JP5870918B2 - Method for purifying alkylnaphthalene formaldehyde polymer - Google Patents
Method for purifying alkylnaphthalene formaldehyde polymer Download PDFInfo
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- JP5870918B2 JP5870918B2 JP2012509315A JP2012509315A JP5870918B2 JP 5870918 B2 JP5870918 B2 JP 5870918B2 JP 2012509315 A JP2012509315 A JP 2012509315A JP 2012509315 A JP2012509315 A JP 2012509315A JP 5870918 B2 JP5870918 B2 JP 5870918B2
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 188
- 229920000642 polymer Polymers 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 34
- 238000000746 purification Methods 0.000 claims description 30
- 230000002378 acidificating effect Effects 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 10
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 10
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical group C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 9
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 8
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 239000011347 resin Substances 0.000 description 33
- 229920005989 resin Polymers 0.000 description 33
- 239000002184 metal Substances 0.000 description 31
- 229910052751 metal Inorganic materials 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 12
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- -1 methoxymethylene naphthalene compound Chemical class 0.000 description 7
- SDDBCEWUYXVGCQ-UHFFFAOYSA-N 1,5-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1C SDDBCEWUYXVGCQ-UHFFFAOYSA-N 0.000 description 6
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 6
- QPUYECUOLPXSFR-UHFFFAOYSA-N alpha-methyl-naphthalene Natural products C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000004780 naphthols Chemical class 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QHJMFSMPSZREIF-UHFFFAOYSA-N 1,3-dimethylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC(C)=C21 QHJMFSMPSZREIF-UHFFFAOYSA-N 0.000 description 4
- APQSQLNWAIULLK-UHFFFAOYSA-N 1,4-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=CC=C(C)C2=C1 APQSQLNWAIULLK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000005967 1,4-Dimethylnaphthalene Substances 0.000 description 2
- CBMXCNPQDUJNHT-UHFFFAOYSA-N 1,6-dimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC=C21 CBMXCNPQDUJNHT-UHFFFAOYSA-N 0.000 description 2
- SPUWFVKLHHEKGV-UHFFFAOYSA-N 1,7-dimethylnaphthalene Chemical compound C1=CC=C(C)C2=CC(C)=CC=C21 SPUWFVKLHHEKGV-UHFFFAOYSA-N 0.000 description 2
- XAABPYINPXYOLM-UHFFFAOYSA-N 1,8-dimethylnaphthalene Chemical compound C1=CC(C)=C2C(C)=CC=CC2=C1 XAABPYINPXYOLM-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- WWGUMAYGTYQSGA-UHFFFAOYSA-N 2,3-dimethylnaphthalene Chemical compound C1=CC=C2C=C(C)C(C)=CC2=C1 WWGUMAYGTYQSGA-UHFFFAOYSA-N 0.000 description 2
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- DXVYLFHTJZWTRF-UHFFFAOYSA-N Ethyl isobutyl ketone Chemical compound CCC(=O)CC(C)C DXVYLFHTJZWTRF-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000005618 Fries rearrangement reaction Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZDPJODSYNODADV-UHFFFAOYSA-N 1,2,3,4-tetramethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=C(C)C(C)=C21 ZDPJODSYNODADV-UHFFFAOYSA-N 0.000 description 1
- XYTKCJHHXQVFCK-UHFFFAOYSA-N 1,3,8-trimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC(C)=C21 XYTKCJHHXQVFCK-UHFFFAOYSA-N 0.000 description 1
- RAYZALBEMJMGEA-UHFFFAOYSA-N 1-cyclohexylnaphthalene Chemical compound C1CCCCC1C1=CC=CC2=CC=CC=C12 RAYZALBEMJMGEA-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- XSRADQOBRZHEOB-UHFFFAOYSA-N 1-methyl-1,2-dihydroacenaphthylene Chemical compound C1=CC(C(C)C2)=C3C2=CC=CC3=C1 XSRADQOBRZHEOB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- UYDSWXLEZXMSOK-UHFFFAOYSA-N CC1OCC1C1(CCC2)C2C2CC1CC2 Chemical compound CC1OCC1C1(CCC2)C2C2CC1CC2 UYDSWXLEZXMSOK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
- C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、アルキルナフタレンホルムアルデヒド重合体の精製方法、特に、金属含有量の低減されたアルキルナフタレンホルムアルデヒド重合体の工業的に有利な精製方法に関する。 The present invention relates to a method for purifying an alkylnaphthalene formaldehyde polymer, and more particularly to an industrially advantageous method for purifying an alkylnaphthalene formaldehyde polymer having a reduced metal content.
モノメチルナフタレン及び／又はジメチルナフタレンを主成分とする多環式芳香族炭化水素とパラホルムアルデヒドとを、芳香族モノスルホン酸の存在下に反応させて得られる芳香族炭化水素樹脂は公知であり、得られる樹脂は、液状エポキシ樹脂との相溶性及びキシレンに対する溶解性が優れている（特許文献１参照）。 Aromatic hydrocarbon resins obtained by reacting polycyclic aromatic hydrocarbons mainly composed of monomethylnaphthalene and / or dimethylnaphthalene with paraformaldehyde in the presence of aromatic monosulfonic acid are known and obtained. The obtained resin is excellent in compatibility with a liquid epoxy resin and in xylene (see Patent Document 1).
また、メトキシメチレンナフタレン化合物と、フェノール、クレゾール又はナフトール等のフェノール性水酸基を有する化合物とを、ジエチル硫酸の存在下に反応させ、ナフタレンとフェノール性水酸基を有する化合物とがメチレン基を介して結合した構造を持つフェノール樹脂を得る方法が公知である（特許文献２参照）。 Further, a methoxymethylene naphthalene compound and a compound having a phenolic hydroxyl group such as phenol, cresol or naphthol were reacted in the presence of diethyl sulfate, and the naphthalene and the compound having a phenolic hydroxyl group were bonded via a methylene group. A method for obtaining a phenol resin having a structure is known (see Patent Document 2).
これらの樹脂は半導体用のコーティング剤、レジスト用樹脂、半導体下層膜形成樹脂として使用されている。これらの用途においては、特に金属含有量が、歩留まり向上のために重要な性能項目となっている。すなわち、金属含有量の多い樹脂を用いた場合には、半導体中に金属が残存し、半導体の電気特性を低下させることから、金属含有量を低減することが求められている。 These resins are used as semiconductor coating agents, resist resins, and semiconductor underlayer film forming resins. In these applications, particularly the metal content is an important performance item for improving the yield. That is, when a resin having a high metal content is used, the metal remains in the semiconductor, which lowers the electrical characteristics of the semiconductor. Therefore, it is required to reduce the metal content.
金属含有量の低減されたアルキルナフタレンホルムアルデヒド重合体の製造方法として、アルキルナフタレンホルムアルデヒド重合体と有機溶媒を含む溶液を、イオン交換樹脂と接触させる方法や、フィルターで濾過する方法等が考えられる。
しかしながら、イオン交換樹脂を用いる方法では、種々の金属イオンを含有する場合は、イオン交換樹脂の選択に難があり、金属の種類によっては除去が困難であるという問題、非イオン性の金属の除去が困難であるという問題、さらには、ランニングコストが大きいという問題がある。一方、フィルターで濾過する方法では、イオン性金属の除去が困難であるという問題がある。
そのため、金属含有量の低減されたアルキルナフタレンホルムアルデヒド重合体の工業的に有利な精製方法の確立が望まれている。As a method for producing an alkylnaphthalene formaldehyde polymer with a reduced metal content, a method of bringing a solution containing an alkylnaphthalene formaldehyde polymer and an organic solvent into contact with an ion exchange resin, a method of filtering with a filter, or the like can be considered.
However, in the method using an ion exchange resin, when various kinds of metal ions are contained, it is difficult to select an ion exchange resin, and it is difficult to remove depending on the type of metal, and removal of nonionic metals. Is difficult, and there is a problem that running cost is high. On the other hand, the method of filtering with a filter has a problem that it is difficult to remove the ionic metal.
Therefore, it is desired to establish an industrially advantageous purification method for alkylnaphthalene formaldehyde polymers having a reduced metal content.
本発明の目的は、金属含有量の低減されたアルキルナフタレンホルムアルデヒド重合体の工業的に有利な精製方法を提供することにある。 An object of the present invention is to provide an industrially advantageous purification method for alkylnaphthalene formaldehyde polymers having a reduced metal content.
本発明者らは上記課題を解決するため鋭意検討した結果、アルキルナフタレンホルムアルデヒド重合体と有機溶媒を含む溶液を、酸性の水溶液と接触させることにより、種々の金属の含有量が著しく低下することを見出し、本発明に到った。 As a result of intensive studies to solve the above problems, the present inventors have found that the content of various metals is significantly reduced by bringing a solution containing an alkylnaphthalene formaldehyde polymer and an organic solvent into contact with an acidic aqueous solution. The headline and the present invention were reached.
すなわち、本発明はつぎの通りである。
１． アルキルナフタレンとホルムアルデヒドとを反応させて得られるアルキルナフタレンホルムアルデヒド重合体、及び、有機溶媒を含む溶液を、酸性の水溶液と接触させることを特徴とするアルキルナフタレンホルムアルデヒド重合体の精製方法。
２． 前記酸性の水溶液が、塩酸、硫酸、硝酸及びリン酸からなる群より選ばれる１種以上の鉱酸の水溶液である第１項記載の精製方法。
３． 前記酸性の水溶液が、酢酸、プロピオン酸、蓚酸、マロン酸、コハク酸、フマル酸、マレイン酸、酒石酸、クエン酸、メタンスルホン酸、フェノールスルホン酸、ｐ−トルエンスルホン酸及びトリフルオロ酢酸からなる群より選ばれる１種以上の有機酸水溶液である第１項記載の精製方法。
４． 前記酸性の水溶液が、硫酸の水溶液である第２項記載の精製方法。
５． 前記酸性の水溶液が、蓚酸の水溶液である第３項記載の精製方法。
６． 前記有機溶媒が、トルエン、２−ヘプタノン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトン、プロピレングリコールモノメチルエーテルアセテート又は酢酸エチルである第１項〜第５項のいずれかに記載の精製方法。
７． 前記有機溶媒が、シクロヘキサノン又はプロピレングリコールモノメチルエーテルアセテートである第６項に記載の精製方法。
８． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（１）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
９． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（２）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
１０． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（３）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
１１． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（４）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
１２． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（５）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
１３． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（６）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
１４． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（７）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
１５． 前記アルキルナフタレンホルムアルデヒド重合体が下記一般式（８）で示される単位を含む第１項〜第７項のいずれかに記載の精製方法。
1. An alkylnaphthalene formaldehyde polymer obtained by reacting an alkylnaphthalene and formaldehyde, and a solution containing an organic solvent is brought into contact with an acidic aqueous solution.
2. The purification method according to claim 1, wherein the acidic aqueous solution is an aqueous solution of one or more mineral acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
3. The acidic aqueous solution is a group consisting of acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. The purification method according to claim 1, which is one or more organic acid aqueous solutions selected from the above.
4). The purification method according to claim 2, wherein the acidic aqueous solution is an aqueous solution of sulfuric acid.
5. The purification method according to claim 3, wherein the acidic aqueous solution is an aqueous solution of oxalic acid.
6). The purification method according to any one of Items 1 to 5, wherein the organic solvent is toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, or ethyl acetate.
7). The purification method according to claim 6, wherein the organic solvent is cyclohexanone or propylene glycol monomethyl ether acetate.
8). The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (1).
9. The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (2).
10. The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (3).
11. The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (4).
12 The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (5).
13. The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (6).
14 The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (7).
15. The purification method according to any one of Items 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (8).
本発明により、種々の金属の含有量の著しく低減されたアルキルナフタレンホルムアルデヒド重合体の精製方法を提供できる。 According to the present invention, it is possible to provide a method for purifying an alkylnaphthalene formaldehyde polymer in which the content of various metals is significantly reduced.
以下、本発明を詳細に説明する。
本発明は、アルキルナフタレンホルムアルデヒド重合体を有機溶媒に溶解させ、その溶液を酸性水溶液と接触させることにより、アルキルナフタレンホルムアルデヒド重合体と有機溶媒を含む溶液に含まれていた金属分を水相に移行させ、金属含有量の低減されたアルキルナフタレンホルムアルデヒド重合体を精製する。Hereinafter, the present invention will be described in detail.
In the present invention, an alkylnaphthalene formaldehyde polymer is dissolved in an organic solvent, and the solution is brought into contact with an acidic aqueous solution to transfer the metal content contained in the solution containing the alkylnaphthalene formaldehyde polymer and the organic solvent to the aqueous phase. And purifying the alkylnaphthalene formaldehyde polymer having a reduced metal content.
本発明で使用されるアルキルナフタレンホルムアルデヒド重合体は、少なくともアルキルナフタレンとホルムアルデヒドとを反応させて得られるアルキルナフタレンホルムアルデヒド重合体であるが、アルキルナフタレン及びホルムアルデヒド以外の原料としてフェノール、フェノール誘導体、ナフトール、ナフトール誘導体等を用いることができる。また、該重合体を得るに際し、例えば、アルキルナフタレン及びホルムアルデヒドを反応させた後、フェノール、フェノール誘導体、ナフトール、ナフトール誘導体等で変性することにより、目的とする重合体を得る方法などの多段階の反応を経て最終的に得られる重合体でも良い。 The alkylnaphthalene formaldehyde polymer used in the present invention is an alkylnaphthalene formaldehyde polymer obtained by reacting at least alkylnaphthalene and formaldehyde, but as raw materials other than alkylnaphthalene and formaldehyde, phenol, phenol derivatives, naphthol, naphthol Derivatives and the like can be used. Further, in obtaining the polymer, for example, after reacting alkylnaphthalene and formaldehyde, it is modified with phenol, a phenol derivative, naphthol, a naphthol derivative, or the like to obtain a desired polymer. A polymer finally obtained through a reaction may be used.
本発明に用いる重合体を得るのに用いられるアルキルナフタレンとしては、α―メチルナフタレン、β―メチルナフタレン、１，２−ジメチルナフタレン、１，３−ジメチルナフタレン、１，４−ジメチルナフタレン、１，５−ジメチルナフタレン、１，６−ジメチルナフタレン、１，７−ジメチルナフタレン、１，８−ジメチルナフタレン、２，３−ジメチルナフタレン、２，６−ジメチルナフタレン、２，７−ジメチルナフタレン、トリメチルナフタレン、テトラメチルナフタレン、アセナフテン、メチルアセナフテン、シクロヘキシルナフタレン、ノルボルニルナフタレン、トリシクロデカニルナフタレン、アダマンチルナフタレン、デカニルナフタレン及びビシクロオクチルナフタレンの群から選ばれる１種、又は２種以上の混合物である。原料調達の優位性と樹脂製造のしやすさ、光学特性等を総合的に考慮した際には１，５−、２，６−、２，７−、１，８−ジメチルナフタレンないしアセナフテンが好ましく、その中でも１，５−ジメチルナフタレンが特に好ましい。 Examples of the alkylnaphthalene used for obtaining the polymer used in the present invention include α-methylnaphthalene, β-methylnaphthalene, 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1, 5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 1,7-dimethylnaphthalene, 1,8-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, 2,7-dimethylnaphthalene, trimethylnaphthalene, One or a mixture of two or more selected from the group consisting of tetramethylnaphthalene, acenaphthene, methylacenaphthene, cyclohexylnaphthalene, norbornylnaphthalene, tricyclodecanylnaphthalene, adamantylnaphthalene, decanylnaphthalene and bicyclooctylnaphthalene is there. 1,5-, 2,6-, 2,7-, 1,8-dimethylnaphthalene or acenaphthene is preferred when comprehensively considering the superiority of raw material procurement, ease of resin production, optical properties, etc. Of these, 1,5-dimethylnaphthalene is particularly preferable.
ジメチルナフタレンはナフタレン環の２つの芳香環双方にメチル基を各１個有する構造であるため、酸性又はアルカリ触媒存在下で、ホルムアルデヒドと縮合反応させた際に、多官能性樹脂となる。無置換のナフタレンやモノメチルナフタレン、及びナフタレン環の片方の芳香環のみがジメチル化された、１，２−ジメチルナフタレン、１，３−ジメチルナフタレン、１，４−ジメチルナフタレンを原料とした場合は、界面反応のような特殊な反応形式を採用しない限り多官能性樹脂は得られない。また、トリメチル置換以上のナフタレン化合物を用いた場合にも、反応点が少なくなり多官能性樹脂は得られない。 Since dimethylnaphthalene has a structure having one methyl group on each of two aromatic rings of the naphthalene ring, it becomes a polyfunctional resin when subjected to a condensation reaction with formaldehyde in the presence of an acidic or alkaline catalyst. In the case where 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, in which only one aromatic ring of unsubstituted naphthalene, monomethylnaphthalene, or naphthalene ring is dimethylated, is used as a raw material, A multifunctional resin cannot be obtained unless a special reaction form such as an interfacial reaction is employed. In addition, when a naphthalene compound having a trimethyl substitution or higher is used, the number of reaction points is reduced and a polyfunctional resin cannot be obtained.
本発明で用いるアルキルナフタレンホルムアルデヒド重合体は、下記一般式（１）で示される構成単位を有することが好ましい。
本発明で用いるアルキルナフタレンホルムアルデヒド重合体は下記一般式（２）で示される構成単位を有していてもよい。
本発明の一般式（２）で示される構成単位を含む変性アルキルナフタレンホルムアルデヒド重合体は、一般式（１）で示される構成単位を有する重合体に下記一般式（９）で示される化合物からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。一般式（９）で示される化合物としてはアセナフテンが特に好ましい。
本発明で用いるアルキルナフタレンホルムアルデヒド重合体は下記式（１０）で示される各単位からなる群から選ばれる構成単位を有していてもよい。
本発明の一般式（１０）で示される構成単位を含む変性アルキルナフタレンホルムアルデヒド重合体は、一般式（１）で示される構成単位を有する重合体にアントラセン、フェナントレン、ピレン、アセナフチレン、アセナフテン、インデン、フルオレン、フラーレン等の芳香族炭化水素類からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。 The modified alkylnaphthalene formaldehyde polymer containing the structural unit represented by the general formula (10) of the present invention includes an anthracene, phenanthrene, pyrene, acenaphthylene, acenaphthene, indene, a polymer having the structural unit represented by the general formula (1). It can be obtained by a condensation reaction of an aromatic hydrocarbon such as fluorene or fullerene under an acidic or alkaline catalyst.
本発明で用いるアルキルナフタレンホルムアルデヒド重合体は、下記一般式（３）で示される構成単位を含むことが好ましい。
本発明の一般式（３）で示される構成単位を含む重合体は前記重合体に下記一般式（１１）で示される化合物からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。
一般式（１１）で示される化合物としてはフェノール又はフェノール誘導体であることが好ましい。フェノール誘導体は、フェノールとアルケンないしアルコールないしハロゲン化物を酸触媒下でアルキル化反応させることにより得られる。また、エステル化物を用いてエステル交換反応後、ルイス酸触媒等によりフリース転位させることにより、カルボニル基を介したケトン化物が得られる。 The compound represented by the general formula (11) is preferably phenol or a phenol derivative. The phenol derivative can be obtained by alkylating a phenol with an alkene, alcohol or halide under an acid catalyst. In addition, after transesterification using an esterified product, a Fries rearrangement is performed using a Lewis acid catalyst or the like to obtain a ketinated product via a carbonyl group.
本発明で用いるアルキルナフタレンホルムアルデヒド重合体は、下記一般式（４）で示される構成単位を含むことが好ましい。
本発明の一般式（４）で示される構成単位を含む重合体は前記重合体に下記一般式（１２）で示される化合物からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。一般式（１２）で示される化合物としてはフェノール誘導体であることが好ましい。
本発明で用いるアルキルナフタレンホルムアルデヒド重合体は、下記一般式（５）で示される構成単位を含むことが好ましい。
本発明の一般式（５）で示される構成単位を含む重合体は前記重合体に下記一般式（１３）で示される化合物からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。
一般式（１３）で示される化合物としてはナフトール又はナフトール誘導体であることが好ましい。ナフトール誘導体ないしナフタレンジオール誘導体は、ナフトールやナフタレンジオールとアルケンないしアルコールないしハロゲン化物を酸触媒下でアルキル化反応させることにより得られる。また、エステル化物を用いてエステル交換反応後、ルイス酸触媒等によりフリース転位させることにより、カルボニル基を介したケトン化物が得られる。 The compound represented by the general formula (13) is preferably naphthol or a naphthol derivative. Naphthol derivatives or naphthalenediol derivatives can be obtained by alkylating naphthol or naphthalenediol with alkenes, alcohols or halides in the presence of an acid catalyst. In addition, after transesterification using an esterified product, a Fries rearrangement is performed using a Lewis acid catalyst or the like to obtain a ketinated product via a carbonyl group.
本発明で用いるアルキルナフタレンホルムアルデヒド重合体は、下記一般（６）で示される構成単位を含むことが好ましい。
本発明の一般式（６）で示される構成単位を含む重合体は前記重合体に下記一般式（１４）で示される化合物からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。一般式（１４）で示される化合物としてはナフトール誘導体であることが好ましい。
本発明のアルキルナフタレンホルムアルデヒド重合体は下記一般式（７）で示される単位を含むことが好ましい。
本発明の一般式（７）で示される構成単位を含む重合体は前記重合体に下記一般式（１５）で示される化合物からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。
本発明のアルキルナフタレンホルムアルデヒド重合体は下記一般式（８）で示される単位を含むことが好ましい。
本発明の一般式（８）で示される構成単位を含む重合体は前記重合体に下記一般式（１６）で示される化合物からなる変性剤を、酸性又はアルカリ触媒下で縮合反応することにより得られる。
本発明で使用するアルキルナフタレンホルムアルデヒド重合体は、フェノール性水酸基にエポキシ基を導入することが出来る。フェノール性水酸基を有する樹脂とエピクロロヒドリン等のエポキシ含有化合物を塩基の作用によりエポキシ基を導入することが出来る。 The alkylnaphthalene formaldehyde polymer used in the present invention can introduce an epoxy group into a phenolic hydroxyl group. An epoxy group can be introduced by the action of a base between a resin having a phenolic hydroxyl group and an epoxy-containing compound such as epichlorohydrin.
本発明で使用するアルキルナフタレンホルムアルデヒド重合体は単独でも良いが、２種以上混合することもできる。また、アルキルナフタレンホルムアルデヒド重合体は、各種界面活性剤、各種架橋剤、各種酸発生剤、各種安定剤等を含有したものであっても良い。 The alkylnaphthalene formaldehyde polymer used in the present invention may be used alone or in combination of two or more. Further, the alkylnaphthalene formaldehyde polymer may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers and the like.
本発明で使用される有機溶媒としては、水と任意に混和しない有機溶媒であれば特に限定されないが、半導体製造プロセスに安全に適用できる有機溶媒が好ましい。使用する有機溶媒の量は、使用する重合体に対して、通常１〜１００重量倍程度使用される。
使用される溶媒の具体例としては、ジエチルエーテル、ジイソプロピルエーテル等のエーテル類、酢酸エチル、酢酸ｎ‐ブチル、酢酸イソアミル等のエステル類、メチルエチルケトン、メチルイソブチルケトン、エチルイソブチルケトン、シクロヘキサノン、シクロペンタノン、２‐ヘプタノン、２−ペンタノン等のケトン類、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブ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アセテート（ＰＧＭＥＡ）、プロピレングリコールモノエチルエーテルアセテート等のグリコールエーテルアセテート類、ｎ‐ヘキサン、ｎ‐ヘプタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、塩化メチレン、クロロホルム等のハロゲン化炭化水素類等が挙げられる。これらの中でも、トルエン、２−ヘプタノン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトン、プロピレングリコールモノメチルエーテルアセテート、酢酸エチル等が好ましく、特にシクロヘキサノン、プロピレングリコールモノメチルエーテルアセテートが好ましい。
これらの溶媒はそれぞれ単独で用いることもできるし、また２種以上を混合して用いることもできる。The organic solvent used in the present invention is not particularly limited as long as it is an organic solvent that is not arbitrarily miscible with water, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable. The amount of the organic solvent to be used is usually about 1 to 100 times by weight with respect to the polymer to be used.
Specific examples of the solvent used include ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone and cyclopentanone. Ketones such as 2-heptanone and 2-pentanone, glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, n- Aliphatic hydrocarbons such as hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogenation such as methylene chloride and chloroform Hydrogen, etc. can be mentioned. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, and cyclohexanone and propylene glycol monomethyl ether acetate are particularly preferable.
These solvents can be used alone or in combination of two or more.
本発明で使用される酸性の水溶液としては、一般に知られる有機、無機系化合物を水に溶解させた水溶液の中から適宜選択される。例えば、塩酸、硫酸、硝酸、リン酸等の鉱酸を水に溶解させた水溶液、又は、酢酸、プロピオン酸、蓚酸、マロン酸、コハク酸、フマル酸、マレイン酸、酒石酸、クエン酸、メタンスルホン酸、フェノールスルホン酸、ｐ−トルエンスルホン酸、トリフルオロ酢酸等の有機酸を水に溶解させた水溶液が挙げられる。これら酸性の水溶液は、それぞれ単独で用いることもできるし、また２種以上を組み合わせて用いることもできる。これら酸性の水溶液の中でも、硫酸、硝酸及び、酢酸、蓚酸、酒石酸、クエン酸等のカルボン酸の水溶液が好ましく、さらに、硫酸、蓚酸、酒石酸、クエン酸の水溶液が好ましく、特に蓚酸の水溶液が好ましい。蓚酸、酒石酸、クエン酸等の多価カルボン酸は金属イオンに配位し、キレート効果が生じるために、より金属を除去できると考えられる。また、ここで用いる水は、本発明の目的に沿って、金属含有量の少ないもの、例えばイオン交換水等が好ましい。 The acidic aqueous solution used in the present invention is appropriately selected from aqueous solutions in which generally known organic and inorganic compounds are dissolved in water. For example, an aqueous solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid is dissolved in water, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfone An aqueous solution in which an organic acid such as acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid or the like is dissolved in water can be used. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, aqueous solutions of sulfuric acid, nitric acid, and carboxylic acids such as acetic acid, succinic acid, tartaric acid, and citric acid are preferable, and aqueous solutions of sulfuric acid, succinic acid, tartaric acid, and citric acid are preferable, and an aqueous solution of succinic acid is particularly preferable. . Since polyvalent carboxylic acids such as succinic acid, tartaric acid, and citric acid are coordinated to metal ions to produce a chelate effect, it is considered that the metal can be removed more. Moreover, the water used here is preferably one having a low metal content, such as ion-exchanged water, for the purpose of the present invention.
本発明で使用する酸性の水溶液のｐＨは特に制限されないが、水溶液の酸性度があまり大きくなるとアルキルナフタレンホルムアルデヒド樹脂に悪影響を及ぼすことがあり好ましくない。通常、ｐＨ範囲は０〜５程度であり、より好ましくはｐＨ０〜３程度である。 The pH of the acidic aqueous solution used in the present invention is not particularly limited, but if the acidity of the aqueous solution becomes too large, it may adversely affect the alkylnaphthalene formaldehyde resin, which is not preferable. Usually, the pH range is about 0 to 5, more preferably about pH 0 to 3.
本発明で使用する酸性の水溶液の使用量は特に制限されないが、その量があまりに少ないと、金属除去のための抽出回数多くする必要があり、逆に水溶液の量があまりに多いと全体の液量が多くなり操作上の問題を生ずることがある。水溶液の使用量は、通常、有機溶媒に溶解したアルキルナフタレンホルムアルデヒド樹脂溶液に対して１０〜２００重量％であり、好ましくは２０〜１００重量％である。 The amount of the acidic aqueous solution used in the present invention is not particularly limited. However, if the amount is too small, it is necessary to increase the number of extractions for removing the metal. Conversely, if the amount of the aqueous solution is too large, May increase operational problems. The usage-amount of aqueous solution is 10-200 weight% normally with respect to the alkylnaphthalene formaldehyde resin solution melt | dissolved in the organic solvent, Preferably it is 20-100 weight%.
本発明は、上記のような酸性の水溶液と、アルキルナフタレンホルムアルデヒド樹脂及び有機溶媒を含む溶液とを接触させることにより、金属分を抽出することを特徴とする。
抽出処理を行う際の温度は通常、２０〜９０℃であり、好ましくは３０〜８０℃の範囲である。抽出操作は、例えば、攪拌等により、よく混合させたあと、静置することにより行われる。これにより、アルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液に含まれていた金属分が水相に移行する。The present invention is characterized in that a metal component is extracted by bringing an acidic aqueous solution as described above into contact with a solution containing an alkylnaphthalene formaldehyde resin and an organic solvent.
The temperature at the time of performing the extraction treatment is usually 20 to 90 ° C, and preferably 30 to 80 ° C. The extraction operation is performed, for example, by mixing the mixture well by stirring or the like and then allowing it to stand. Thereby, the metal content contained in the solution containing the alkylnaphthalene formaldehyde resin and the organic solvent is transferred to the aqueous phase.
得られる混合物は、アルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液相と水相に分離するのでデカンテーション等によりアルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液を回収する。静置する時間は特に制限されないが、静置する時間があまりに短いと有機溶媒を含む溶液相と水相との分離が悪くなり好ましくない。通常、静置する時間は１０分以上であり、より好ましくは３０分以上である。
また、抽出処理は１回だけでもかまわないが、混合、静置、分離という操作を複数回繰り返して行うのも有効である。Since the resulting mixture is separated into a solution phase containing an alkylnaphthalene formaldehyde resin and an organic solvent and an aqueous phase, a solution containing the alkylnaphthalene formaldehyde resin and the organic solvent is recovered by decantation or the like. The standing time is not particularly limited. However, if the standing time is too short, the separation between the solution phase containing the organic solvent and the aqueous phase is not preferable. Usually, the time to stand still is 10 minutes or more, More preferably, it is 30 minutes or more.
The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.
酸性の水溶液を用いてこのような抽出処理を行った場合は、処理を行ったあとに、該水溶液から抽出し、回収したアルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液は、さらに水との抽出処理を行うことが好ましい。抽出操作は、攪拌等により、よく混合させたあと、静置することにより行われる。そして得られる溶液は、アルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液相と水相に分離するのでデカンテーション等によりアルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液相を回収する。また、ここで用いる水は、本発明の目的に沿って、金属含有量の少ないもの、例えばイオン交換水等が好ましい。抽出処理は１回だけでもかまわないが、混合、静置、分離という操作を複数回繰り返して行うのも有効である。また、抽出処理における両者の使用割合や、温度、時間等の条件は特に制限されないが、先の酸性の水溶液との接触処理の場合と同様で構わない。 When such an extraction process is performed using an acidic aqueous solution, the solution containing the extracted alkylnaphthalene formaldehyde resin and the organic solvent extracted from the aqueous solution after the process is further extracted with water. It is preferable to carry out. The extraction operation is performed by allowing the mixture to stand after mixing well by stirring or the like. The obtained solution is separated into a solution phase containing an alkylnaphthalene formaldehyde resin and an organic solvent and an aqueous phase, and therefore a solution phase containing the alkylnaphthalene formaldehyde resin and the organic solvent is recovered by decantation or the like. Moreover, the water used here is preferably one having a low metal content, such as ion-exchanged water, for the purpose of the present invention. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times. In addition, the use ratio of both in the extraction process, conditions such as temperature and time are not particularly limited, but may be the same as in the case of the contact process with the acidic aqueous solution.
こうして得られたアルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液に混入する水分は減圧蒸留等の操作を施すことにより容易に除去できる。また、必要により有機溶媒を加え、アルキルナフタレンホルムアルデヒド樹脂の濃度を任意の濃度に調整することができる。 Water contained in the solution containing the alkylnaphthalene formaldehyde resin thus obtained and the organic solvent can be easily removed by performing an operation such as vacuum distillation. Moreover, an organic solvent can be added as needed, and the density | concentration of alkyl naphthalene formaldehyde resin can be adjusted to arbitrary density | concentrations.
得られたアルキルナフタレンホルムアルデヒド樹脂と有機溶媒を含む溶液から、アルキルナフタレンホルムアルデヒド樹脂のみ得る方法は、減圧除去や再沈殿による分離、及びそれらの組み合わせ等、公知の方法で行うことができる。 A method for obtaining only the alkylnaphthalene formaldehyde resin from the solution containing the obtained alkylnaphthalene formaldehyde resin and an organic solvent can be performed by a known method such as separation under reduced pressure, separation by reprecipitation, or a combination thereof.
以下、実施例を挙げて、本発明の実施の形態をさらに具体的に説明する。但し、本発明は、これらの実施例に限定はされない。以下の合成例において、化合物の構造は１Ｈ−ＮＭＲ測定で確認した。Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following synthesis examples, the structure of the compound was confirmed by 1 H-NMR measurement.
＜合成例＞ アルキルナフタレンホルムアルデヒド重合体の合成
（ジメチルナフタレン樹脂（ＤＭＮ樹脂）の合成）
・ＤＭＮ樹脂の合成例１
ジム・ロート氏冷却管、温度計、攪拌翼を設置した四つ口フラスコ（２０００ｍL）に、窒素気流下で、三菱ガス化学製１，５‐ジメチルナフタレン(１，５ＤＭＮ)（２１８ｇ、１．４ｍｏｌ）、三菱ガス化学製ホルマリン４０％水溶液（４２０ｇ，５．６ｍｏｌ）、関東化学製９８％硫酸(１９４ｇ)を仕込み、常圧下、７時間１００℃で還流させた。エチルベンゼンで希釈後、中和及び水洗を行い、脱溶媒並びに１，５ＤＭＮを減圧除去し、淡褐色固体（１，５ＤＭＮ‐Ｒ）２５０ｇを得た。ＧＰＣ測定の結果、Ｍｎ：５５０、Ｍｗ：１１３０、Ｍｗ／Ｍｎ：２．０５であった。<Synthesis Example> Synthesis of alkylnaphthalene formaldehyde polymer (Synthesis of dimethylnaphthalene resin (DMN resin))
DMN resin synthesis example 1
In a four-necked flask (2000 mL) equipped with a Jim Roth condenser, thermometer, and stirring blade, under a nitrogen stream, 1,5-dimethylnaphthalene (1,5DMN) (218 g, 1.4 mol) manufactured by Mitsubishi Gas Chemical ), A 40% formalin aqueous solution (420 g, 5.6 mol) manufactured by Mitsubishi Gas Chemical Co., Ltd. and 98% sulfuric acid (194 g) manufactured by Kanto Chemical Co. were charged and refluxed at 100 ° C. for 7 hours under normal pressure. After dilution with ethylbenzene, neutralization and water washing were performed, and the solvent was removed and 1,5DMN was removed under reduced pressure to obtain 250 g of a light brown solid (1,5DMN-R). It was Mn: 550, Mw: 1130, and Mw / Mn: 2.05 as a result of the GPC measurement.
（ナフトール変性ＤＭＮ‐Ｒの合成）
・変性樹脂の合成例１
ジム・ロート氏冷却管、温度計、攪拌翼を設置した四つ口フラスコ（５００ｍL）に、窒素気流下で、合成例１で得た１，５ＤＭＮ‐Ｒ（９０ｇ）、関東化学製α‐ナフトール（７１．１ｇ，０．４９ｍｏｌ）、パラトルエンスルホン酸(０．３６ｇ)を加え、４時間、１８５℃まで昇温させ反応させた。溶媒希釈後、中和及び水洗を行い、脱溶媒並びに減圧除去し、淡褐色固体（ＮＦ−１）１６０ｇを得た。ＧＰＣ測定の結果、Ｍｎ：８４８、Ｍｗ：１６３０、Ｍｗ／Ｍｎ：１．９３であり、また、水酸基価は１７５ｍｇＫＯＨ／ｇであった。なお、前記ＮＦ−１については、上記一般式（１）及び（５）で示される構成単位を含むアルキルナフタレンホルムアルデヒド重合体である。(Synthesis of naphthol-modified DMN-R)
・ Synthetic example 1 of modified resin
In a four-necked flask (500 mL) equipped with a Jim Roth condenser, thermometer, and stirring blades, 1,5DMN-R (90 g) obtained in Synthesis Example 1 and α-naphthol manufactured by Kanto Chemical Co., Ltd. under a nitrogen stream (71.1 g, 0.49 mol) and paratoluenesulfonic acid (0.36 g) were added, and the reaction was allowed to warm to 185 ° C for 4 hours. After solvent dilution, neutralization and water washing were performed, and the solvent was removed and removed under reduced pressure to obtain 160 g of a light brown solid (NF-1). As a result of GPC measurement, Mn: 848, Mw: 1630, Mw / Mn: 1.93, and the hydroxyl value was 175 mgKOH / g. The NF-1 is an alkylnaphthalene formaldehyde polymer containing the structural units represented by the general formulas (1) and (5).
・変性樹脂の合成例２
変性樹脂の合成例１におけるα‐ナフトールの仕込み量を（５０．１ｇ，０．３５ｍｏｌ）に代えた以外は変性樹脂の合成例１と同様に合成し、淡褐色固体（ＮＦ−２）１２５ｇを得た。ＧＰＣ測定の結果、Ｍｎ：８７１、Ｍｗ：２１７４、Ｍｗ／Ｍｎ：２．５０であり、また、水酸基価は１２２ｍｇＫＯＨ／ｇであった。・ Synthetic example 2 of modified resin
Synthesized in the same manner as modified resin synthesis example 1 except that the amount of α-naphthol used in modified resin synthesis example 1 was changed to (50.1 g, 0.35 mol), and 125 g of a light brown solid (NF-2) was obtained. Obtained. As a result of GPC measurement, Mn: 871, Mw: 2174, Mw / Mn: 2.50, and the hydroxyl value was 122 mgKOH / g.
＜実施例＞ 金属含有量の低減された変性樹脂のシクロヘキサノン溶液の製造
（実施例１）
１０００ｍＬ容量の四つ口フラスコ（底抜き型）に、ＮＦ‐１をシクロヘキサノンに溶解させた溶液（１５ｗｔ％）を４００g仕込み、攪拌しながら７５℃まで加熱した。次いで、蓚酸水溶液（ｐＨ１．３）４００ｇを加え、３分間攪拌後、１時間静置した。これにより油相と水相に分離したので、水相を除去した。この操作を２回繰り返した後、得られた油相に、超純水４００ｇを仕込み、３分間攪拌後、１時間静置し、水相を除去した。この操作を３回繰り返すことにより、金属含有量の低減されたＮＦ−１シクロヘキサノン溶液を得た。<Example> Production of cyclohexanone solution of modified resin with reduced metal content (Example 1)
A 1000 mL four-necked flask (bottomed mold) was charged with 400 g of a solution (15 wt%) of NF-1 dissolved in cyclohexanone and heated to 75 ° C. with stirring. Next, 400 g of an aqueous oxalic acid solution (pH 1.3) was added, and the mixture was stirred for 3 minutes and allowed to stand for 1 hour. Since it separated into the oil phase and the water phase by this, the water phase was removed. After repeating this operation twice, 400 g of ultrapure water was added to the obtained oil phase, stirred for 3 minutes, and allowed to stand for 1 hour to remove the aqueous phase. By repeating this operation three times, an NF-1 cyclohexanone solution with a reduced metal content was obtained.
（実施例２）
実施例１における蓚酸水溶液（ｐＨ１．３）４００ｇを仕込む代わりに、硫酸水溶液（ｐＨ１．３）４００ｇを仕込んだ以外は同様に処理して金属含有量の低減されたＮＦ−１シクロヘキサノン溶液を得た。(Example 2)
Instead of charging 400 g of aqueous oxalic acid solution (pH 1.3) in Example 1, an NF-1 cyclohexanone solution having a reduced metal content was obtained in the same manner except that 400 g of sulfuric acid aqueous solution (pH 1.3) was charged. .
＜実施例＞ 金属含有量の低減された変性樹脂のＰＧＭＥＡ溶液の製造
（実施例３）
１０００ｍＬ容量の四つ口フラスコ（底抜き型）に、ＮＦ‐２をＰＧＭＥＡに溶解させた溶液（１０ｗｔ％）を４００g仕込み、攪拌しながら４０℃まで加熱した。次いで、蓚酸水溶液（ｐＨ１．３）１００ｇを加え、３分間攪拌後、１時間静置した。これにより油相と水相に分離したので、水相を除去した。この操作を２回繰り返した後、得られた油相に、超純水１００ｇを仕込み、３分間攪拌後、１時間静置し、水相を除去した。この操作を３回繰り返すことにより、金属含有量の低減されたＮＦ−２ＰＧＭＥＡ溶液を得た。<Example> Production of PGMEA solution of modified resin with reduced metal content (Example 3)
A 1000 mL four-necked flask (bottomed mold) was charged with 400 g of a solution (10 wt%) of NF-2 dissolved in PGMEA and heated to 40 ° C. with stirring. Next, 100 g of an aqueous oxalic acid solution (pH 1.3) was added, and the mixture was stirred for 3 minutes and allowed to stand for 1 hour. Since it separated into the oil phase and the water phase by this, the water phase was removed. After repeating this operation twice, 100 g of ultrapure water was added to the obtained oil phase, stirred for 3 minutes, and allowed to stand for 1 hour to remove the aqueous phase. By repeating this operation three times, an NF-2PGMEA solution with a reduced metal content was obtained.
（実施例４）
実施例３における蓚酸水溶液（ｐＨ１．３）１００ｇを仕込む代わりに、クエン酸水溶液（ｐＨ１．３）１００ｇを仕込んだ以外は同様に処理して金属含有量の低減されたＮＦ−２ＰＧＭＥＡ溶液を得た。Example 4
An NF-2PGMEA solution with a reduced metal content was obtained in the same manner as in Example 3 except that 100 g of an aqueous citric acid solution (pH 1.3) was charged instead of 100 g of an aqueous citric acid solution (pH 1.3). .
（実施例５）
実施例３における蓚酸水溶液（ｐＨ１．３）１００ｇを仕込む代わりに、硫酸水溶液（ｐＨ１．３）１００ｇを仕込んだ以外は同様に処理して金属含有量の低減されたＮＦ−２ＰＧＭＥＡ溶液を得た。(Example 5)
Instead of charging 100 g of the oxalic acid aqueous solution (pH 1.3) in Example 3, the same treatment was performed except that 100 g of sulfuric acid aqueous solution (pH 1.3) was charged to obtain an NF-2PGMEA solution with a reduced metal content.
処理前のＮＦ‐１シクロヘキサノン溶液及び実施例１、２における各種金属含有量をＩＣＰ−ＭＳによって測定した。測定結果を表１に示した。 The NF-1 cyclohexanone solution before treatment and various metal contents in Examples 1 and 2 were measured by ICP-MS. The measurement results are shown in Table 1.
処理前のＮＦ‐２ＰＧＭＥＡ溶液及び実施例３、４、５における各種金属含有量をＩＣＰ−ＭＳによって測定した。測定結果を表２に示した。 The NF-2PGMEA solution before treatment and various metal contents in Examples 3, 4, and 5 were measured by ICP-MS. The measurement results are shown in Table 2.
本発明は、金属含有量の低減されたアルキルナフタレンホルムアルデヒド樹脂を工業的に有利に製造することができる。 INDUSTRIAL APPLICABILITY The present invention can industrially advantageously produce an alkylnaphthalene formaldehyde resin with a reduced metal content.
Claims (15)
（式（６）中、Ｘは−(O CH2)t−であり、ｔは０〜２であり、Ｙは−CO−又は単結合を示し、Ｚは酸素原子又は硫黄原子を示し、Ｒ３はそれぞれ独立にノルボルニル基、シクロヘキシル基、トリシクロデシル基、アダマンチル基、デカヒドロナフチル基及びビシクロオクチル基からなる群から選択される１種以上の官能基を示す。Ｒ５はそれぞれ独立に水素原子又は炭素数１〜３の炭化水素基を示す。ｑは１〜２であり、ｒは０〜４である。） The purification method according to any one of claims 1 to 7, wherein the alkylnaphthalene formaldehyde polymer contains a unit represented by the following general formula (6).
(In the formula (6), X is - (O CH 2) a t-, t is 0 to 2, Y is -CO- or a single bond, Z is shown an oxygen atom or a sulfur atom, R 3 independently represents one or more functional groups selected from the group consisting of a norbornyl group, a cyclohexyl group, a tricyclodecyl group, an adamantyl group, a decahydronaphthyl group and a bicyclooctyl group, and R 5 each independently represents hydrogen. An atom or a hydrocarbon group having 1 to 3 carbon atoms, q is 1 to 2, and r is 0 to 4)
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| PCT/JP2011/002025 WO2011125326A1 (en) | 2010-04-07 | 2011-04-05 | Method for purifying alkylnaphthalene formaldehyde polymer |
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| CN104137235B (en) * | 2012-01-19 | 2017-02-22 | 布鲁尔科技公司 | Nonpolymeric antireflection compositions containing adamantyl groups |
| KR20140136931A (en) * | 2012-02-27 | 2014-12-01 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Acidified mono alkyl naphthalene formaldehyde resin |
| JP6466650B2 (en) | 2014-04-03 | 2019-02-06 | 信越化学工業株式会社 | Method for producing resist composition |
| JP6165690B2 (en) * | 2014-08-22 | 2017-07-19 | 信越化学工業株式会社 | Method for producing composition for forming organic film |
| JP6445382B2 (en) | 2015-04-24 | 2018-12-26 | 信越化学工業株式会社 | Method for producing composition for forming coating film for lithography and method for forming pattern |
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| JPS61223016A (en) * | 1985-03-29 | 1986-10-03 | Mitsubishi Gas Chem Co Inc | Production of polybenzyl type xylene resin |
| JPH01192586A (en) * | 1988-01-29 | 1989-08-02 | Sumitomo Deyurezu Kk | Color developer for pressure-sensitive recording paper and production thereof |
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| JPH051157A (en) * | 1991-04-16 | 1993-01-08 | Dainippon Ink & Chem Inc | Curable prepreg and its cured molded article |
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| TW201144342A (en) | 2011-12-16 |
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