JP4900557B2 - Polycarbosilane - Google Patents
Polycarbosilane Download PDFInfo
- Publication number
- JP4900557B2 JP4900557B2 JP2005263629A JP2005263629A JP4900557B2 JP 4900557 B2 JP4900557 B2 JP 4900557B2 JP 2005263629 A JP2005263629 A JP 2005263629A JP 2005263629 A JP2005263629 A JP 2005263629A JP 4900557 B2 JP4900557 B2 JP 4900557B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polycarbosilane
- general formula
- following general
- bond
- 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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- 229920003257 polycarbosilane Polymers 0.000 title claims description 65
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 239000002994 raw material Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 230000003595 spectral effect Effects 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229910018557 Si O Inorganic materials 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000010354 integration Effects 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 5
- -1 lithium aluminum hydride Chemical compound 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 238000006462 rearrangement reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910008045 Si-Si Inorganic materials 0.000 description 2
- 229910006411 Si—Si Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
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- Silicon Polymers (AREA)
Description
本発明は、新規なポリカルボシランおよびその製造方法に関する。 The present invention relates to a novel polycarbosilane and a method for producing the same.
炭化ケイ素繊維やセラミックス材料の前駆体としてポリカルボシランが着目され、工業的に利用されている。特に、主鎖がケイ素原子と炭素原子との繰り返し構造からなるポリカルボシランは耐熱性に優れており、広く利用されている。また、ポリカルボシランは、光機能材料や導電性材料などへの応用が期待されている。 Polycarbosilane has attracted attention as a precursor for silicon carbide fibers and ceramic materials, and is used industrially. In particular, polycarbosilane whose main chain is a repeating structure of silicon atoms and carbon atoms is excellent in heat resistance and is widely used. Polycarbosilane is expected to be applied to optical functional materials and conductive materials.
ケイ素原子と炭素原子との繰り返し構造からなる主鎖を有するポリカルボシランの製造方法としては、例えば、ポリ（ジメチルシラン）の熱転位による方法が挙げられる（非特許文献１）。この方法では、ポリ（ジメチルシラン）中のケイ素原子に結合するメチル基の一部が主鎖のＳｉ−Ｓｉ結合に挿入されて、Ｓｉ−Ｃ結合を形成するとともに、転位したＳｉ−ＣＨ３部分がＳｉ−Ｈ結合に置き換わる。 Examples of a method for producing polycarbosilane having a main chain composed of a repeating structure of silicon atoms and carbon atoms include a method based on thermal rearrangement of poly (dimethylsilane) (Non-patent Document 1). In this method, a part of the methyl group bonded to the silicon atom in poly (dimethylsilane) is inserted into the Si—Si bond of the main chain to form a Si—C bond, and a rearranged Si—CH 3 moiety. Replaces the Si-H bond.
また、他のポリカルボシランの製造方法としては、例えば、クロロメチルトリクロロシランからグリニャール反応を経てポリカルボシランを得る方法（非特許文献２）や、ジシラシクロブタン類の開環重合によりポリカルボシランを得る方法（非特許文献３）が挙げられる。非特許文献２および３には、モノマー中のケイ素原子上の置換基を塩素原子にしたうえでこのモノマーの重合を行なった後、水素化リチウムアルミニウム等を用いて還元することにより、Ｓｉ−Ｈ結合を有するポリカルボシランを製造する方法が記載されている。 Other polycarbosilane production methods include, for example, a method of obtaining polycarbosilane from a chloromethyltrichlorosilane through a Grignard reaction (Non-patent Document 2), or polycarbosilane by ring-opening polymerization of disilacyclobutanes. (Non-patent Document 3). In Non-Patent Documents 2 and 3, the monomer is polymerized after the substituent on the silicon atom in the monomer is changed to a chlorine atom, and then reduced using lithium aluminum hydride or the like. A method for producing a polycarbosilane having a bond is described.
これまでの技術において、前述ポリカルボシランの硬化を行なうには、（１）酸化雰囲気下での焼成によるSi-O-Si架橋の形成（特許文献１、２）、もしくは（２）Si-H結合同士のカップリングによるSi-Si結合の形成、およびそれに続く転位反応でのSi-C-Si結合の形成（特許文献２）によるものが一般的であった。しかしながら、前記（１）の方法に関しては、半導体集積回路製造工程に利用した場合、既に基板上に組み込まれている金属配線が酸化されて配線抵抗が上昇する懸念があった。また前記（２）の方法に関しては、ポリマー中のSi-H結合の含有量が多いほど硬化は進行しやすいものの、その分貯蔵時にも徐々に脱水素カップリング反応が起こり、ポリマーの劣化につながる問題を有していた。 In the conventional technology, the polycarbosilane can be cured by (1) forming Si—O—Si bridges by baking in an oxidizing atmosphere (Patent Documents 1 and 2), or (2) Si—H. The formation of Si—Si bonds by coupling of bonds and the formation of Si—C—Si bonds in the subsequent rearrangement reaction (Patent Document 2) has been common. However, regarding the method (1), when used in the semiconductor integrated circuit manufacturing process, there is a concern that the metal wiring already incorporated on the substrate is oxidized and the wiring resistance increases. As for the method (2), the higher the Si-H bond content in the polymer, the easier it is to cure. However, the dehydrogenation coupling reaction occurs gradually during storage, leading to polymer degradation. Had a problem.
上記の問題点を解決し、減圧下、あるいは不活性ガス雰囲気下で硬化を行なうことができ、かつ化学的に安定なポリカルボシランとしては、（１）ケイ素―水素結合以外の架橋可能な側鎖を有するか、あるいは架橋前にある程度架橋を促進させた構造を導入し、熱などで硬化が進行しやすいようにしたものや、（２）さらに脱水素カップリング反応が可能となるケイ素―水素結合側鎖が適度に存在するものが好ましい。（１）の機構のみで硬化が可能なポリカルボシランの場合ポリマー中の架橋部分が多くなり、架橋部位が有機基のときは熱安定性、機械的強度の低下が、また架橋部位がシロキサン構造となるときは半導体集積回路用途において、エッチング、プラズマなどの処理プロセスに対する耐性が低下することがそれぞれ懸念される。前述の特許文献２には、Si-O結合を有さないポリカルボシランをシリコンウエハ上に膜組成物を塗布したのちに空気中加熱し、酸化によりSi-O-Si結合を形成する方法が開示され、特許文献３、４には、ケイ素―水素結合を有するポリカルボシランを有機溶剤中アルカリ・水存在下を用いて変性したポリマーが開示されている。しかしながら、半導体集積回路の製造工程に適用した場合に配線などの他材料への影響がなく、保存安定性にもすぐれたポリカルボシランは見出されていなかった。
本発明の目的は、架橋硬化が容易であり、かつ保存安定性に優れたポリカルボシランおよびその製造方法を提供することである。 An object of the present invention is to provide a polycarbosilane that is easily crosslinked and cured and has excellent storage stability and a method for producing the same.
本発明のポリカルボシランは、
ケイ素原子と炭素原子とが交互に連続してなる主鎖を有し、下記一般式（１）で表される繰り返し構造単位、下記一般式（２）で表される繰り返し構造単位、および下記一般式（３）で表される繰り返し構造単位を有する。
The polycarbosilane of the present invention is
It has a main chain in which silicon atoms and carbon atoms are alternately continued. The repeating structural unit represented by the following general formula (1), the repeating structural unit represented by the following general formula (2), and the following general It has a repeating structural unit represented by Formula (3).
本発明のポリカルボシランにおいて、下記一般式（４）〜（１０）で表される繰り返し構造単位のうち少なくとも１つをさらに含むことができる。 The polycarbosilane of the present invention may further include at least one of repeating structural units represented by the following general formulas (4) to (10).
本発明のポリカルボシランにおいて、重量平均分子量が３００〜１，０００，０００であり、有機溶剤に可溶であることができる。 The polycarbosilane of the present invention has a weight average molecular weight of 300 to 1,000,000 and can be soluble in an organic solvent.
本発明のポリカルボシランの製造方法は、
ケイ素原子と炭素原子とが交互に連続してなる主鎖を有し、下記一般式（１）で表される繰り返し構造単位および下記一般式（２）で表される繰り返し構造単位を有する原料ポリマーに、塩基性触媒の存在下で水および／またはアルコールを反応させる工程を含む。
The method for producing the polycarbosilane of the present invention comprises:
A raw material polymer having a main chain in which silicon atoms and carbon atoms are alternately continuous and having a repeating structural unit represented by the following general formula (1) and a repeating structural unit represented by the following general formula (2) And reacting water and / or alcohol in the presence of a basic catalyst.
本発明のポリカルボシランの製造方法において、前記原料ポリマーは、下記一般式（４）で表される繰り返し構造単位および／または下記一般式（５）あるいは（８）で表される繰り返し構造単位を有することができる。 In the method for producing polycarbosilane of the present invention, the raw material polymer includes a repeating structural unit represented by the following general formula (4) and / or a repeating structural unit represented by the following general formula (5) or (8). Can have.
本発明のポリカルボシランによれば、Ｓｉ−Ｈ結合およびＳｉ−Ｏ結合の両方を含むことにより、不活性ガス雰囲気や減圧下など酸化雰囲気でない環境下での焼成でも、ポリマーの架橋・硬化が可能になる。また耐エッチング性、アッシング性などにおいて重要なケイ素―メチル基も適度に含まれている。 According to the polycarbosilane of the present invention, by including both the Si—H bond and the Si—O bond, the polymer can be crosslinked and cured even in firing in an environment that is not an oxidizing atmosphere such as an inert gas atmosphere or a reduced pressure. It becomes possible. In addition, silicon-methyl groups that are important for etching resistance, ashing properties, etc. are also contained moderately.
本発明のポリカルボシランは、セラミックス、耐熱性プラスチック、電子材料用層間膜などへの利用が可能である。 The polycarbosilane of the present invention can be used for ceramics, heat resistant plastics, interlayer films for electronic materials, and the like.
また、本発明のポリカルボシランの製造方法によれば、Ｓｉ−Ｈ結合およびＳｉ−Ｏ結合の両方を任意の割合で含むポリカルボシランを高収率で得ることができる。すなわち、使用する水および／またはアルコールの量を調節することにより、Ｓｉ−Ｈ結合から変換されるＳｉ−Ｏ結合の割合を制御することができる。これにより、Ｓｉ−Ｈ結合およびＳｉ−Ｏ結合の含有比率が制御されたポリカルボシランを得ることができる。 In addition, according to the method for producing polycarbosilane of the present invention, polycarbosilane containing both Si—H bonds and Si—O bonds in an arbitrary ratio can be obtained in high yield. That is, by adjusting the amount of water and / or alcohol used, the ratio of Si—O bonds converted from Si—H bonds can be controlled. Thereby, polycarbosilane in which the content ratio of Si—H bond and Si—O bond is controlled can be obtained.
以下、本発明のポリカルボシランおよびその製造方法について説明する。 Hereinafter, the polycarbosilane of the present invention and the production method thereof will be described.
１．ポリカルボシラン
本発明のポリカルボシランは、ケイ素原子と炭素原子とが交互に連続してなる主鎖を有し、下記一般式（１）で表される繰り返し構造単位、下記一般式（２）で表される繰り返し構造単位、および下記一般式（３）で表される繰り返し構造単位を有する。すなわち、本発明のポリカルボシランは、ケイ素原子と炭素原子とが交互に連続してなる主鎖と、主鎖のケイ素原子に結合する水素原子、酸素原子、および炭素原子を含む側鎖とを含む。
1. Polycarbosilane The polycarbosilane of the present invention has a main chain in which silicon atoms and carbon atoms are alternately continued, and is a repeating structural unit represented by the following general formula (1), the following general formula (2) And a repeating structural unit represented by the following general formula (3). That is, the polycarbosilane of the present invention comprises a main chain in which silicon atoms and carbon atoms are alternately continued, and a hydrogen atom, an oxygen atom, and a side chain containing carbon atoms bonded to the silicon atom of the main chain. Including.
上記一般式（３）において、酸素原子は、水素原子、ケイ素原子、および炭素原子のいずれかに結合可能である。 In the general formula (3), the oxygen atom can be bonded to any one of a hydrogen atom, a silicon atom, and a carbon atom.
本発明において、「ケイ素原子と炭素原子とが交互に連続してなる主鎖」とは、例えば下記一般式（１１）で表される構造を有する。なお、下記一般式（１１）においては、主鎖に結合する側鎖の記載は省略する。また、主鎖に含まれるケイ素原子および炭素原子の数はこれに限定されるわけではない。前記主鎖において、側鎖の種類は特に限定されないが、側鎖としては例えば、−Ｈ、−ＯＨ、−ＯＲ（ここで、Ｒは本発明のポリカルボシランを製造する際に用いるアルコール由来であってもよく、例えば炭素数１〜６のアルキル基）、−Ｏ−Ｓｉであってもよい。 In the present invention, the “main chain in which silicon atoms and carbon atoms are alternately continuous” has, for example, a structure represented by the following general formula (11). In the following general formula (11), the description of the side chain bonded to the main chain is omitted. Further, the numbers of silicon atoms and carbon atoms contained in the main chain are not limited thereto. In the main chain, the type of the side chain is not particularly limited, but examples of the side chain include -H, -OH, -OR (where R is derived from an alcohol used for producing the polycarbosilane of the present invention. It may be, for example, an alkyl group having 1 to 6 carbon atoms) or -O-Si.
本発明のポリカルボシランにおいて、上記一般式（１）〜（３）で表される繰り返し構造単位の数はそれぞれ、５〜５０％、１０〜７０％、５〜５０％であることが好ましい。 In the polycarbosilane of the present invention, the number of the repeating structural units represented by the general formulas (1) to (3) is preferably 5 to 50%, 10 to 70%, and 5 to 50%, respectively.
本発明のポリカルボシランは、下記一般式（４）〜（１０）で表される繰り返し構造単位のうち少なくとも１つをさらに含むことができる。 The polycarbosilane of the present invention may further include at least one of repeating structural units represented by the following general formulas (4) to (10).
上記一般式（６）および（７）において、酸素原子は、水素原子、ケイ素原子、および炭素原子のいずれかに結合可能である。また、上記一般式（８）において、メチレン（−ＣＨ２−）の炭素原子は、酸素原子、ケイ素原子、および炭素原子のいずれかに結合可能である。 In the general formulas (6) and (7), the oxygen atom can be bonded to any one of a hydrogen atom, a silicon atom, and a carbon atom. In the general formula (8), the carbon atom of methylene (—CH 2 —) can be bonded to any of an oxygen atom, a silicon atom, and a carbon atom.
本発明のポリカルボシランは有機溶剤に可溶であり、かつ、その重量平均分子量は３００〜１，０００，０００であることが好ましく、５００〜１００，０００であることがより好ましい。重量平均分子量が３００未満であると、焼成時にポリマーが揮発することがあり、一方、重量平均分子量が１，０００，０００を超えると、ポリマーが溶液に不溶になり、塗布組成物を得ることができない。 The polycarbosilane of the present invention is soluble in an organic solvent, and its weight average molecular weight is preferably 300 to 1,000,000, more preferably 500 to 100,000. When the weight average molecular weight is less than 300, the polymer may volatilize during firing. On the other hand, when the weight average molecular weight exceeds 1,000,000, the polymer becomes insoluble in the solution and a coating composition can be obtained. Can not.
２．ポリカルボシランの製造方法
本発明のポリカルボシランの製造方法は、ケイ素原子と炭素原子とが交互に連続してなる主鎖を有し、下記一般式（１）で表される繰り返し構造単位および下記一般式（２）で表される繰り返し構造単位を有する原料ポリマーに、塩基性触媒の存在下で水および／またはアルコールを反応させる工程を含む。
2. Method for Producing Polycarbosilane The method for producing polycarbosilane of the present invention has a main chain in which silicon atoms and carbon atoms are alternately and continuously represented, and a repeating structural unit represented by the following general formula (1): It includes a step of reacting a raw material polymer having a repeating structural unit represented by the following general formula (2) with water and / or alcohol in the presence of a basic catalyst.
また、前記原料ポリマーは、下記一般式（４）で表される繰り返し構造単位および／または下記一般式（５）あるいは（８）で表される繰り返し構造単位を有することができる。 The raw material polymer may have a repeating structural unit represented by the following general formula (4) and / or a repeating structural unit represented by the following general formula (5) or (8).
本発明のポリカルボシランの製造において、前記原料ポリマーとしては、例えば、下記一般式（１２）、一般式（１３）、および一般式（１４）に示すものがある。 In the production of the polycarbosilane of the present invention, examples of the starting polymer include those represented by the following general formula (12), general formula (13), and general formula (14).
本発明のポリカルボシランの製造において使用可能な塩基性触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化セリウム、水酸化バリウム、水酸化カルシウム、ピリジン、ピロール、ピペラジン、ピロリジン、ピペリジン、ピコリン、アンモニア、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、モノエタノールアミン、ジエタノールアミン、ジメチルモノエタノールアミン、モノメチルジエタノールアミン、トリエタノールアミン、ジアザビシクロオクラン、ジアザビシクロノナン、ジアザビシクロウンデセン、尿素、テトラメチルアンモニウムハイドロオキサイド、テトラエチルアンモニウムハイドロオキサイド、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ハイドロオキサイド、ベンジルトリメチルアンモニウムハイドロオキサイド、コリン、などを挙げることができる。これらの中で、アンモニア、有機アミン類、アンモニウムハイドロオキサイド類を好ましい例として挙げることができ、テトラメチルアンモニウムハイドロオキサイド、テトラエチルアンモニウムハイドロオキサイド、テトラプロピルアンモニウムハイドロオキサイドが特に好ましい。これらの塩基性触媒は、１種あるいは２種以上を同時に使用してもよい。 Examples of the basic catalyst that can be used in the production of the polycarbosilane of the present invention include sodium hydroxide, potassium hydroxide, lithium hydroxide, cerium hydroxide, barium hydroxide, calcium hydroxide, pyridine, pyrrole, piperazine, Pyrrolidine, piperidine, picoline, ammonia, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, dimethylmonoethanol Amine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, urea, tetramethyl Nmo iodonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, may be mentioned benzyl trimethylammonium hydroxide, choline, and the like. Among these, ammonia, organic amines, and ammonium hydroxides can be given as preferred examples, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide are particularly preferable. These basic catalysts may be used alone or in combination of two or more.
塩基性触媒の使用量は、原料ポリカルボシランに含まれるケイ素―水素結合の数によって決定される。 The amount of the basic catalyst used is determined by the number of silicon-hydrogen bonds contained in the raw material polycarbosilane.
本発明のポリカルボシランの製造において使用可能なアルコールとしては、例えば、炭素数１〜６のアルコールが挙げられ、具体的には、メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｔｅｒｔ−ブタノール、ｓｅｃ−ブタノール、ｎ−プロパノール、エチレングリコール、プロピレングリコール、グリセリンなどが挙げられる。 Examples of the alcohol that can be used in the production of the polycarbosilane of the present invention include alcohols having 1 to 6 carbon atoms, specifically, methanol, ethanol, n-propanol, iso-propanol, n-butanol, Examples include tert-butanol, sec-butanol, n-propanol, ethylene glycol, propylene glycol, and glycerin.
本発明のポリカルボシランは、具体的には、塩基性触媒の存在下、有機溶媒中に原料ポリマーと、水および／またはアルコール（ＲＯＨ；Ｒはアルキル基）とを反応させることにより、Ｓｉ−Ｈ結合の一部がＳｉ−Ｏ結合に変換される。より具体的には、Ｓｉ−Ｈ結合の一部を、シラノール（Ｓｉ−ＯＨ）部位、アルコキシシラン（Ｓｉ−ＯＲ）部位、Ｓｉ−Ｏ−Ｓｉ結合のいずれかに変換することができる。水を反応剤として用いる場合、シラノール部位形成後に、当該シラノール部位同士の脱水縮合反応が起こり得る。これにより、Ｓｉ−Ｏ−Ｓｉ結合が形成される。なおＳｉ−Ｈ結合を金属あるいは酸、または塩基触媒の存在下、水またはアルコールを用いてＳｉ−Ｏ結合に変換する方法については、上述の特許文献３，４に示されている。 Specifically, the polycarbosilane of the present invention is obtained by reacting a raw material polymer with water and / or alcohol (ROH; R is an alkyl group) in an organic solvent in the presence of a basic catalyst. Part of the H bond is converted to a Si—O bond. More specifically, a part of the Si—H bond can be converted into any of a silanol (Si—OH) moiety, an alkoxysilane (Si—OR) moiety, and a Si—O—Si bond. When water is used as a reactant, a dehydration condensation reaction between the silanol sites can occur after the silanol sites are formed. Thereby, a Si—O—Si bond is formed. Note that a method for converting a Si—H bond into a Si—O bond using water or alcohol in the presence of a metal, an acid, or a base catalyst is disclosed in Patent Documents 3 and 4 described above.
本発明のポリカルボシランの第１の合成例を下記一般式（１５）に示す。第１の合成例においては、原料ポリマーが上記一般式（１２）で表される場合を例にとり説明する。 A first synthesis example of the polycarbosilane of the present invention is shown in the following general formula (15). In the first synthesis example, the case where the raw material polymer is represented by the general formula (12) will be described as an example.
上記一般式（１５）において、ｚはｘ＞ｚを満たす整数であり、酸素原子は、水素原子、ケイ素原子、および炭素原子のいずれかに結合可能である。すなわち、上記一般式（１２）で表される原料ポリマーのうち、Ｓｉ−Ｈ結合の一部が転位反応によりＳｉ−Ｏ結合に変換されることにより、上記一般式（１５）で表されるポリカルボシランが得られる。 In the general formula (15), z is an integer satisfying x> z, and the oxygen atom can be bonded to any one of a hydrogen atom, a silicon atom, and a carbon atom. That is, in the raw material polymer represented by the general formula (12), a part of the Si—H bond is converted to an Si—O bond by a rearrangement reaction, thereby producing a polycrystal represented by the general formula (15). Carbosilane is obtained.
本発明のポリカルボシランの第２の合成例を下記一般式（１６）に示す。第２の合成例においては、原料ポリマーが上記一般式（１３）で表される場合を例にとり説明する。 A second synthesis example of the polycarbosilane of the present invention is shown in the following general formula (16). In the second synthesis example, the case where the raw material polymer is represented by the general formula (13) will be described as an example.
上記一般式（１６）において、ｅはａ＞ｅを満たす整数であり、ｆ，ｇはｃ＞ｆ＋ｇを満たす整数であり、ｐは０または１であり、酸素原子は、水素原子、ケイ素原子、および炭素原子のいずれかに結合可能である。すなわち、上記一般式（１３）で表される原料ポリマーのうち、Ｓｉ−Ｈ結合の一部が転位反応によりＳｉ−Ｏ結合に変換されることにより、上記一般式（１６）で表されるポリカルボシランが得られる。 In the general formula (16), e is an integer satisfying a> e, f and g are integers satisfying c> f + g, p is 0 or 1, oxygen atoms are hydrogen atoms, silicon atoms, And any carbon atom. That is, in the raw material polymer represented by the general formula (13), a part of the Si—H bond is converted into a Si—O bond by a rearrangement reaction, thereby producing a polypolymer represented by the general formula (16). Carbosilane is obtained.
本発明のポリカルボシランの第３の合成例を下記一般式（１７）に示す。第３の合成例においては、原料ポリマーが上記一般式（１４）で表される場合を例にとり説明する。 A third synthesis example of the polycarbosilane of the present invention is shown in the following general formula (17). In the third synthesis example, the case where the raw material polymer is represented by the general formula (14) will be described as an example.
上記一般式（１７）において、ｅはａ＞ｅを満たす整数であり、ｆ，ｇはｃ＞ｆ＋ｇを満たす整数であり、ｐは０または１であり、酸素原子は、水素原子、ケイ素原子、および炭素原子のいずれかに結合可能である。すなわち、上記一般式（１４）で表される原料ポリマーのうち、Ｓｉ−Ｈ結合の一部が転位反応によりＳｉ−Ｏ結合に変換されることにより、上記一般式（１７）で表されるポリカルボシランが得られる。 In the general formula (17), e is an integer satisfying a> e, f and g are integers satisfying c> f + g, p is 0 or 1, oxygen atoms are hydrogen atoms, silicon atoms, And any carbon atom. That is, in the raw material polymer represented by the general formula (14), a part of the Si—H bond is converted into an Si—O bond by a rearrangement reaction, thereby causing the polypolymer represented by the general formula (17). Carbosilane is obtained.
また、本発明のポリカルボシランの製造方法において、反応系内に酸性水溶液を加えて失活させることにより、Ｓｉ−Ｈ結合形成反応を停止させることができる。さらに、反応剤として水を用いている場合には、生成が予想されるシラノール部位の更なる脱水縮合を抑制することができる。酸性水溶液としては特に限定されないが、例えば、有機酸または無機酸が例示できる。有機酸としては、例えば、酢酸、プロピオン酸、ブタン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、シュウ酸、マレイン酸、メチルマロン酸、アジピン酸、セバシン酸、没食子酸、酪酸、メリット酸、アラキドン酸、シキミ酸、２−エチルヘキサン酸、オレイン酸、ステアリン酸、リノール酸、リノレイン酸、サリチル酸、安息香酸、ｐ−アミノ安息香酸、ｐ−トルエンスルホン酸、ベンゼンスルホン酸、モノクロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、トリフルオロ酢酸、ギ酸、マロン酸、スルホン酸、フタル酸、フマル酸、クエン酸、酒石酸、無水マレイン酸、フマル酸、イタコン酸、コハク酸、メサコン酸、シトラコン酸、リンゴ酸、マロン酸、グルタル酸の加水分解物、無水マレイン酸の加水分解物、無水フタル酸の加水分解物などを挙げることができる。無機酸としては、例えば、塩酸、硝酸、硫酸、フッ酸、リン酸などを挙げることができる。なかでも、ポリマーの析出やゲル化のおそれが少ない点で有機酸が好ましく、このうち、カルボキシル基を有する化合物がより好ましく、なかでも、酢酸、シュウ酸、マレイン酸、ギ酸、マロン酸、フタル酸、フマル酸、イタコン酸、コハク酸、メサコン酸、シトラコン酸、リンゴ酸、マロン酸、グルタル酸、無水マレイン酸の加水分解物が特に好ましい。これらは１種あるいは２種以上を同時に使用してもよい。 Moreover, in the manufacturing method of the polycarbosilane of this invention, Si-H bond formation reaction can be stopped by adding an acidic aqueous solution in a reaction system and making it deactivate. Furthermore, when water is used as the reactant, it is possible to suppress further dehydration condensation of the silanol moiety expected to be produced. Although it does not specifically limit as acidic aqueous solution, For example, an organic acid or an inorganic acid can be illustrated. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid Acid, butyric acid, meritic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, succinic acid, mesaconic acid, Citraconic acid, malic acid, malonic acid, hydrolyzed glutaric acid, hydrolyzed maleic anhydride Objects, and the like hydrolyzate of phthalic anhydride. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Of these, organic acids are preferred because they are less likely to cause polymer precipitation and gelation. Among these, compounds having a carboxyl group are more preferred, and among them, acetic acid, oxalic acid, maleic acid, formic acid, malonic acid, and phthalic acid. Particularly preferred are hydrolysates of fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid and maleic anhydride. These may be used alone or in combination of two or more.
本発明のポリカルボシランの製造方法においては、下記の有機溶剤を使用することができる。本発明に使用する有機溶剤としては、使用する水および／またはアルコールと、原料ポリマーとの両方を溶解させることができるものが好ましい。有機溶剤としては、例えば、ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン、ｉ−ヘキサン、ｎ−ヘプタン、ｉ−ヘプタン、２，２，４−トリメチルペンタン、ｎ−オクタン、ｉ−オクタン、シクロヘキサン、メチルシクロヘキサンなどの脂肪族炭化水素系溶媒；ベンゼン、トルエン、キシレン、エチルベンゼン、トリメチルベンゼン、メチルエチルベンゼン、ｎ−プロピルベンセン、ｉ−プロピルベンセン、ジエチルベンゼン、ｉ−ブチルベンゼン、トリエチルベンゼン、ジ−ｉ−プロピルベンセン、ｎ−アミルナフタレン、トリメチルベンゼンなどの芳香族炭化水素系溶媒（炭化水素系溶媒を用いる場合であって、水を使用する場合、炭化水素系溶媒と他の溶媒とを組み合わせて使用可能である）；アセトン、メチルエチルケトン、メチル−ｎ−プロピルケトン、メチル−ｎ−ブチルケトン、ジエチルケトン、メチル−ｉ−ブチルケトン、メチル−ｎ−ペンチルケトン、エチル−ｎ−ブチルケトン、メチル−ｎ−ヘキシルケトン、ジ−ｉ−ブチルケトン、トリメチルノナノン、シクロヘキサノン、２−ヘキサノン、メチルシクロヘキサノン、２，４−ペンタンジオン、アセトニルアセトン、ジアセトンアルコール、アセトフェノン、フェンチョンなどのケトン系溶媒；エチルエーテル、ｉ−プロピルエーテル、ｎ−ブチルエーテル、ｎ−ヘキシルエーテル、２−エチルヘキシルエーテル、エチレンオキシド、１，２−プロピレンオキシド、ジオキソラン、４−メチルジオキソラン、ジオキサン、ジメチルジオキサン、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ジエチルエーテル、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モノ−ｎ−ヘキシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ−２−エチルブチルエーテル、エチレングリコールジブチルエーテル、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ジメチルエーテル（ジグライム）、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ジエチルエーテル、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−ｎ−ブチルエーテル、ジエチレングリコールモノ−ｎ−ヘキシルエーテル、エトキシトリグリコール、テトラエチレングリコールジ−ｎ−ブチルエーテル、トリプロピレングリコールモノメチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフランなどのエーテル系溶媒；Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、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、Ｎ−メチルプロピオンアミド、Ｎ−メチルピロリドンなどの含窒素系溶媒；硫化ジメチル、硫化ジエチル、チオフェン、テトラヒドロチオフェン、ジメチルスルホキシド、スルホラン、１，３−プロパンスルトンなどの含硫黄系溶媒;メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｔｅｒｔ−ブタノール、ｓｅｃ−ブタノール、ｎ−プロパノールなどのアルコール系溶媒（この場合、アルコール系溶媒は反応剤としての作用も有する。）などを挙げることができる。これらは、１種あるいは２種以上を混合して使用することができる。また上記溶剤との混合で用いる場合は、ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン、ｉ−ヘキサン、ｎ−ヘプタン、ｉ−ヘプタン、２，２，４−トリメチルペンタン、ｎ−オクタン、ｉ−オクタン、シクロヘキサン、メチルシクロヘキサンなどの脂肪族炭化水素系溶媒；ベンゼン、トルエン、キシレン、エチルベンゼン、トリメチルベンゼン、メチルエチルベンゼン、ｎ−プロピルベンセン、ｉ−プロピルベンセン、ジエチルベンゼン、ｉ−ブチルベンゼン、トリエチルベンゼン、ジ−ｉ−プロピルベンセン、ｎ−アミルナフタレン、トリメチルベンゼンなどの芳香族炭化水素系溶媒などを使用することもできる。 In the method for producing polycarbosilane of the present invention, the following organic solvents can be used. The organic solvent used in the present invention is preferably one that can dissolve both the water and / or alcohol to be used and the raw material polymer. Examples of the organic solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, Aliphatic hydrocarbon solvents such as methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propyl Aromatic hydrocarbon solvents such as benzene, n-amylnaphthalene, and trimethylbenzene (in the case of using a hydrocarbon solvent and using water, it is possible to use a combination of a hydrocarbon solvent and another solvent. Yes); acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, Ketone solvents such as cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol No ethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, Diethylene glycol dimethyl ether (diglyme), diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, Tripropylene Ether solvents such as recall monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N Nitrogen-containing solvents such as methylpropionamide and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane and 1,3-propane sultone; methanol, ethanol, n -Alcohol solvents such as propanol, iso-propanol, n-butanol, tert-butanol, sec-butanol, n-propanol (in this case, the alcohol solvent acts as a reactant) Also have. ) And the like. These can be used alone or in combination of two or more. When used in the mixture with the above solvent, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di Aromatic hydrocarbon solvents such as -i-propyl benzene, n-amyl naphthalene, and trimethyl benzene can also be used.
３．実施例
以下、本発明の実施例について説明するが、本発明はこれらの実施例に限定されるものではない。実験例および比較例における各評価は以下に示す方法で行なった。
3. EXAMPLES Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. Each evaluation in the experimental examples and the comparative examples was performed by the following methods.
３．１ 分子量
ポリカルボシランの重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、下記条件によるゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した。
試料：テトラヒドロフランを溶媒として使用し、重合体１［ｇ］を、１００［ｃｃ］のテトラヒドロフランに溶解して調製した。
標準ポリスチレン：米国プレッシャーケミカル社製の標準ポリスチレンを使用した。
装置：米国ウオーターズ社製の高温高速ゲル浸透クロマトグラム（モデル１５０−ＣＡＬＣ／ＧＰＣ）
カラム：昭和電工（株）製のＳＨＯＤＥＸ Ａ−８０Ｍ（長さ５０ｃｍ）
測定温度：４０℃流速：１ｃｃ／分
3.1 Molecular Weight The weight average molecular weight (Mw) and number average molecular weight (Mn) of polycarbosilane were measured by gel permeation chromatography (GPC) method under the following conditions.
Sample: Tetrahydrofuran was used as a solvent, and polymer 1 [g] was prepared by dissolving in 100 [cc] tetrahydrofuran.
Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company was used.
Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-CALC / GPC) manufactured by Waters, USA
Column: SHODEX A-80M (length: 50 cm) manufactured by Showa Denko K.K.
Measurement temperature: 40 ° C. Flow rate: 1 cc / min
３．２ ＮＭＲスペクトル
下記の装置を用いて、１Ｈ ＮＭＲスペクトル（５００ＭＨｚ）および２９Ｓｉ ＮＭＲスペクトル（１００ＭＨｚ）の測定を行なった。
装置：BRUKER AVANCE 500型（ブルカー（Bruker）社製）
3.2 NMR spectrum Using the following apparatus, a 1 H NMR spectrum (500 MHz) and a 29 Si NMR spectrum (100 MHz) were measured.
Equipment: BRUKER AVANCE 500 (Bruker)
３．３ 実験例１
（株）日本カーボン社製ニプシＴｙｐｅ−Ｓ（商品名，以下「原料ポリマー１」ともいう）20[g]をテトラヒドロフランに溶解させて400[g]とし、ここに1.0[mol/L]のTMAH(テトラメチルアンモニウムハイドロオキサイド)水溶液を5.0[ml]加えた後、この反応液を５０℃で３時間加熱した。次に、この反応液を室温まで冷却した後、2.0[mol/L]のシュウ酸水溶液10[ml]を加えて反応を停止させた。次いで、この反応液にシクロヘキサノン100[g]と0.02[mol/L]のシュウ酸水溶液400[g]とを加えて振り混ぜた後、静置して有機相と水相とに分離した。この有機相を取り出して濃縮することにより、実験例１のポリカルボシラン19.8[g]を得た。
3.3 Experimental Example 1
Nisshi Type-S (trade name, hereinafter also referred to as “raw polymer 1”) 20 [g] manufactured by Nippon Carbon Co., Ltd. was dissolved in tetrahydrofuran to 400 [g], and 1.0 [mol / L] TMAH was added here. After adding 5.0 [ml] of (tetramethylammonium hydroxide) aqueous solution, the reaction solution was heated at 50 ° C. for 3 hours. Next, after the reaction solution was cooled to room temperature, 2.0 [mol / L] oxalic acid aqueous solution 10 [ml] was added to stop the reaction. Next, 100 [g] of cyclohexanone and 400 [g] of an aqueous oxalic acid solution of 0.02 [mol / L] were added to this reaction solution, shaken and mixed, and then allowed to stand to separate into an organic phase and an aqueous phase. The organic phase was taken out and concentrated to obtain 19.8 [g] of polycarbosilane of Experimental Example 1.
実験例１のポリカルボシランの理化学的データを以下に示す。実験例１のポリカルボシランの構造およびＮＭＲスペクトルデータとの帰属を、下記一般式（１８）および表１，２に示す。なお、下記一般式（１８）において、ｘは４０％（０．４）であり、ｙは６０％（０．６）であり、ｚは１０％（０．１）である。ＩＲスペクトルデータの結果から、実験例１のポリカルボシランは、Ｓｉ−ＯＨ部位を含むと推測される。 The physicochemical data of the polycarbosilane of Experimental Example 1 are shown below. The structure of the polycarbosilane of Experimental Example 1 and its attribution to the NMR spectrum data are shown in the following general formula (18) and Tables 1 and 2. In the following general formula (18), x is 40% (0.4), y is 60% (0.6), and z is 10% (0.1). From the result of IR spectrum data, it is estimated that the polycarbosilane of Experimental Example 1 includes a Si—OH site.
１Ｈ ＮＭＲ（重ベンゼン中）スペクトルデータ：-2.0〜1.0ppm（broad），3.5-4.5ppm（broad）
２９Ｓｉ ＮＭＲ（重ベンゼン中）スペクトルデータ：-40〜-30ppm（broad），-20〜10ppm（broad），10〜30ppm（broad）；後者２つのピークは重なっている。３つのピークの積分比はおよそ３：６：１であった。
1 H NMR (in heavy benzene) spectral data: -2.0 to 1.0 ppm (broad), 3.5-4.5 ppm (broad)
29 Si NMR (in heavy benzene) spectral data: −40 to −30 ppm (broad), −20 to 10 ppm (broad), 10 to 30 ppm (broad); the latter two peaks overlap. The integration ratio of the three peaks was approximately 3: 6: 1.
ＩＲスペクトルデータ（液膜法）： 3670cm-1(Si-OHに対応)， 2950cm-1, 2900cm-1, 2096cm-1, 1360cm-1, 1250cm-1, 1030cm-1, 820cm-1
分子量（ＧＰＣ）：Ｍｗ＝７，１００，Ｍｎ＝７２０
IR spectral data (Ekimakuho): 3670cm -1 (corresponding to Si-OH), 2950cm -1, 2900cm -1, 2096cm -1, 1360cm -1, 1250cm -1, 1030cm -1, 820cm -1
Molecular weight (GPC): Mw = 7,100, Mn = 720
また、得られたポリマーを４[%]の酢酸ブチル溶液とし、これをシリコンウエハ上に2500[rpm]にてスピンコートして得た膜を、窒素雰囲気下150[℃]で１分間、続いて400[℃]で１分間ホットプレート上にて焼成した。この膜厚（表９における「成膜後の膜厚」に相当）を測定したのち、このウエハ上にシクロヘキサノン（溶剤）を同じく2500[rpm]にてスピンコートした後、同様に150[℃]、続いて400[℃]で焼成させて、この後の膜厚（表９における「溶剤塗布・焼成後の膜厚」に相当）を測定して、シクロヘキサノン塗布前後の比較を行った。その結果を表９に示す。なお、表９において、「減膜率（％）」＝「｛（成膜後の膜厚）−（溶剤塗布・焼成後の膜厚）｝／（成膜後の膜厚）×１００」を表す。 In addition, the obtained polymer was made into a 4% butyl acetate solution, and this was spin-coated on a silicon wafer at 2500 rpm, followed by 1 minute in a nitrogen atmosphere at 150 ° C. for 1 minute. And baked on a hot plate at 400 [° C.] for 1 minute. After measuring this film thickness (corresponding to “film thickness after film formation” in Table 9), cyclohexanone (solvent) was spin-coated on this wafer at 2500 [rpm], and then 150 [° C.] Subsequently, the film was fired at 400 [° C.], and the film thickness after this (corresponding to “film thickness after solvent coating / firing” in Table 9) was measured, and comparison before and after cyclohexanone coating was performed. The results are shown in Table 9. In Table 9, “film reduction rate (%)” = “{(film thickness after film formation) − (film thickness after solvent application / firing)} / (film thickness after film formation) × 100” To express.
３．４ 実験例２
（株）日本カーボン社製ニプシＴｙｐｅ−ＵＨ（商品名，以下「原料ポリマー２」ともいう）20[g]をジオキサンに溶解させて400[g]とし、これにピリジン3.0[ml]および水4.0[ml]を加えた後、この反応液を80[℃]で５時間加熱した。次に、この反応液を室温まで冷却した後、2.0 [mol/L]の酢酸水溶液10[ml]を加えて反応を停止させた。次いで、この反応液にシクロヘキサノン100[g]と0.02[mol/L]の酢酸水溶液400[g]とを加えて振り混ぜた後、静置して有機相と水相とに分離した。この有機相を取り出して濃縮することにより、実験例２のポリカルボシラン19.3[g]を得た。
3.4 Experimental Example 2
Nisshi Type-UH (trade name, hereinafter also referred to as “raw polymer 2”) 20 [g] manufactured by Nippon Carbon Co., Ltd. was dissolved in dioxane to 400 [g], and pyridine 3.0 [ml] and water 4.0 After adding [ml], the reaction solution was heated at 80 [° C.] for 5 hours. Next, the reaction solution was cooled to room temperature, and then 2.0 [mol / L] acetic acid aqueous solution 10 [ml] was added to stop the reaction. Next, cyclohexanone 100 [g] and 0.02 [mol / L] acetic acid aqueous solution 400 [g] were added to this reaction solution, shaken and mixed, and then allowed to stand to separate into an organic phase and an aqueous phase. The organic phase was taken out and concentrated to obtain 19.3 [g] of polycarbosilane of Experimental Example 2.
実験例２のポリカルボシランの理化学的データを以下に示す。実験例２のポリカルボシランの構造およびＮＭＲスペクトルデータとの帰属を、下記一般式（１９）および表３，４に示す。なお、下記一般式（１９）において、ｘは４０％（０．４）であり、ｙは６０％（０．６）であり、ｚは１０％（０．１）である。ＩＲスペクトルデータの結果から、実験例２のポリカルボシランは、Ｓｉ−ＯＨ部位を含むと推測される。 The physicochemical data of the polycarbosilane of Experimental Example 2 are shown below. The structure of the polycarbosilane of Experimental Example 2 and the attribution with the NMR spectrum data are shown in the following general formula (19) and Tables 3 and 4. In the following general formula (19), x is 40% (0.4), y is 60% (0.6), and z is 10% (0.1). From the result of IR spectrum data, it is estimated that the polycarbosilane of Experimental Example 2 includes a Si—OH site.
１Ｈ ＮＭＲ（重ベンゼン中）スペクトルデータ：-2.0〜1.0ppm（broad），3.5-4.5ppm（broad）
２９Ｓｉ ＮＭＲ（重ベンゼン中）スペクトルデータ：-40〜-30ppm（broad），-20〜10ppm（broad），10〜30ppm（broad）；後者２つのピークは重なっている。３つのピークの積分比はおよそ３．５：６：０．５であった。
1 H NMR (in heavy benzene) spectral data: -2.0 to 1.0 ppm (broad), 3.5-4.5 ppm (broad)
29 Si NMR (in heavy benzene) spectral data: −40 to −30 ppm (broad), −20 to 10 ppm (broad), 10 to 30 ppm (broad); the latter two peaks overlap. The integration ratio of the three peaks was approximately 3.5: 6: 0.5.
ＩＲスペクトルデータ（液膜法）： 3670cm-1(Si-OHに対応)， 2950cm-1, 2900cm-1, 2096cm-1, 1360cm-1, 1250cm-1, 1030cm-1, 820cm-1
分子量（ＧＰＣ）：Ｍｗ＝１０，２００、Ｍｎ＝１，５００
IR spectral data (Ekimakuho): 3670cm -1 (corresponding to Si-OH), 2950cm -1, 2900cm -1, 2096cm -1, 1360cm -1, 1250cm -1, 1030cm -1, 820cm -1
Molecular weight (GPC): Mw = 10,200, Mn = 1,500
また、得られたポリマーをシリコンウエハ上に塗布・焼成して、溶剤に対する耐溶解性を実験例１と同様に評価した。その結果を表９に示す。 Further, the obtained polymer was applied and baked on a silicon wafer, and the dissolution resistance to a solvent was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 9.
３．５ 比較例１
（株）日本カーボン社製ニプシＴｙｐｅ−Ｓ（原料ポリマー１）の理化学的データ
１Ｈ ＮＭＲ（重ベンゼン中）スペクトルデータ：-2.0〜1.0ppm（broad），3.5-4.5ppm（broad）
２９Ｓｉ ＮＭＲ（重ベンゼン中）スペクトルデータ：-40〜-30ppm（broad），-20〜10ppm（broad）；２つのピークの積分比はおよそ４：６であった。
3.5 Comparative Example 1
Physicochemical data of Nippon Carbon Co., Ltd. Nypsi Type-S (raw polymer 1)
1 H NMR (in heavy benzene) spectral data: -2.0 to 1.0 ppm (broad), 3.5-4.5 ppm (broad)
29 Si NMR (in heavy benzene) spectral data: −40 to −30 ppm (broad), −20 to 10 ppm (broad); the integration ratio of the two peaks was approximately 4: 6.
ＩＲスペクトルデータ（液膜法）： 2950cm-1， 2900cm-1， 2096cm-1， 1360cm-1， 1250cm-1， 1030cm-1， 820cm-1
分子量（ＧＰＣ）：Ｍｗ＝３，０００，Ｍｎ＝５００
比較例１（原料ポリマー１）の構造およびＮＭＲスペクトルデータとの帰属を、下記一般式（２０）および表５，６に示す。なお、下記一般式（２０）において、ｘは４０％（０．４）であり、ｙは６０％（０．６）である。
IR spectral data (Ekimakuho): 2950cm -1, 2900cm -1, 2096cm -1, 1360cm -1, 1250cm -1, 1030cm -1, 820cm -1
Molecular weight (GPC): Mw = 3,000, Mn = 500
The structure of Comparative Example 1 (starting polymer 1) and the attribution of the NMR spectrum data are shown in the following general formula (20) and Tables 5 and 6. In the following general formula (20), x is 40% (0.4) and y is 60% (0.6).
実験例１のポリカルボシランの２９Ｓｉ ＮＭＲスペクトルデータは、比較例１（原料ポリマー１）の２９Ｓｉ ＮＭＲスペクトルデータと比較すると、10〜30[ppm]に新たなピークを有する。このピークは、酸素原子に結合したケイ素原子を示すものと推測される。 29 Si NMR spectral data for the polycarbosilane of Experimental Example 1, compared with 29 Si NMR spectral data for Comparative Example 1 (raw material polymer 1), with a new peak at 10 to 30 [ppm]. This peak is presumed to indicate a silicon atom bonded to an oxygen atom.
加えて、実験例１のポリカルボシランの２９Ｓｉ ＮＭＲスペクトルデータ中の３つのピークの積分比がおよそ３：６：１であるのに対し、比較例１である原料ポリマー１の２９Ｓｉ ＮＭＲスペクトルデータ中の２つのピークの積分比がおよそ４：６であった。これにより、原料ポリマー１中のＳｉ−Ｈ結合のうち一部（Ｓｉ−Ｈ結合の約２５モル％）がＳｉ−Ｏ結合に変換されて、実験例１のポリカルボシランが得られたと推測される。すなわち、実験例１のポリカルボシランは、Ｓｉ−Ｈ結合およびＳｉ−Ｏ結合の両方を有することが確認された。 In addition, the integration ratio of three peaks in the 29 Si NMR spectrum data of the polycarbosilane of Experimental Example 1 is approximately 3: 6: 1, whereas the 29 Si NMR spectrum of the raw material polymer 1 of Comparative Example 1 The integration ratio of the two peaks in the data was approximately 4: 6. Thereby, it is speculated that a part of the Si—H bonds in the raw material polymer 1 (about 25 mol% of the Si—H bonds) was converted to Si—O bonds, and the polycarbosilane of Experimental Example 1 was obtained. The That is, it was confirmed that the polycarbosilane of Experimental Example 1 has both a Si—H bond and a Si—O bond.
また、原料ポリマー１をシリコンウエハ上に塗布・焼成して、溶剤に対する耐溶解性を実験例１と同様に評価した。その結果を表９に示す。 Moreover, the raw material polymer 1 was apply | coated and baked on the silicon wafer, and the dissolution resistance with respect to a solvent was evaluated similarly to Experimental Example 1. The results are shown in Table 9.
３．６ 比較例２
（株）日本カーボン社製ニプシＴｙｐｅ−ＵＨ（原料ポリマー２）の理化学的データ
１Ｈ ＮＭＲ（重ベンゼン中）スペクトルデータ：-2.0〜1.0ppm（broad），3.5-4.5ppm（broad）
２９Ｓｉ ＮＭＲ（重ベンゼン中）スペクトルデータ：-40〜-30ppm（broad），-20〜10ppm（broad）；２つのピークの積分比はおよそ４：６であった。
3.6 Comparative Example 2
Physicochemical data of Nippon Carbon Co., Ltd. Nipsi Type-UH (raw polymer 2)
1 H NMR (in heavy benzene) spectral data: -2.0 to 1.0 ppm (broad), 3.5-4.5 ppm (broad)
29 Si NMR (in heavy benzene) spectral data: −40 to −30 ppm (broad), −20 to 10 ppm (broad); the integration ratio of the two peaks was approximately 4: 6.
ＩＲスペクトルデータ（液膜法）： 2950cm-1， 2900cm-1， 2096cm-1， 1360cm-1， 1250cm-1， 1030cm-1， 820cm-1
分子量（ＧＰＣ）：Ｍｗ＝５，０００、Ｍｎ＝１，０００
比較例２（原料ポリマー２）の構造およびＮＭＲスペクトルデータとの帰属を、下記一般式（２１）および表７，８に示す。なお、下記一般式（２１）において、ｘは４０％（０．４）であり、ｙは６０％（０．６）である。
IR spectral data (Ekimakuho): 2950cm -1, 2900cm -1, 2096cm -1, 1360cm -1, 1250cm -1, 1030cm -1, 820cm -1
Molecular weight (GPC): Mw = 5,000, Mn = 1,000
The structure of Comparative Example 2 (Raw Material Polymer 2) and attribution with NMR spectrum data are shown in the following general formula (21) and Tables 7 and 8. In the following general formula (21), x is 40% (0.4), and y is 60% (0.6).
実験例２のポリカルボシランの２９Ｓｉ ＮＭＲスペクトルデータは、比較例２（原料ポリマー２）の２９Ｓｉ ＮＭＲスペクトルデータと比較すると、10〜30ppmに新たなピークを有する。このピークは、酸素原子に結合したケイ素原子を示すものと推測される。 29 Si NMR spectral data for the polycarbosilane of Experimental Example 2 has when compared to 29 Si NMR spectral data for Comparative Example 2 (raw material polymer 2), a new peak at 10 to 30 ppm. This peak is presumed to indicate a silicon atom bonded to an oxygen atom.
加えて、実験例２のポリカルボシランの２９Ｓｉ ＮＭＲスペクトルデータ中の３つのピークの積分比がおよそ３。５：６：０．５であるのに対し、比較例２である原料ポリマー２の２９Ｓｉ ＮＭＲスペクトルデータ中の２つのピークの積分比がおよそ４：６であった。これにより、原料ポリマー２中のＳｉ−Ｈ結合のうち一部（Ｓｉ−Ｈ結合の約１３モル％）がＳｉ−Ｏ結合に変換されて、実験例２のポリカルボシランが得られたと推測される。すなわち、実験例２のポリカルボシランは、Ｓｉ−Ｈ結合およびＳｉ−Ｏ結合の両方を有することが確認された。 In addition, the integration ratio of the three peaks in the 29 Si NMR spectrum data of the polycarbosilane of Experimental Example 2 is approximately 3.5: 6: 0.5, while that of the raw material polymer 2 of Comparative Example 2 The integration ratio of the two peaks in the 29 Si NMR spectral data was approximately 4: 6. Thereby, it is speculated that a part of Si—H bonds in the raw material polymer 2 (about 13 mol% of the Si—H bonds) was converted to Si—O bonds, and the polycarbosilane of Experimental Example 2 was obtained. The That is, it was confirmed that the polycarbosilane of Experimental Example 2 has both a Si—H bond and a Si—O bond.
また、原料ポリマー２をシリコンウエハ上に塗布・焼成して、溶剤に対する耐溶解性を実験例１と同様に評価した。その結果を表９に示す。 Moreover, the raw material polymer 2 was apply | coated and baked on the silicon wafer, and the dissolution resistance with respect to a solvent was evaluated similarly to Experimental Example 1. The results are shown in Table 9.
Claims (1)
下記一般式（１）で表される繰り返し構造単位、下記一般式（２）で表される繰り返し構造単位、および下記一般式（９）で表される繰り返し構造単位を有し、
重量平均分子量が３００〜１，０００，０００であり、有機溶剤に可溶である、ポリカルボシラン。
Having a repeating structural unit represented by the following general formula (1), a repeating structural unit represented by the following general formula (2), and a repeating structural unit represented by the following general formula ( 9 ),
Polycarbosilane having a weight average molecular weight of 300 to 1,000,000 and being soluble in an organic solvent.
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