminating it, and packing it into an aluminum capsule. The measurement was performed in two cycles from room temperature to 280°C at a heating rate of 10°C/min.
（６）反応性：フェノキシ樹脂のＭｗから以下の基準で評価した。
○：Ｍｗが３００００～１０００００の範囲のもの
×：Ｍｗが３００００未満又は１０００００を超えたもの
(6) Reactivity: Evaluation was made based on the Mw of the phenoxy resin based on the following criteria.
○: Mw is in the range of 30,000 to 100,000 ×: Mw is less than 30,000 or exceeds 100,000
（７）貯蔵安定性：樹脂組成物ワニスについて、２５℃で２４時間放置した後の状態を目視で観察し、以下の基準で貯蔵安定性を評価した。
○：ゲル化せずに流動性があるもの
×：ゲル化し流動性をもたなくなったもの
(7) Storage stability: The resin composition varnish was visually observed after being left at 25° C. for 24 hours, and the storage stability was evaluated based on the following criteria.
○: Something that does not gel and has fluidity ×: Something that gels and no longer has fluidity
以下の実施例で使用したエポキシ樹脂、硬化剤、触媒、及び溶媒は以下の通りである。 The epoxy resin, curing agent, catalyst, and solvent used in the following examples are as follows.
［２官能エポキシ樹脂］
Ａ１：ビスフェノールＡ型液状エポキシ樹脂（日鉄ケミカル＆マテリアル株式会社製、エポトートＹＤ－１２８、エポキシ当量１８６）
Ａ２：３，３’，５，５’－テトラメチル－４，４’－ビフェノールのエポキシ樹脂（三菱ケミカル株式会社製、ＹＸ－４０００、エポキシ当量１９６）
[Bifunctional epoxy resin]
A1: Bisphenol A type liquid epoxy resin (manufactured by Nippon Steel Chemical & Materials Co., Ltd., Epotote YD-128, epoxy equivalent 186)
A2: 3,3',5,5'-tetramethyl-4,4'-biphenol epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent weight 196)
［２官能フェノール化合物］
Ｂ１：ビスフェノールＡ（日鉄ケミカル＆マテリアル株式会社製、水酸基当量１１４）
Ｂ２：９，９’－ビス（４－ヒドロキシフェニル）フルオレン（大阪ガスケミカル株式会社製、ＢＰＦ、水酸基当量１７５）
Ｂ３：１０－（２，５－ジヒドロキシフェニル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド（三光株式会社製、ＨＣＡ－ＨＱ、水酸基当量１６２、リン含有率９．５％）
[Bifunctional phenol compound]
B1: Bisphenol A (manufactured by Nippon Steel Chemical & Materials Co., Ltd., hydroxyl equivalent: 114)
B2: 9,9'-bis(4-hydroxyphenyl)fluorene (manufactured by Osaka Gas Chemical Co., Ltd., BPF, hydroxyl equivalent weight 175)
B3: 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., HCA-HQ, hydroxyl equivalent 162, phosphorus content 9.5%)
［触媒］
Ｃ１：テトラブチルホスホニウムテトラフェニルボレート（日本化学工業株式会社製、ヒシコーリンＰＸ－４ＰＢ）
Ｃ２：テトラフェニルホスホニウムテトラフェニルボレート（試薬）
Ｃ３：テトラフェニルホスホニウムテトラ－ｐ－トリルボレート（試薬）
Ｃ４：トリ－ｔ－ブチルホスホニウムテトラフェニルボレート（試薬）
Ｃ５：テトラフェニルホスホニウムテトラフルオロボレート（試薬）
Ｃ６：テトラエチルホスホニウムテトラフルオロボレート（試薬）
Ｃ７：トリフェニルホスフィン（試薬）
Ｃ８：トリス（２，６－ジメトキシフェニル）ホスフィン（試薬）
Ｃ９：２－エチル－４－メチルイミダゾール（四国化成工業株式会社製、キュアゾール２Ｅ４ＭＺ）
[catalyst]
C1: Tetrabutylphosphonium tetraphenylborate (manufactured by Nihon Kagaku Kogyo Co., Ltd., Hishicolin PX-4PB)
C2: Tetraphenylphosphonium tetraphenylborate (reagent)
C3: Tetraphenylphosphonium tetra-p-tolylborate (reagent)
C4: Tri-t-butylphosphonium tetraphenylborate (reagent)
C5: Tetraphenylphosphonium tetrafluoroborate (reagent)
C6: Tetraethylphosphonium tetrafluoroborate (reagent)
C7: Triphenylphosphine (reagent)
C8: Tris(2,6-dimethoxyphenyl)phosphine (reagent)
C9: 2-ethyl-4-methylimidazole (Curezol 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
［溶媒］
Ｓ１：シクロヘキサノン
Ｓ２：メチルエチルケトン
Ｓ３：ジエチレングリコールジメチルエーテル
[solvent]
S1: Cyclohexanone S2: Methyl ethyl ketone S3: Diethylene glycol dimethyl ether
［硬化剤］
Ｄ１：ポリメリックＭＤＩ（ＢＡＳＦ ＩＮＯＡＣ ポリウレタン株式会社製、ルプラネートＭ５Ｓ、イソシアネート当量１３２）
[Curing agent]
D1: Polymeric MDI (manufactured by BASF INOAC Polyurethane Co., Ltd., Lupranate M5S, isocyanate equivalent weight 132)
実施例１
撹拌装置、温度計、窒素ガス導入装置、冷却管、及び滴下装置を備えたガラス製反応容器に、室温下で、Ａ１を１００部、Ｂ１を６０部、Ｓ１を１８部仕込み、窒素ガスを流し撹拌しながら１４０℃まで昇温し、Ｃ１を０．０１部添加した後、１６５℃まで昇温し、同温度で８時間反応を行った。希釈溶媒としてＳ１を６２部、Ｓ２を１６０部使用して希釈混合して、不揮発分４０％のフェノキシ樹脂ワニスを得た。
Example 1
At room temperature, 100 parts of A1, 60 parts of B1, and 18 parts of S1 were charged into a glass reaction vessel equipped with a stirring device, a thermometer, a nitrogen gas introducing device, a cooling tube, and a dropping device, and nitrogen gas was introduced. The temperature was raised to 140°C while stirring, and 0.01 part of C1 was added, and then the temperature was raised to 165°C, and the reaction was carried out at the same temperature for 8 hours. A phenoxy resin varnish with a non-volatile content of 40% was obtained by diluting and mixing 62 parts of S1 and 160 parts of S2 as diluting solvents.
得られたフェノキシ樹脂ワニスを離型フィルム（ポリイミドフィルム製）に溶剤乾燥後の厚みが６０μｍになる様にローラーコーターにて塗布し、１８０℃で２０分間乾燥した後、離形フィルムから得られた乾燥フィルムをはがした。この乾燥フィルム２枚を重ねて、真空プレス機を使用して、真空度０．５ｋＰａ、乾燥温度２００℃、プレス圧力２ＭＰａの条件で６０分間プレスして、厚さ１００μｍのフェノキシ樹脂フィルムを得た。なお、厚み調整のために、厚さ１００μｍのスペーサーを使用した。
また、得られたフェノキシ樹脂ワニス１００部に対して、Ｄ１を１５部配合して、樹脂組成物ワニスを得た。
The obtained phenoxy resin varnish was applied to a release film (made of polyimide film) using a roller coater so that the thickness after drying with the solvent would be 60 μm, and after drying at 180°C for 20 minutes, the film obtained from the release film was coated with a roller coater. The dry film was peeled off. These two dried films were stacked and pressed using a vacuum press machine for 60 minutes at a vacuum degree of 0.5 kPa, a drying temperature of 200°C, and a press pressure of 2 MPa to obtain a phenoxy resin film with a thickness of 100 μm. . Note that a spacer with a thickness of 100 μm was used to adjust the thickness.
Further, 15 parts of D1 was added to 100 parts of the obtained phenoxy resin varnish to obtain a resin composition varnish.
実施例２～１３、比較例１～６
表１～３に示す各原料の仕込み量（部）に従い、実施例１と同様操作を行い、フェノキシ樹脂ワニス、フェノキシ樹脂フィルム、及び樹脂組成物ワニスを得た。
Examples 2 to 13, Comparative Examples 1 to 6
According to the amount (parts) of each raw material shown in Tables 1 to 3, the same operation as in Example 1 was performed to obtain a phenoxy resin varnish, a phenoxy resin film, and a resin composition varnish.
得られたフェノキシ樹脂ワニスを用いて、エポキシ当量、リン含有率、及びＭｗを測定した。フェノキシ樹脂フィルムを用いて、Ｔｇを測定し反応性を確認した。樹脂組成物ワニスを用いて、貯蔵安定性を確認した。その結果を表１～表３に示す。なお、表中の「モル比」は使用した２官能フェノール化合物の水酸基（ＯＨ）に対する２官能エポキシ樹脂のエポキシ基（ＥＰ）のモル比（ＥＰ／ＯＨ）を表し、「－」は未測定を表す。 Using the obtained phenoxy resin varnish, the epoxy equivalent, phosphorus content, and Mw were measured. Tg was measured using a phenoxy resin film to confirm reactivity. Storage stability was confirmed using the resin composition varnish. The results are shown in Tables 1 to 3. In addition, "mole ratio" in the table represents the molar ratio (EP/OH) of the epoxy group (EP) of the bifunctional epoxy resin to the hydroxyl group (OH) of the bifunctional phenol compound used, and "-" indicates an unmeasured value. represent.
表１～表２からわかるように、上記一般式（１）で表されるホスホニウムボレート化合物を用いた実施例１～１３は重合反応性が高く、また、得られたフェノキシ樹脂からなる樹脂組成物は貯蔵安定性に優れる。一方、表３から比較例１～６では重合反応性と貯蔵安定性の両方を満足するものが無かった。
As can be seen from Tables 1 and 2, Examples 1 to 13 using the phosphonium borate compound represented by the above general formula (1) had high polymerization reactivity, and the resin compositions made of the obtained phenoxy resin has excellent storage stability. On the other hand, from Table 3, none of Comparative Examples 1 to 6 satisfied both polymerization reactivity and storage stability.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348358A (en) | 2001-05-24 | 2002-12-04 | Hokko Chem Ind Co Ltd | Epoxy resin composition for sealing optical semiconductor that gives cured product retaining colorless transparency |
| JP2008208315A (en) | 2007-02-28 | 2008-09-11 | Toto Kasei Co Ltd | Non-halogen flame retardant adhesive and material for flexible printed wiring board using the same |
| WO2014157132A1 (en) | 2013-03-28 | 2014-10-02 | 新日鉄住金化学株式会社 | Phenoxy resin composition and cured product thereof |
| JP2015178592A (en) | 2014-02-27 | 2015-10-08 | 新日鉄住金化学株式会社 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product |
| JP2017119779A (en) | 2015-12-28 | 2017-07-06 | 新日鉄住金化学株式会社 | Bisphenol F skeleton-containing phenoxy resin, production method thereof, and resin composition using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348358A (en) | 2001-05-24 | 2002-12-04 | Hokko Chem Ind Co Ltd | Epoxy resin composition for sealing optical semiconductor that gives cured product retaining colorless transparency |
| JP2008208315A (en) | 2007-02-28 | 2008-09-11 | Toto Kasei Co Ltd | Non-halogen flame retardant adhesive and material for flexible printed wiring board using the same |
| WO2014157132A1 (en) | 2013-03-28 | 2014-10-02 | 新日鉄住金化学株式会社 | Phenoxy resin composition and cured product thereof |
| JP2015178592A (en) | 2014-02-27 | 2015-10-08 | 新日鉄住金化学株式会社 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product |
| JP2017119779A (en) | 2015-12-28 | 2017-07-06 | 新日鉄住金化学株式会社 | Bisphenol F skeleton-containing phenoxy resin, production method thereof, and resin composition using the same |
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