JP2023103684A - Polysilazane-containing composition, cured film, and article - Google Patents
Polysilazane-containing composition, cured film, and article Download PDFInfo
- Publication number
- JP2023103684A JP2023103684A JP2022004341A JP2022004341A JP2023103684A JP 2023103684 A JP2023103684 A JP 2023103684A JP 2022004341 A JP2022004341 A JP 2022004341A JP 2022004341 A JP2022004341 A JP 2022004341A JP 2023103684 A JP2023103684 A JP 2023103684A
- Authority
- JP
- Japan
- Prior art keywords
- polysilazane
- component
- group
- containing composition
- cured film
- 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.)
- Pending
Links
- 229920001709 polysilazane Polymers 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000005227 gel permeation chromatography Methods 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 abstract description 13
- 238000001723 curing Methods 0.000 description 52
- -1 7-octenyl group Chemical group 0.000 description 50
- 238000000576 coating method Methods 0.000 description 38
- 239000011248 coating agent Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000059 patterning Methods 0.000 description 14
- 238000011161 development Methods 0.000 description 13
- 230000018109 developmental process Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 4
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 4
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 4
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 230000007261 regionalization Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- XMGQYMWWDOXHJM-SNVBAGLBSA-N (-)-α-limonene Chemical compound CC(=C)[C@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-SNVBAGLBSA-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
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- 229940117955 isoamyl acetate Drugs 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 2
- 229930004008 p-menthane Natural products 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical group CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YYRVEGVDWDWZGG-UHFFFAOYSA-N C1(CCCCC1)N(C(OCC=1C2=CC=CC=C2C=C2C=CC=CC=12)=O)C1CCCCC1 Chemical compound C1(CCCCC1)N(C(OCC=1C2=CC=CC=C2C=C2C=CC=CC=12)=O)C1CCCCC1 YYRVEGVDWDWZGG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ZWDNVDDEDBXBMD-UHFFFAOYSA-N anthracen-9-ylmethyl n,n-diethylcarbamate Chemical compound C1=CC=C2C(COC(=O)N(CC)CC)=C(C=CC=C3)C3=CC2=C1 ZWDNVDDEDBXBMD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- JHAYEQICABJSTP-UHFFFAOYSA-N decoquinate Chemical group N1C=C(C(=O)OCC)C(=O)C2=C1C=C(OCC)C(OCCCCCCCCCC)=C2 JHAYEQICABJSTP-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UWGIJJRGSGDBFJ-UHFFFAOYSA-N dichloromethylsilane Chemical compound [SiH3]C(Cl)Cl UWGIJJRGSGDBFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000006316 iso-butyl amino group Chemical group [H]N(*)C([H])([H])C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000006318 tert-butyl amino group Chemical group [H]N(*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、ポリシラザン含有組成物、該組成物より形成された硬化膜、および該硬化膜を含む物品に関する。 TECHNICAL FIELD The present invention relates to a polysilazane-containing composition, a cured film formed from the composition, and an article containing the cured film.
電子機器の小型化や電子部品の高集積化に伴い、電子部品の小型化が進んでいる。電子機器の高性能化のためには長時間使用時でも性能が劣化しにくい高い耐久性が求められている。電子部品の特性を劣化させる要因として腐食性ガスや水分の影響がある。腐食性ガスや水分の影響を低減させる１つの方法としては、電子部品に保護材を適用することが挙げられる。特許文献１では、電子部品間や電子部品と封止樹脂間に含浸することで電極部の腐食を抑制する電子部品用ポリイミドシリコーン含浸材が報告されている。 With the miniaturization of electronic equipment and the high integration of electronic components, the miniaturization of electronic components is progressing. In order to improve the performance of electronic equipment, high durability is required so that the performance does not easily deteriorate even when used for a long time. Corrosive gases and moisture are factors that degrade the characteristics of electronic components. One method of reducing the effects of corrosive gases and moisture is to apply protective materials to electronic components. Patent Literature 1 reports a polyimide silicone impregnating material for electronic parts that suppresses corrosion of electrode portions by being impregnated between electronic parts or between an electronic part and a sealing resin.
ポリシラザン化合物は硬化により良質なガラス質の硬化膜を形成することから、優れたガスバリア性や耐熱性、絶縁性を示す。電子部品は高温環境下での使用において高い信頼性が求められる。そこで、上記硬化膜は電子部品への水分や腐食性ガスの侵入を防ぐコーティングとして有用である。特許文献２では、有機ＥＬ素子の封止を目的とした樹脂シートの表面にポリシラザン化合物を塗布してガラス質硬化膜を形成させることで、樹脂シートの水蒸気透過量を低くできることが報告されている。 Since the polysilazane compound forms a high-quality glassy cured film when cured, it exhibits excellent gas barrier properties, heat resistance, and insulating properties. Electronic components are required to be highly reliable when used in high temperature environments. Therefore, the cured film is useful as a coating for preventing penetration of moisture and corrosive gas into electronic parts. Patent Document 2 reports that the water vapor permeation amount of the resin sheet can be reduced by applying a polysilazane compound to the surface of the resin sheet for the purpose of encapsulating an organic EL element to form a vitreous cured film. .
上記の背景から、ポリシラザン化合物によるガスバリアコーティングを一例とする機能性コーティングは、電子部品の性能を向上させるものである。しかし、表面実装型の電子部品をコーティングする場合には問題が発生する。その問題とは、素体だけでなく電極部もコーティングで覆われた状態で半田実装を試みると、回路基板への固着強度の著しい低下や導通不良が引き起こされうることである。そこで特許文献３では、水溶性ポリマーまたは脂肪族塩をマスク剤として用いることで、基材の所望の箇所にポリシラザン硬化被膜をパターニングする方法が報告されている。この方法を用いれば表面実装型の電子部品において電極部以外をコーティングで覆うことが可能である。 In view of the above background, functional coatings such as gas barrier coatings using polysilazane compounds improve the performance of electronic components. However, problems arise when coating surface-mounted electronic components. The problem is that if soldering is attempted in a state in which not only the element body but also the electrode portion is covered with the coating, a significant reduction in the bonding strength to the circuit board and poor conduction may occur. Therefore, Patent Document 3 reports a method of patterning a cured polysilazane film on a desired portion of a base material by using a water-soluble polymer or an aliphatic salt as a masking agent. By using this method, it is possible to coat the surfaces other than the electrode portions of the surface-mounted electronic component.
しかしながら、電気電子工学分野における近年のさらなる技術開発により、電子部品では一辺の長さがミリメートルオーダー未満の大きさの製品加工、半導体回路ではナノメートルオーダーでのパターン形成が行われている。このような微細加工において、物理的な接触によるハンドリングには限界があるために、特許文献３の技術を適用することが困難になる場合がある。 However, due to the further technological development in the field of electrical and electronic engineering in recent years, the processing of electronic parts with a side length of less than millimeter order and the pattern formation of nanometer order in semiconductor circuits are being carried out. In such microfabrication, there is a limit to handling by physical contact, so it may be difficult to apply the technique of Patent Document 3.
半導体回路のパターン形成においては、フォトマスクを用いた感光性樹脂への露光による微細パターン形成の技術が開発され、今日では広く普及している。特許文献４では、ポリシラザンと光酸発生剤を含む感光性組成物を用いて、基板上にパターンを形成する方法が報告されている。しかし、この感光性組成物から発生した酸の影響により、保護される電子部品や実装後の周囲部材が腐食される懸念がある。 In the pattern formation of semiconductor circuits, a technique for forming a fine pattern by exposing a photosensitive resin using a photomask has been developed and is widely used today. Patent Document 4 reports a method of forming a pattern on a substrate using a photosensitive composition containing polysilazane and a photoacid generator. However, the acid generated from the photosensitive composition may corrode protected electronic components and surrounding members after mounting.
特許文献２で述べられているようにガスバリアコーティングとしての用途ではペルヒドロポリシラザンを使用することが好ましい。特許文献５では、パターン形成に好適な変性ポリシルセスキアザンの構造が報告されているが、ペルヒドロポリシラザンを含む場合の最適な組成が検討されているとは言い難い。 It is preferred to use perhydropolysilazanes for gas barrier coating applications as described in US Pat. Although Patent Document 5 reports the structure of modified polysilsesquiazane suitable for pattern formation, it is difficult to say that the optimum composition when perhydropolysilazane is included has been investigated.
以上のことから、硬化時に酸を発生せず、光線照射を経る硬化膜のパターニング性に優れ、基材の所望の箇所および所望の形にて硬化膜を作製することができる技術の開発が求められている。 From the above, there is a demand for the development of a technology that does not generate acid during curing, has excellent patterning properties of a cured film that undergoes light irradiation, and can produce a cured film in a desired location and in a desired shape on a substrate. It is
本発明は、上記問題を解決するためになされたものであり、硬化時に酸を発生せず、光線照射を経る硬化膜のパターニング性に優れ、基材の所望の箇所および所望の形にて硬化膜を作製することができるポリシラザン含有組成物を提供することを目的とする。 The present invention was made to solve the above problems, does not generate acid during curing, has excellent patterning properties of a cured film that undergoes light irradiation, and cures at a desired location and in a desired form on a substrate. An object of the present invention is to provide a polysilazane-containing composition from which a film can be produced.
上記課題を解決するために、本発明では、
（Ａ－１）下記式（ａ－１）で示されるペルヒドロポリシラザン、
（Ｂ）有機溶剤、
を含むポリシラザン含有組成物であって、
前記（Ａ－１）成分の配合量が、前記（Ａ－１）成分と前記（Ａ－２）成分の合計１００質量部に対して、３０～９５質量部であり、
ゲルパーミエーションクロマトグラフィによって求められる、前記（Ａ－１）成分の重量平均分子量をｗ１、前記（Ａ－２）成分の重量平均分子量をｗ２としたとき、ｗ１＞２ｗ２、となるものであるポリシラザン含有組成物
を提供する。
In order to solve the above problems, in the present invention,
(A-1) a perhydropolysilazane represented by the following formula (a-1),
(B) an organic solvent,
A polysilazane-containing composition comprising
The blending amount of the component (A-1) is 30 to 95 parts by mass with respect to a total of 100 parts by mass of the component (A-1) and the component (A-2),
Where w 1 is the weight average molecular weight of the component (A-1) and w 2 is the weight average molecular weight of the component (A-2), w 1 >2w 2 as determined by gel permeation chromatography. A polysilazane-containing composition is provided.
このようなポリシラザン含有組成物であれば、硬化時に酸を発生せず、光線照射を経る硬化膜のパターニング性に優れ、基材の所望の箇所・所望の形にて硬化膜を作製することができるポリシラザン含有組成物となる。 With such a polysilazane-containing composition, no acid is generated during curing, the patterning of the cured film through irradiation with light is excellent, and a cured film can be produced in a desired location and in a desired shape on a substrate. It becomes a polysilazane-containing composition that can be obtained.
また、本発明では、前記（Ａ－２）成分は、前記式（ａ－２）のＲ1とＲ２のどちらか一方が水素原子であり、かつ、Ｒ３が水素原子である変性ポリシラザンであることが好ましい。 In the present invention, the component (A-2) is a modified polysilazane in which one of R 1 and R 2 in the formula (a-2) is a hydrogen atom and R 3 is a hydrogen atom. Preferably.
このようなポリシラザン含有組成物であれば、本発明の効果を向上させることができる。 With such a polysilazane-containing composition, the effects of the present invention can be improved.
また、本発明では、前記（Ｂ）成分がジ－ｎ－ブチルエーテルであることが好ましい。 Further, in the present invention, the component (B) is preferably di-n-butyl ether.
このようなポリシラザン含有組成物であれば、組成物の安定性とハンドリング性を向上させることができる。 Such a polysilazane-containing composition can improve the stability and handleability of the composition.
また、本発明では、前記ポリシラザン含有組成物は、２５℃における前記（Ｂ）成分１ｇへの溶解度が１ｍｇ以上である（Ｃ）光塩基発生剤をさらに含むものであることが好ましい。 In the present invention, the polysilazane-containing composition preferably further contains (C) a photobase generator having a solubility of 1 mg or more in 1 g of the component (B) at 25°C.
このようなポリシラザン含有組成物であれば、硬化時に酸が発生せず、透明な組成物溶液が得られ、（Ａ－１）成分および（Ａ－２）成分の硬化反応が促進され、硬化時の成分揮発による炉内や周辺基板の汚染や硬化物の膜減りを低減することができる。 With such a polysilazane-containing composition, no acid is generated during curing, a transparent composition solution can be obtained, and the curing reaction of the components (A-1) and (A-2) is accelerated. It is possible to reduce the contamination of the inside of the furnace and peripheral substrates and the reduction of the film of the cured product due to the volatilization of the components.
また、本発明では、前記（Ｃ）成分の配合量が、前記（Ａ－１）成分と前記（Ａ－２）成分の合計１００質量部に対して、２～１５質量部であることが好ましい。 Further, in the present invention, the amount of component (C) to be blended is preferably 2 to 15 parts by mass with respect to a total of 100 parts by mass of component (A-1) and component (A-2). .
このようなポリシラザン含有組成物であれば、本発明の効果を向上させることができる。 With such a polysilazane-containing composition, the effects of the present invention can be improved.
また、本発明では、前記（Ｃ）成分が下記式（ｃ－１）～（ｃ－４）から選ばれる少なくとも１種の光塩基発生剤であることが好ましい。
このようなポリシラザン含有組成物であれば、より確実に本発明の効果を向上させることができる。 With such a polysilazane-containing composition, the effects of the present invention can be improved more reliably.
また、本発明では、前記ポリシラザン含有組成物の硬化物である硬化膜を提供する。 The present invention also provides a cured film, which is a cured product of the polysilazane-containing composition.
このような硬化膜であれば、基材の所望の箇所に所望の形で緻密なガラス膜を提供することができる。 With such a cured film, it is possible to provide a dense glass film in a desired shape on a desired portion of the base material.
また、本発明では、基材と、該基材の表面に形成された硬化膜を含む物品を提供する。 The present invention also provides an article comprising a substrate and a cured film formed on the surface of the substrate.
このような物品であれば、基材の所望の箇所に所望の形で緻密なガラス膜が形成された物品を提供できる。 With such an article, it is possible to provide an article in which a dense glass film is formed in a desired shape on a desired portion of the base material.
また、本発明では、前記物品に含まれる前記硬化膜は、前記物品の一部分だけに形成されることが好ましい。 Moreover, in the present invention, it is preferable that the cured film contained in the article is formed only on a part of the article.
このような物品であれば、基材の所望の箇所に所望の形で緻密なガラス膜が形成された物品を提供できる。 With such an article, it is possible to provide an article in which a dense glass film is formed in a desired shape on a desired portion of the base material.
以上のように、本発明によれば、ペルヒドロポリシラザンと、好ましい構造を有する変性ポリシラザンを適切に組み合わせ、場合により光塩基発生剤を加えたポリシラザン含有組成物は、光線照射を含む工程を経て作製される硬化膜のパターニング性に優れ、基材の所望の箇所、所望の形にて硬化膜を作製することができる。さらに本発明であれば、光酸発生剤を含む必要がないので、硬化時に酸を発生させることがなく、周辺部材の腐食を抑制できる。 As described above, according to the present invention, a polysilazane-containing composition in which a perhydropolysilazane and a modified polysilazane having a preferred structure are appropriately combined, and optionally a photobase generator is added, is produced through a process including light irradiation. The resulting cured film has excellent patterning properties, and the cured film can be produced at a desired location and in a desired shape on the substrate. Furthermore, according to the present invention, since it is not necessary to contain a photoacid generator, no acid is generated during curing, and corrosion of peripheral members can be suppressed.
上述のように、パターニング性に優れる硬化膜を提供することができるポリシラザン含有組成物の開発が求められていた。
特に、上述のようなガラス質膜の特徴を最大限に発揮させるには、硬化時に酸を発生せず、光線照射を経る硬化膜のパターニング性に優れ、基材の所望の箇所および所望の形にて硬化膜を作製できる必要がある。そこで本発明者らは、ペルヒドロポリシラザンに、変性ポリシラザンおよび場合により光塩基発生剤を添加した配合組成を探索することに想到した。
As described above, there has been a demand for the development of a polysilazane-containing composition capable of providing a cured film with excellent patterning properties.
In particular, in order to maximize the characteristics of the glassy film as described above, it is necessary not to generate acid during curing, to have excellent patterning properties of the cured film through light irradiation, and to obtain a desired portion and desired shape of the substrate. It is necessary to be able to prepare a cured film at. Accordingly, the present inventors have conceived of searching for a compounding composition in which a modified polysilazane and optionally a photobase generator are added to perhydropolysilazane.
本発明者らは、上記課題について鋭意検討を重ねた結果、適切な構造を有するポリシラザンの組み合わせからなるポリシラザン含有組成物は、光照射によって活性化されることで未照射部位よりも熱硬化速度が向上し、パターニング性に優れることを見出し、本発明を完成させた。 The inventors of the present invention have extensively studied the above problems, and found that a polysilazane-containing composition composed of a combination of polysilazanes having an appropriate structure exhibits a thermosetting speed higher than that of an unirradiated portion when activated by light irradiation. The inventors have found that the patterning property is improved and the patterning property is excellent, and completed the present invention.
即ち、本発明は、
（Ａ－１）下記式（ａ－１）で示されるペルヒドロポリシラザン、
（Ｂ）有機溶剤、
を含むポリシラザン含有組成物であって、
前記（Ａ－１）成分の配合量が、前記（Ａ－１）成分と前記（Ａ－２）成分の合計１００質量部に対して、３０～９５質量部であり、
ゲルパーミエーションクロマトグラフィによって求められる、前記（Ａ－１）成分の重量平均分子量をｗ１、前記（Ａ－２）成分の重量平均分子量をｗ２としたとき、ｗ１＞２ｗ２、となるものであるポリシラザン含有組成物
である。
That is, the present invention
(A-1) a perhydropolysilazane represented by the following formula (a-1),
(B) an organic solvent,
A polysilazane-containing composition comprising
The blending amount of the component (A-1) is 30 to 95 parts by mass with respect to a total of 100 parts by mass of the component (A-1) and the component (A-2),
Where w 1 is the weight average molecular weight of the component (A-1) and w 2 is the weight average molecular weight of the component (A-2), w 1 >2w 2 as determined by gel permeation chromatography. It is a polysilazane-containing composition.
以下に本発明の実施の形態を詳細に説明するが、これは例示的に示されるもので、本発明はこれらに限定されず種々の変形が可能なことは言うまでもない。 Although the embodiments of the present invention will be described in detail below, they are shown as examples, and the present invention is not limited to these, and it goes without saying that various modifications are possible.
＜ポリシラザン含有組成物＞
＜（Ａ）ポリシラザン＞
本発明のポリシラザン含有組成物を構成する（Ａ）ポリシラザンは、硬化することによってガラス質の硬化膜を形成するものである。なお、本明細書におけるガラス質の定義は、Ｓｉ－Ｏ結合を有し、硬化すると流動せず固体状である状態である。
<Polysilazane-containing composition>
<(A) Polysilazane>
The (A) polysilazane constituting the polysilazane-containing composition of the present invention forms a vitreous cured film when cured. In this specification, the definition of vitreous is a state that has Si—O bonds and does not flow when hardened and is in a solid state.
本発明を構成する（Ａ）ポリシラザンは、（Ａ－１）ペルヒドロポリシラザン、（Ａ－２）変性ポリシラザンを含む。 (A) polysilazane constituting the present invention includes (A-1) perhydropolysilazane and (A-2) modified polysilazane.
本発明におけるポリシラザン含有組成物では、（Ａ－１）ペルヒドロポリシラザンの非常に高い硬化反応性を調節することによる優れたパターニング性の発現のために、（Ａ－１）成分に対して（Ａ－２）成分を添加した２種類以上の構造を持つポリシラザンを含む。 In the polysilazane-containing composition of the present invention, (A -2) Contains polysilazanes having two or more types of structures to which components are added.
また、（Ａ）ポリシラザン（（Ａ－１）成分と（Ａ－２）成分）は（Ｂ）成分である有機溶剤への溶解性や塗布時の作業性の観点から、重量平均分子量が１００～１，０００，０００であることが好ましく、３００～１００，０００であることがより好ましく、５００～５０，０００の範囲内であることがさらに好ましい。重量平均分子量が１００以上だと揮発性が低く、有機溶剤の揮発および硬化工程時にポリシラザンそのものが揮発することで塗膜の膜質が劣化する恐れがないため好ましく、１，０００，０００以下だと、有機溶剤に対する溶解性が高いため好ましい。 In addition, (A) polysilazane ((A-1) component and (A-2) component) has a weight-average molecular weight of 100 to 100 from the viewpoint of solubility in an organic solvent (component (B)) and workability during coating. It is preferably 1,000,000, more preferably 300 to 100,000, even more preferably in the range of 500 to 50,000. When the weight-average molecular weight is 100 or more, the volatility is low, and there is no fear that the polysilazane itself volatilizes during the volatilization of the organic solvent and the curing process, which may cause deterioration of the film quality of the coating film. It is preferred because of its high solubility in organic solvents.
なお、本明細書中で言及する重量平均分子量は、下記条件で測定したゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレンを標準物質として得られた値を指す。
［測定条件］
展開溶媒：テトラヒドロフラン（ＴＨＦ）
流量：０．３５ｍＬ／ｍｉｎ
検出器：示差屈折率検出器
カラム：ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＭＰ（ＨＺ）－Ｍ
ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ ＨＺ－Ｍ
（４．６ｍｍＩ．Ｄ．×１５ｃｍ，４μｍ×４）
（いずれも東ソー社製）
カラム温度：４０℃
試料注入量：２０μＬ（濃度０．５質量％のＴＨＦ溶液）
The weight average molecular weight referred to in this specification refers to a value obtained using polystyrene as a standard material by gel permeation chromatography (GPC) measured under the following conditions.
[Measurement condition]
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential refractive index detector Column: TSKguardcolumn SuperMP (HZ)-M
TSKgel Super Multipore HZ-M
(4.6 mm I.D.×15 cm, 4 μm×4)
(both manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5% by mass)
（Ａ）ポリシラザンのうち、（Ａ－１）成分のポリシラザンは、下記式（ａ－１）で示されるペルヒドロポリシラザンである。
（Ａ－１）成分
（Ａ－１）成分はペルヒドロポリシラザンであることから、（Ａ－２）成分よりも架橋密度が高く緻密なガラス膜を形成することから、本発明における硬化膜の物性を支配する主骨格を形成する。
(A-1) Component Since component (A-1) is perhydropolysilazane, it forms a dense glass film with a higher crosslinking density than component (A-2). form the main skeleton that governs
前記（Ａ－１）成分は、１種単独、もしくは同様のポリシラザン骨格を有する重量平均分子量が異なる２種以上の中から選定されたペルヒドロポリシラザン混合物から任意に選択して使用できる。 The component (A-1) can be arbitrarily selected from a single type or a perhydropolysilazane mixture selected from two or more types having the same polysilazane skeleton but different weight average molecular weights.
（Ａ－２）成分
（Ａ－２）成分は上記式（ａ－２）で示されるポリシラザンのうち、Ｒ１とＲ２が同時に水素原子でない変性ポリシラザンである。なお、本明細書における変性の定義は、上記式（ａ－２）の置換基が全て同時に水素原子ではなく、少なくとも１つは有機置換基であることである。
(A-2) Component (A-2) is a modified polysilazane in which both R 1 and R 2 are not hydrogen atoms among the polysilazanes represented by the above formula (a-2). The definition of modification in this specification is that all the substituents in formula (a-2) above are not hydrogen atoms at the same time, but at least one is an organic substituent.
上記式（ａ－２）中、Ｒ１、Ｒ２の前記脂肪族炭化水素基は、炭素数１～１０、好ましくは炭素数１～４であり、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基などのアルキル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基などのシクロアルキル基、ビニル基、アリル基、７－オクテニル基などのアルケニル基が挙げられ、中でもメチル基、ビニル基が好ましく、メチル基がより好ましい。 In the above formula (a-2), the aliphatic hydrocarbon groups of R 1 and R 2 have 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, alkyl group such as decyl group, cyclopentyl group, cyclohexyl group, norbornyl group , cycloalkyl groups such as adamantyl group, alkenyl groups such as vinyl group, allyl group and 7-octenyl group, among which methyl group and vinyl group are preferred, and methyl group is more preferred.
上記式（ａ－２）中、Ｒ１、Ｒ２の前記芳香族炭化水素基は、炭素数６～１２、好ましくは炭素数６～７であり、例えば、フェニル基、トリル基、キシリル基、ナフチル基などのアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基、ｐ－ビニルベンジルなどのアラルキル基などが挙げられ、中でもフェニル基が好ましい。 In the above formula (a-2), the aromatic hydrocarbon groups of R 1 and R 2 have 6 to 12 carbon atoms, preferably 6 to 7 carbon atoms, and examples thereof include phenyl, tolyl, xylyl, Examples include aryl groups such as naphthyl groups, benzyl groups, phenylethyl groups, phenylpropyl groups, and aralkyl groups such as p-vinylbenzyl groups, among which phenyl groups are preferred.
上記式（ａ－２）中、Ｒ１、Ｒ２の前記アルコキシ基は、炭素数１～１０、好ましくは炭素数１～４であり、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘキソキシ基、ヘプトキシ基、オクトキシ基、ノノキシ基、デコキシ基などが挙げられ、中でもメトキシ基、エトキシ基が好ましく、メトキシ基がより好ましい。 In the above formula (a-2), the alkoxy groups of R 1 and R 2 have 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, butoxy, pentoxy group, hexoxy group, heptoxy group, octoxy group, nonoxy group, decoxy group and the like, among which methoxy group and ethoxy group are preferred, and methoxy group is more preferred.
上記式（ａ－２）中、Ｒ3は水素原子またはメチル基であり、水素原子が好ましい。 In formula (a-2) above, R 3 is a hydrogen atom or a methyl group, preferably a hydrogen atom.
中でも（Ａ－２）成分は、上記式（ａ－２）のＲ1とＲ２のどちらか一方が水素原子であり、かつ、Ｒ３が水素原子である変性ポリシラザンであることが好ましい。 Among them, the component (A-2) is preferably a modified polysilazane in which one of R 1 and R 2 in the above formula (a-2) is a hydrogen atom and R 3 is a hydrogen atom.
（Ａ－２）成分は（Ａ－１）成分よりも立体障害が大きいこと等を理由として硬化反応速度が遅いことから、（Ａ－１）成分に（Ａ－２）成分を添加することで硬化反応速度を好適に調節することができる。 Component (A-2) has a slower curing reaction rate than component (A-1) due to factors such as greater steric hindrance. The curing reaction rate can be suitably adjusted.
上記の理由から前記（Ａ－１）成分の配合量は、前記（Ａ－１）成分と（Ａ－２）成分の合計１００質量部に対して、３０～９５質量部であり、５０～９０質量部であることがより好ましい。配合量が９５質量部よりも多いと、硬化反応速度が速すぎることで、パターニング時の仮硬化工程において露光部が十分に硬化するのみならず未露光部の硬化も進みすぎるために、未露光部を洗浄除去してパターンを現像することが困難になる。配合量が３０質量部よりも少ないと、硬化速度が遅すぎることで、短時間の仮硬化工程では露光部の仮硬化が満足に進行しない。そのために現像工程によって未露光部だけでなく露光部も洗浄されてしまい、硬化膜のパターンが崩れてしまう。 For the above reasons, the amount of the component (A-1) is 30 to 95 parts by mass and 50 to 90 parts by mass with respect to the total 100 parts by mass of the components (A-1) and (A-2). Parts by mass are more preferable. If the amount is more than 95 parts by mass, the curing reaction rate is too fast, and not only the exposed portion is sufficiently cured in the temporary curing step during patterning, but also the unexposed portion is cured too much. It becomes difficult to wash away the part and develop the pattern. If the blending amount is less than 30 parts by mass, the curing speed is too slow, and the temporary curing of the exposed areas does not proceed satisfactorily in a temporary curing step for a short period of time. Therefore, not only the unexposed area but also the exposed area is washed by the developing process, and the pattern of the cured film is destroyed.
本発明では、反応性の高い（Ａ－１）成分を用いるので、（Ａ－１）成分と（Ａ－２）成分の上記組成での組み合わせにより十分な硬化速度が得られる。従って、硬化反応を促進するために光酸発生剤を含む必要はない。 In the present invention, since highly reactive component (A-1) is used, a sufficient curing speed can be obtained by combining component (A-1) and component (A-2) in the above composition. Therefore, it is not necessary to include a photoacid generator to accelerate the curing reaction.
前記（Ａ－２）成分のポリシラザンは、１種単独、もしくは２種以上の中から選定されたポリシラザン混合物、あるいは２種以上のポリシラザン構造からなるポリシラザン共重合体から任意に選択して使用できる。 The polysilazane of the component (A-2) can be arbitrarily selected from polysilazane mixtures selected from one type, two or more types, or a polysilazane copolymer composed of two or more types of polysilazane structures.
前記（Ａ－１）成分で緻密なガラス質硬化膜を形成するが、その隙間に前記（Ａ－２）成分が入り込むことによって現像工程の後に精度の高いパターンを形成することができる。このことから、ゲルパーミエーションクロマトグラフィによって求められる、前記（Ａ－１）成分の重量平均分子量をｗ１、前記（Ａ－２）成分の重量平均分子量をｗ２としたとき、ｗ１＞２ｗ２であり、組成物への相溶性を考慮した場合、２００ｗ２＞ｗ１＞３ｗ２であることがより好ましく、１００ｗ２＞ｗ１＞４ｗ２であることがさらに好ましい。 The component (A-1) forms a dense glassy cured film, and the component (A-2) enters into the gaps between the components, so that a highly accurate pattern can be formed after the development step. From this, when the weight average molecular weight of the component (A-1) is w 1 and the weight average molecular weight of the component (A-2) is w 2 , w 1 >2w 2 as determined by gel permeation chromatography. , more preferably 200w 2 >w 1 >3w 2 and even more preferably 100w 2 >w 1 >4w 2 in consideration of compatibility with the composition.
＜（Ｂ）有機溶剤＞
本発明で用いる前記（Ａ）ポリシラザンは、塗布時の作業性や保存安定性を改善することを目的として、（Ｂ）有機溶剤で希釈して用いられる。前記有機溶剤としては、前記（Ａ－１）成分および前記（Ａ－２）成分を溶解する有機溶剤であれば特に限定されない。例えば、ｎ－ペンタン、イソペンタン、ｎ－ヘキサン、イソヘキサン、ｎ－ヘプタン、イソヘプタン、ｎ－オクタン、イソオクタン、ｎ－ノナン、イソノナン、ｎ－デカン、イソデカンなどの飽和脂肪族炭化水素、１－オクテン、１－ノネン、１－デセン、１－ドデセン、β－ミルセンなどの不飽和脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、エチルシクロヘキサン、デカヒドロナフタレンなどの飽和脂環式炭化水素、シクロヘキセンなどの不飽和脂環式炭化水素、ｐ－メンタン、ｄ－リモネン、ｌ－リモネン、ジペンテンなどのテルペン化合物、ベンゼン、トルエン、キシレン、エチルベンゼン、ジエチルベンゼン、トリメチルベンゼン、トリエチルベンゼン、テトラヒドロナフタレンなどの芳香族炭化水素、アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、ジ－ｎ－ブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノン、ダイアセトンアルコールなどのケトン化合物、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸イソアミル、アセト酢酸エチル、カプロン酸エチルなどのエステル化合物、ジエチルエーテル、ジ－ｎ－プロピルエーテル、ジ－ｎ－ブチルエーテル、ジ－ｎ－ペンチルエーテル、ジ－ｎ－ヘキシルエーテル、ｔｅｒｔ－ブチルメチルエーテルなどのアルキルエーテル化合物、アニソール、ジフェニルエーテルなどのアリールエーテル化合物、ビス（２－メトキシエチル）エーテル、ビス（２－エトキシエチル）エーテル、ビス（２－ブトキシエチル）エーテルなどのグリコールエーテル化合物などが挙げられる。
<(B) Organic solvent>
The (A) polysilazane used in the present invention is used after being diluted with (B) an organic solvent for the purpose of improving workability during coating and storage stability. The organic solvent is not particularly limited as long as it dissolves the components (A-1) and (A-2). For example, saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, 1-octene, 1 -unsaturated aliphatic hydrocarbons such as nonene, 1-decene, 1-dodecene and β-myrcene, saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, decahydronaphthalene, cyclohexene terpene compounds such as p-menthane, d-limonene, l-limonene and dipentene; aromatics such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene and tetrahydronaphthalene Ketone compounds such as hydrocarbons, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, n-propyl acetate, isopropyl acetate, n-butyl acetate, Ester compounds such as isobutyl acetate, isoamyl acetate, ethyl acetoacetate, ethyl caproate, diethyl ether, di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether, di-n-hexyl ether, tert- Alkyl ether compounds such as butyl methyl ether, aryl ether compounds such as anisole and diphenyl ether, glycol ether compounds such as bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether, bis(2-butoxyethyl) ether, etc. is mentioned.
塗布時の作業性やポリシラザンの保存安定性の観点から、希釈比率は（Ａ－１）成分と（Ａ－２）成分のポリシラザンの合計１００質量部に対して（Ｂ）成分が１００～１００，０００質量部の範囲内であることが好ましく、４００～１０，０００質量部であることがより好ましい。 From the viewpoint of workability during application and storage stability of polysilazane, the dilution ratio is 100 to 100 parts by weight of component (B) per 100 parts by mass of polysilazane of components (A-1) and (A-2). It is preferably in the range of 000 parts by mass, more preferably 400 to 10,000 parts by mass.
上述したように、塗布時の作業性や、比較的吸湿しにくく保存安定性を向上できるという観点から、（Ｂ）成分としてはジ－ｎ－ブチルエーテルが好ましい。 As described above, di-n-butyl ether is preferable as the component (B) from the viewpoints of workability during application, relatively low moisture absorption, and improved storage stability.
本発明のポリシラザン含有組成物に含まれる水分量は５００ｐｐｍ以下であることが好ましく、３００ｐｐｍ以下であることがより好ましい。水分量が５００ｐｐｍ以下であれば、ポリシラザンと含有水分とが反応しないため、発熱したり、水素ガスやアンモニアガスが発生したりする恐れがなく、また、増粘、ゲル化などを引き起こす恐れもないので好ましい。従って、（Ｂ）成分中の水分量は、本発明のポリシラザン含有組成物に含まれる水分量が上記範囲となるように制御されていることが好ましい。 The amount of water contained in the polysilazane-containing composition of the present invention is preferably 500 ppm or less, more preferably 300 ppm or less. If the water content is 500 ppm or less, the polysilazane does not react with the contained water, so there is no risk of heat generation, generation of hydrogen gas or ammonia gas, and thickening or gelation. Therefore, it is preferable. Therefore, the water content in component (B) is preferably controlled so that the water content in the polysilazane-containing composition of the present invention falls within the above range.
また、本発明のポリシラザン含有組成物は光酸発生剤を使用しないため、硬化時に酸を発生せず、電子部品の保護剤として使用する際に、保護される電子部品や実装後の周囲部材の腐食を回避することができる。 In addition, since the polysilazane-containing composition of the present invention does not use a photoacid generator, it does not generate acid during curing, and when used as a protective agent for electronic parts, it can be used to protect electronic parts and surrounding members after mounting. Corrosion can be avoided.
＜（Ｃ）光塩基発生剤＞
（Ｃ）成分の光塩基発生剤は、特定波長の光線を吸収することで有機塩基を放出する化合物である。光吸収によって発生した有機塩基によって、（Ａ－１）成分および（Ａ－２）成分の硬化反応が促進され、硬化時に（Ａ－１）成分および（Ａ－２）成分の一部が揮発することによる、硬化反応炉内や周辺基板の汚染や硬化物の膜減りを低減することができる。また、本発明のポリシラザン含有組成物に（Ｃ）成分の光塩基発生剤を使用すれば、本発明のポリシラザン含有組成物の硬化時に酸を発生しないため、電子部品の保護剤として使用する際に、保護される電子部品や実装後の周囲部材の腐食を回避することができる。
<(C) Photobase generator>
The photobase generator of component (C) is a compound that releases an organic base upon absorption of light of a specific wavelength. The organic base generated by light absorption accelerates the curing reaction of components (A-1) and (A-2), and part of components (A-1) and (A-2) volatilizes during curing. As a result, it is possible to reduce the contamination of the inside of the curing reaction furnace and peripheral substrates and the decrease in the film thickness of the cured product. In addition, when the polysilazane-containing composition of the present invention uses the photobase generator as the component (C), no acid is generated when the polysilazane-containing composition of the present invention is cured. , it is possible to avoid corrosion of the protected electronic components and surrounding members after mounting.
また、（Ｃ）成分は、特定波長の光線を吸収することに伴う電子励起を引き金として有機塩基を放出することから、照射される光線の波長は２００～１，０００ｎｍの範囲内であることが好ましい。さらに、４００～７００ｎｍの波長の光線を用いて（Ｃ）成分を電子励起する場合、（Ｃ）成分はその時に照射される光線の波長の吸収を持つため、４００～７００ｎｍは可視領域の波長域であることを勘案すると、硬化膜が着色する恐れがある。このことから、照射される光線の波長は２００～４００ｎｍまたは７００～１０００ｎｍであることがより好ましく、２００～４００ｎｍであることがさらに好ましい。 In addition, since component (C) releases an organic base triggered by electronic excitation accompanying absorption of light of a specific wavelength, the wavelength of the light to be irradiated should be in the range of 200 to 1,000 nm. preferable. Furthermore, when the component (C) is electronically excited using a light beam with a wavelength of 400 to 700 nm, the component (C) absorbs the wavelength of the light beam irradiated at that time, so the wavelength range of 400 to 700 nm is in the visible region. Considering that, the cured film may be colored. For this reason, the wavelength of the irradiated light is more preferably 200 to 400 nm or 700 to 1000 nm, and even more preferably 200 to 400 nm.
（Ｃ）成分が（Ａ）成分と（Ｂ）成分を含む溶液に溶解していない場合、基材への塗工時に（Ｃ）成分の存在箇所に偏りが生じ、最終的に硬化膜の膜質が不均一になることが懸念される。（Ｃ）成分は、本発明における組成物への溶解性の観点から、２５℃における（Ｂ）成分の有機溶剤１ｇへの溶解度が１ｍｇ以上であることが好ましい。 If the component (C) is not dissolved in the solution containing the components (A) and (B), the presence of the component (C) is unevenly distributed during application to the substrate, and the final cured film quality There is concern that the From the viewpoint of solubility in the composition of the present invention, component (C) preferably has a solubility of 1 mg or more in 1 g of the organic solvent of component (B) at 25°C.
（Ｃ）成分は光線吸収によって塩基を放出する化合物であればその構造は特に制限がないが、上述したような（Ｂ）成分への溶解性の観点から、非イオン性化合物であることが好ましい。 The structure of component (C) is not particularly limited as long as it is a compound that releases a base upon absorption of light, but from the viewpoint of solubility in component (B) as described above, it is preferably a nonionic compound. .
（Ｃ）成分は、光吸収による塩基発生効率に優れる観点から、下記式（ｃ－１）アントリル基含有カルバメート化合物、（ｃ－２）アントラキニル基含有カルバメート化合物、（ｃ－３）ニトロフェニル基含有カルバメート化合物または（ｃ－４）ヒドロキシフェニル基含有アミド化合物から選ばれる構造であることがより好ましい。 Component (C) has the following formulas (c-1) an anthryl group-containing carbamate compound, (c-2) anthraquinyl group-containing carbamate compound, and (c-3) a nitrophenyl group-containing compound, from the viewpoint of excellent base generation efficiency by light absorption. A structure selected from carbamate compounds and (c-4) hydroxyphenyl group-containing amide compounds is more preferred.
中でも、３６５ｎｍにおける光吸収強度が大きいことから、（ｃ－１）アントリル基含有カルバメート化合物がより好ましい。 Among them, the (c-1) anthryl group-containing carbamate compound is more preferable because of its high light absorption intensity at 365 nm.
上記式（ｃ－１）、（ｃ－２）、（ｃ－３）または（ｃ－４）中のＲ４で表されるアミノ基として、例えば、メチルアミノ基、ジメチルアミノ基、エチルアミノ基、ジエチルアミノ基、ｎ－プロピルアミノ基、イソプロピルアミノ基、ジ－ｎ－プロピルアミノ基、ジイソプロピルアミノ基、ｎ－ブチルアミノ基、ｓｅｃ－ブチルアミノ基、イソブチルアミノ基、ｔｅｒｔ－ブチルアミノ基、ジ－ｎ－ブチルアミノ基、ジ－ｓｅｃ－ブチルアミノ基、ジイソブチルアミノ基、ジ－ｔｅｒｔ－ブチルアミノ基、ｎ－ペンチルアミノ基、２－ペンチルアミノ基、３－ペンチルアミノ基、イソペンチルアミノ基、ネオペンチルアミノ基、ジ－ｎ－ペンチルアミノ基、ジイソペンチルアミノ基、ジネオペンチルアミノ基、ｎ－ヘキシルアミノ基、ジ－ｎ－ヘキシルアミノ基、ｎ－ヘプチルアミノ基、ジ－ｎ－ヘプチルアミノ基、ｎ－オクチルアミノ基、ジ－ｎ－オクチルアミノ基、ｎ－ノニルアミノ基、ジ－ｎ－ノニルアミノ基、ｎ－デシルアミノ基、ジ－ｎ－デシルアミノ基、シクロヘキシルアミノ基、ジシクロヘキシルアミノ基、ビシクロ［２．２．１］ヘプチルアミノ基、ビシクロ［２．２．２］ヘキシルアミノ基などのアルキルアミノ基、ピペリジニル基、ヒドロキシピペリジニル基、メタクリロイルオキシピペリジニル基、イミダゾール基、メチルイミダゾール基、エチルイミダゾール基、ベンゾイミダゾール基などの環状アミノ基などが挙げられ、中でも、ジエチルアミノ基またはジシクロヘキシル基が好ましい。 Examples of the amino group represented by R 4 in the above formula (c-1), (c-2), (c-3) or (c-4) include methylamino group, dimethylamino group and ethylamino group. , diethylamino group, n-propylamino group, isopropylamino group, di-n-propylamino group, diisopropylamino group, n-butylamino group, sec-butylamino group, isobutylamino group, tert-butylamino group, di- n-butylamino group, di-sec-butylamino group, diisobutylamino group, di-tert-butylamino group, n-pentylamino group, 2-pentylamino group, 3-pentylamino group, isopentylamino group, neo pentylamino group, di-n-pentylamino group, diisopentylamino group, dineopentylamino group, n-hexylamino group, di-n-hexylamino group, n-heptylamino group, di-n-heptylamino group, n-octylamino group, di-n-octylamino group, n-nonylamino group, di-n-nonylamino group, n-decylamino group, di-n-decylamino group, cyclohexylamino group, dicyclohexylamino group, bicyclo[ 2.2.1]heptylamino group, alkylamino group such as bicyclo[2.2.2]hexylamino group, piperidinyl group, hydroxypiperidinyl group, methacryloyloxypiperidinyl group, imidazole group, methylimidazole group, Cyclic amino groups such as an ethylimidazole group and a benzimidazole group are included, and among them, a diethylamino group or a dicyclohexyl group is preferable.
（Ｃ）成分の配合量は、前記（Ａ－１）成分と（Ａ－２）成分の合計１００質量部に対して、２～１５質量部であることが好ましく、５～１０質量部であることがより好ましい。 The amount of component (C) to be blended is preferably 2 to 15 parts by mass, more preferably 5 to 10 parts by mass, with respect to the total of 100 parts by mass of components (A-1) and (A-2). is more preferable.
（Ｃ）成分はそれぞれ単独で用いてもよく、２種以上を併用して用いてもよい。 Component (C) may be used alone, or two or more of them may be used in combination.
＜ポリシラザン含有組成物の製造方法＞
本発明のポリシラザン含有組成物は、その製造方法に制限はなく、例えば、（Ａ－１）成分、（Ａ－２）成分、および（Ｂ）成分を混合した溶液に、場合により（Ｃ）成分を加えて、超音波を当てながら撹拌することで得ることができる。
<Method for Producing Polysilazane-Containing Composition>
The polysilazane-containing composition of the present invention can be produced by any method without limitation. can be obtained by adding and stirring while applying ultrasonic waves.
その他、本発明の組成物には目的に応じ、これら以外の添加剤を添加することができる。 In addition, additives other than these can be added to the composition of the present invention depending on the purpose.
＜硬化膜＞
本発明の硬化膜は、ポリシラザン含有組成物の硬化物である硬化膜である。
このような硬化膜であれば、基材の所望の箇所に所望の形で緻密なガラス膜を提供することができる。
<Cured film>
The cured film of the present invention is a cured film that is a cured product of a polysilazane-containing composition.
With such a cured film, it is possible to provide a dense glass film in a desired shape on a desired portion of the base material.
＜硬化膜を含む物品＞
本発明の物品は、基材と、該基材の表面に形成されたポリシラザン含有組成物の硬化物である硬化膜を含む物品である。
<Article containing cured film>
The article of the present invention is an article comprising a substrate and a cured film, which is a cured product of a polysilazane-containing composition formed on the surface of the substrate.
また、本発明の物品は、基材と、該基材の表面に形成されたポリシラザン含有組成物の硬化物である硬化膜を含む物品の一部分だけに形成された硬化膜を含む物品である。
このような物品であれば、基材の所望の箇所に所望の形で緻密なガラス膜が形成された物品を提供できる。
Further, the article of the present invention is an article comprising a substrate and a cured film formed only on a part of the article comprising a cured film of a cured product of the polysilazane-containing composition formed on the surface of the substrate.
With such an article, it is possible to provide an article in which a dense glass film is formed in a desired shape on a desired portion of the base material.
＜パターニングされた硬化膜の形成方法＞
本発明のポリシラザン含有組成物を用いてパターニングされた硬化膜を形成する方法としては、特に制限はなく、例えば、下記の工程を含む：
（ｉ）前記ポリシラザン含有組成物を基材上に塗布してポリシラザン含有塗膜を形成させる塗布工程、
（ｉｉ）ポリシラザン含有塗膜を像様露光する露光工程、
（ｉｉｉ）ポリシラザン含有塗膜の露光部をゲル化させる仮硬化工程、
（ｉｖ）ポリシラザン含有塗膜の未露光部分を除去して現像する現像工程、
（ｖ）現像された露光部を硬化させる本硬化工程。
<Method for forming patterned cured film>
The method for forming a patterned cured film using the polysilazane-containing composition of the present invention is not particularly limited, and includes, for example, the following steps:
(i) a coating step of coating the polysilazane-containing composition on a substrate to form a polysilazane-containing coating film;
(ii) an exposure step of imagewise exposing the polysilazane-containing coating film;
(iii) a temporary curing step of gelling the exposed portion of the polysilazane-containing coating film;
(iv) a developing step of removing and developing the unexposed portion of the polysilazane-containing coating;
(v) A main curing step of curing the developed exposed area.
（ｉ）塗布工程
基材に対して本発明のポリシラザン含有組成物を塗布する方法としては、例えば、ダイレクトグラビアコータ、チャンバードクターコータ、オフセットグラビアコータ、リバースキスコータ、リバースロールコータ、スロットダイ、リップコータ、エアードクターコータ、一本ロールキスコータ、正回転ロールコータ、ブレードコータ、含浸コータ、ＭＢコータ、ＭＢリバースコータ、ナイフコータ、バーコータなどのロールコート法やスピンコート法、ディスペンス法、ディップ法、スプレー法、転写法、スリットコート法などが挙げられる。
(i) Coating process Examples of methods for coating the polysilazane-containing composition of the present invention on a substrate include a direct gravure coater, a chamber doctor coater, an offset gravure coater, a reverse kiss coater, a reverse roll coater, a slot die, and a lip coater. , air doctor coater, single roll kiss coater, forward rotation roll coater, blade coater, impregnation coater, MB coater, MB reverse coater, knife coater, bar coater, spin coat method, dispense method, dip method, spray method , a transfer method, a slit coating method, and the like.
塗膜の厚さは硬化膜の使用目的などにより異なるが、硬化膜厚で１０～１００，０００ｎｍであることが好ましく、５０～１０，０００ｎｍであることがより好ましい。 The thickness of the coating film varies depending on the intended use of the cured film, but the cured film thickness is preferably 10 to 100,000 nm, more preferably 50 to 10,000 nm.
ポリシラザン含有組成物を塗布する前に基材に対して表面改質処理を行っても良い。表面改質処理は主に基材とポリシラザンとの密着性を向上させる目的で行われ、基材表面に付着した有機物の分解除去や、基材表面に化学反応点を形成することで実現される。表面改質処理方法としては例えば、アルゴンプラズマ処理、酸素プラズマ処理、オゾン処理、ＵＶ照射処理、キセノンエキシマ光照射処理などが挙げられ、基材の種類などにより使い分けられる。 Before applying the polysilazane-containing composition, the substrate may be subjected to a surface modification treatment. Surface modification treatment is mainly performed for the purpose of improving the adhesion between the base material and polysilazane, and is realized by decomposing and removing organic matter adhering to the base material surface and by forming chemical reaction points on the base material surface. . Examples of the surface modification treatment method include argon plasma treatment, oxygen plasma treatment, ozone treatment, UV irradiation treatment, xenon excimer light irradiation treatment, etc., which are selected according to the type of substrate.
（ｉｉ）露光工程
ポリシラザン含有塗膜に光線を照射することで像様するための光線の光源としては、例えば、メタルハライドランプ、ＬＥＤ、高圧水銀灯、低圧水銀灯、エキシマレーザー、電子線などが挙げられる。照射エネルギーは、５～５０００ｍＪ／ｃｍ２が好ましく、１０～２０００ｍＪ／ｃｍ２がより好ましく、５０～１０００ｍＪ／ｃｍ２がさらに好ましい。照射エネルギーが５ｍＪ／ｃｍ２より小さいと、当該ポリシラザン含有塗膜が十分に活性化されず、露光部と未露光部で硬化速度に差が生じないために、現像後にパターンが形成されない恐れがある。照射エネルギーが５０００ｍＪ／ｃｍ２より大きいと、露光過多となり、ハレーションが発生する恐れがある。
(ii) Exposure step Examples of the light source for forming an image by irradiating the polysilazane-containing coating film with light include metal halide lamps, LEDs, high-pressure mercury lamps, low-pressure mercury lamps, excimer lasers, and electron beams. The irradiation energy is preferably 5 to 5000 mJ/cm 2 , more preferably 10 to 2000 mJ/cm 2 and even more preferably 50 to 1000 mJ/cm 2 . If the irradiation energy is less than 5 mJ/cm 2 , the polysilazane-containing coating film is not sufficiently activated, and there is no difference in the curing speed between the exposed and unexposed areas, which may result in failure to form a pattern after development. . If the irradiation energy is higher than 5000 mJ/cm 2 , the exposure may be excessive and halation may occur.
当該ポリシラザン含有塗膜は、空気中の水分と反応することで硬化反応が進行するために、硬化反応が活性化された露光部のみならず、未露光部のポリシラザン含有塗膜も経時で硬化が進行する。その理由から、精度の高いパターンを得るためには、露光工程は短時間で行う必要があり、５分以内が好ましく、１分以内がより好ましい。 The polysilazane-containing coating film undergoes a curing reaction by reacting with moisture in the air. Therefore, not only the exposed areas where the curing reaction is activated, but also the unexposed areas of the polysilazane-containing coating film are hardened over time. proceed. For this reason, in order to obtain a highly accurate pattern, the exposure process must be performed in a short time, preferably within 5 minutes, more preferably within 1 minute.
像様露光するために、塗膜上で露光部と未露光部を区別する方法としては、例えば、フォトマスクの利用、光線の走査露光などが挙げられ、様々な光源への汎用性の高さから、フォトマスクの利用が好ましい。 For imagewise exposure, methods for distinguishing the exposed and unexposed areas on the coating film include, for example, the use of photomasks, scanning exposure of light, etc. High versatility for various light sources Therefore, the use of a photomask is preferred.
（ｉｉｉ）仮硬化工程
仮硬化工程は、光線照射によって加熱硬化反応に対して活性化された露光部を、次工程の現像工程で除去されない程度まで硬化反応を進行させる目的で行う。
(iii) Temporary Curing Step The temporary curing step is carried out for the purpose of allowing the curing reaction to proceed to such an extent that the exposed portions that have been activated against the heat curing reaction by irradiation with light are not removed in the development step in the next step.
仮硬化の方法は硬化反応が進行する方法であれば特に制約はないが、露光部は加熱硬化に対する活性が高まっていることから、基材を変質させない温度範囲での加熱処理を行ってもよい。 The temporary curing method is not particularly limited as long as the curing reaction proceeds, but since the exposed part has increased activity for heat curing, heat treatment may be performed in a temperature range that does not deteriorate the base material. .
前記仮硬化温度は２０～２００℃で行うことが好ましく、５０～１５０℃がより好ましく、８０～１２０℃で行うことがさらに好ましい。仮硬化温度が２０℃以上であれば、露光により熱硬化に対する活性が高まっている露光部と未露光部の熱硬化速度に有意差が得られ、現像によるパターンの形成が可能になる。２００℃以下であれば、未露光部がすぐに加熱硬化しないため、現像によるパターンの形成ができる。 The temporary curing temperature is preferably 20 to 200°C, more preferably 50 to 150°C, and even more preferably 80 to 120°C. If the temporary curing temperature is 20° C. or higher, a significant difference is obtained in the heat curing rate between the exposed portion and the unexposed portion, where the activity for heat curing is increased by exposure, and a pattern can be formed by development. If the temperature is 200° C. or less, the unexposed portion is not immediately cured by heating, so that a pattern can be formed by development.
上記の理由により、本発明で用いる（Ｂ）有機溶剤の沸点は、大気圧下（１０１３ｈＰａ）において２０～２００℃であることが好ましく、２５～１５０℃であることがより好ましい。この範囲内であれば、有機溶剤が仮硬化膜内に残存することもなく、パターンの精度に悪影響を与えない。 For the reasons described above, the boiling point of the (B) organic solvent used in the present invention is preferably 20 to 200° C., more preferably 25 to 150° C. under atmospheric pressure (1013 hPa). Within this range, the organic solvent does not remain in the temporarily cured film and does not adversely affect pattern accuracy.
当該ポリシラザン含有塗膜は、（Ａ－１）ペルヒドロポリシラザンを含むことから、空気中の水分と反応することで硬化反応が進行するために、露光部だけでなく未露光部のポリシラザン塗膜も仮硬化工程で部分的に硬化が進行しうる。その理由から、精度の高いパターンを得るためには、仮硬化は短時間で行う必要があり、３０分以内が好ましく、１５分以内がさらに好ましい。 Since the polysilazane-containing coating contains (A-1) perhydropolysilazane, the curing reaction proceeds by reacting with moisture in the air, so not only the exposed areas but also the unexposed areas of the polysilazane coating Curing may proceed partially in the temporary curing step. For this reason, in order to obtain a highly accurate pattern, the temporary curing should be performed in a short time, preferably within 30 minutes, more preferably within 15 minutes.
前記露光工程において使用される光源によっては、光源が発熱することで、露光時に基材および塗膜が加熱される場合がある。この場合は、露光と同時に熱による仮硬化も進行するため、必ずしも仮硬化工程を行う必要はない。 Depending on the light source used in the exposure step, heat generated by the light source may heat the substrate and the coating during exposure. In this case, temporary curing by heat proceeds simultaneously with exposure, so the temporary curing step does not necessarily need to be performed.
（ｉｖ）現像工程
未露光部は上記仮硬化工程において硬化が進行しない、あるいは露光部と比較して硬化度が極めて低い。このことから、現像工程により未露光部の塗膜を除去し露光部のみを残存させることでネガ型のパターニングをすることができる。
(iv) Developing step The unexposed area does not cure in the temporary curing step, or has a very low degree of curing compared to the exposed area. Therefore, negative patterning can be performed by removing the coating film in the unexposed areas and leaving only the exposed areas in the developing process.
現像方法は、後述する洗浄剤と塗膜を接触させ、未露光部の塗膜を除去する方法であれば特に制限がないが、例えば、塗膜を浸漬させ、必要に応じて洗浄剤の液を撹拌する、あるいは洗浄剤を塗膜にかけ流してリンスする方法が挙げられる。 The developing method is not particularly limited as long as it is a method of bringing the coating film into contact with the cleaning agent described below and removing the coating film in the unexposed areas. Alternatively, a method of rinsing by pouring a detergent over the coating film may be mentioned.
洗浄剤は、未露光部のポリシラザンを溶解しやすく、露光部の仮硬化した塗膜を溶解しないものであれば特に制限がないが、例えば、ｎ－ペンタン、イソペンタン、ｎ－ヘキサン、イソヘキサン、ｎ－ヘプタン、イソヘプタン、ｎ－オクタン、イソオクタン、ｎ－ノナン、イソノナン、ｎ－デカン、イソデカンなどの飽和脂肪族炭化水素、１－オクテン、１－ノネン、１－デセン、１－ドデセン、β－ミルセンなどの不飽和脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、エチルシクロヘキサン、デカヒドロナフタレンなどの飽和脂環式炭化水素、シクロヘキセンなどの不飽和脂環式炭化水素、ｐ－メンタン、ｄ－リモネン、ｌ－リモネン、ジペンテンなどのテルペン化合物、ベンゼン、トルエン、キシレン、エチルベンゼン、ジエチルベンゼン、トリメチルベンゼン、トリエチルベンゼン、テトラヒドロナフタレンなどの芳香族炭化水素、アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、ジ－ｎ－ブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノン、ダイアセトンアルコールなどのケトン化合物、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸イソアミル、アセト酢酸エチル、カプロン酸エチルなどのエステル化合物、ジエチルエーテル、ジ－ｎ－プロピルエーテル、ジ－ｎ－ブチルエーテル、ジ－ｎ－ペンチルエーテル、ジ－ｎ－ヘキシルエーテル、ｔｅｒｔ－ブチルメチルエーテルなどのアルキルエーテル化合物、アニソール、ジフェニルエーテルなどのアリールエーテル化合物、ビス（２－メトキシエチル）エーテル、ビス（２－エトキシエチル）エーテル、ビス（２－ブトキシエチル）エーテルなどのグリコールエーテル化合物が挙げられ、トルエン、キシレン、またはジ－ｎ－ブチルエーテルが好ましい。 The cleaning agent is not particularly limited as long as it easily dissolves the polysilazane in the unexposed area and does not dissolve the temporarily cured coating film in the exposed area. - Saturated aliphatic hydrocarbons such as heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, and isodecane, 1-octene, 1-nonene, 1-decene, 1-dodecene, β-myrcene, etc. saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, decahydronaphthalene, unsaturated alicyclic hydrocarbons such as cyclohexene, p-menthane, d - terpene compounds such as limonene, l-limonene and dipentene, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, tetrahydronaphthalene, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, di - Ketone compounds such as n-butyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, ethyl acetoacetate, ethyl caproate, etc. Ester compounds, alkyl ether compounds such as diethyl ether, di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether, di-n-hexyl ether and tert-butyl methyl ether, aryls such as anisole and diphenyl ether Ether compounds, glycol ether compounds such as bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether, bis(2-butoxyethyl) ether, and toluene, xylene, or di-n-butyl ether are preferred. .
現像工程において、洗浄剤に含まれる水分により、未露光部のポリシラザンがゲル化することを防ぐために、洗浄剤中の水分量は５００ｐｐｍ以下であることが好ましく、３００ｐｐｍ以下であることがより好ましい。 In order to prevent polysilazane in unexposed areas from gelling due to moisture contained in the detergent in the development step, the water content in the detergent is preferably 500 ppm or less, more preferably 300 ppm or less.
（ｖ）本硬化工程
本硬化のための硬化処理は硬化反応が進行する方法であれば特に制約はないが、基材を変質させない方法より適宜選択される必要がある。硬化処理方法としては例えば、加熱処理、水蒸気加熱処理、大気圧プラズマ処理、低温プラズマ処理、ＵＶ処理、エキシマ光処理などが挙げられる。
(v) Main curing step The curing treatment for the main curing is not particularly limited as long as it is a method that allows the curing reaction to proceed, but it is necessary to appropriately select a method that does not alter the properties of the base material. Examples of curing treatment methods include heat treatment, steam heat treatment, atmospheric pressure plasma treatment, low temperature plasma treatment, UV treatment, and excimer light treatment.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記実施例によって限定されるものではない。なお、重量平均分子量は、上記条件でＧＰＣにより測定した値である。 EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The weight average molecular weight is a value measured by GPC under the above conditions.
（Ａ）ポリシラザン
（合成例）
（Ａ－１）ペルヒドロポリシラザンの合成
窒素雰囲気下で脱水ピリジン（４，５００ｇ）を－１０℃まで冷却し、ジクロロシラン（６４Ｌ）を吹き込んだ後－１０℃で１時間撹拌した。アンモニア（２１６Ｌ）を吹き込み、２５℃に戻しながら１２時間撹拌した。生じた固体をろ別し、ろ液にジ－ｎ－ブチルエーテル（１，０００ｇ）を加えた。液中のピリジンをジ－ｎ－ブチルエーテルと共沸させながら減圧留去し、留出液が４，５００ｇに達した時点で、ジ－ｎ－ブチルエーテル（１，０００ｇ）をさらに加えた。続けてピリジンをジ－ｎ－ブチルエーテルと共沸させながら減圧留去することでペルヒドロポリシラザンのジ－ｎ－ブチルエーテル溶液を得た。なお、このペルヒドロポリシラザンの重量平均分子量は６，１００であった。その後、溶液全体を１００質量部としたときにポリシラザンが２０質量部となるようにジ－ｎ－ブチルエーテルを添加した。以下の実施例、比較例では、この溶液を（Ａ－１）成分としてペルヒドロポリシラザン２０質量部、（Ｂ）成分としてジ－ｎ－ブチルエーテル８０質量部を含有するものとみなして使用した。
(A) Polysilazane (synthesis example)
(A-1) Synthesis of perhydropolysilazane
Dehydrated pyridine (4,500 g) was cooled to -10°C under a nitrogen atmosphere, dichlorosilane (64 L) was blown thereinto, and the mixture was stirred at -10°C for 1 hour. Ammonia (216 L) was blown in, and the mixture was stirred for 12 hours while returning to 25°C. The resulting solid was filtered off, and di-n-butyl ether (1,000 g) was added to the filtrate. Pyridine in the liquid was distilled off under reduced pressure while azeotroping di-n-butyl ether, and di-n-butyl ether (1,000 g) was further added when the distillate reached 4,500 g. Subsequently, pyridine and di-n-butyl ether were azeotropically distilled under reduced pressure to obtain a di-n-butyl ether solution of perhydropolysilazane. The weight average molecular weight of this perhydropolysilazane was 6,100. Thereafter, di-n-butyl ether was added so that the amount of polysilazane was 20 parts by mass when the total solution was 100 parts by mass. In the following examples and comparative examples, this solution was used as containing 20 parts by mass of perhydropolysilazane as component (A-1) and 80 parts by mass of di-n-butyl ether as component (B).
（Ａ－１）′ペルヒドロポリシラザン（低分子量）の合成
窒素雰囲気下で脱水ピリジン（４，５００ｇ）を－１０℃まで冷却し、ジクロロシラン（１６Ｌ）を吹き込んだ後－１０℃で１時間撹拌した。アンモニア（５４Ｌ）を吹き込み、２５℃に戻しながら１２時間撹拌した。生じた固体をろ別し、ろ液にジ－ｎ－ブチルエーテル（１，０００ｇ）を加えた。液中のピリジンをジ－ｎ－ブチルエーテルと共沸させながら減圧留去し、留出液が４，５００ｇに達した時点で、ジ－ｎ－ブチルエーテル（１，０００ｇ）をさらに加えた。続けてピリジンをジ－ｎ－ブチルエーテルと共沸させながら減圧留去することでペルヒドロポリシラザンのジ－ｎ－ブチルエーテル溶液を得た。なお、このペルヒドロポリシラザンの重量平均分子量は１，８００であった。その後、溶液全体を１００質量部としたときにポリシラザンが２０質量部となるようにジ－ｎ－ブチルエーテルを添加した。以下の実施例、比較例では、この溶液を（Ａ－１）′成分としてペルヒドロポリシラザン２０質量部、（Ｂ）成分としてジ－ｎ－ブチルエーテル８０質量部を含有するものとみなして使用した。
(A-1)'Synthesis of perhydropolysilazane (low molecular weight) Dehydrated pyridine (4,500 g) was cooled to -10°C under a nitrogen atmosphere, dichlorosilane (16 L) was blown in, and then stirred at -10°C for 1 hour. bottom. Ammonia (54 L) was blown in, and the mixture was stirred for 12 hours while returning to 25°C. The resulting solid was filtered off, and di-n-butyl ether (1,000 g) was added to the filtrate. Pyridine in the liquid was distilled off under reduced pressure while azeotroping di-n-butyl ether, and di-n-butyl ether (1,000 g) was further added when the distillate reached 4,500 g. Subsequently, pyridine and di-n-butyl ether were azeotropically distilled under reduced pressure to obtain a di-n-butyl ether solution of perhydropolysilazane. The weight average molecular weight of this perhydropolysilazane was 1,800. Thereafter, di-n-butyl ether was added so that the amount of polysilazane was 20 parts by mass when the total solution was 100 parts by mass. In the following examples and comparative examples, this solution was used assuming that it contained 20 parts by mass of perhydropolysilazane as component (A-1)' and 80 parts by mass of di-n-butyl ether as component (B).
（Ａ－２）メチルヒドロポリシラザンの合成
窒素雰囲気下で脱水ピリジン（４，０００ｇ）を－１０℃まで冷却し、ジクロロメチルシラン（８７３ｇ）を滴下し、－１０℃で１時間撹拌した。アンモニア（５１０Ｌ）を吹き込み、２５℃に戻しながら１２時間撹拌した。ろ過し、ろ液にジ－ｎ－ブチルエーテル（１，０００ｇ）を加えた。液中のピリジンをジ－ｎ－ブチルエーテルと共沸させながら減圧留去し、留出液が４，０００ｇに達した時点で、ジ－ｎ－ブチルエーテル（１，０００ｇ）をさらに加えた。続けてピリジンをジ－ｎ－ブチルエーテルと共沸させながら減圧留去することでメチルヒドロポリシラザンのジ－ｎ－ブチルエーテル溶液を得た。なお、このメチルヒドロポリシラザンの重量平均分子量は１，２００であった。その後、溶液全体を１００質量部としたときにポリシラザンが２０質量部となるようにジ－ｎ－ブチルエーテルを添加した。以下の実施例、比較例では、この溶液を（Ａ－２）成分としメチルヒドロポリシラザン２０質量部、（Ｂ）成分としてジ－ｎ－ブチルエーテル８０質量部を含有するものとみなして使用した。
(A-2) Synthesis of methylhydropolysilazane Dehydrated pyridine (4,000 g) was cooled to -10°C under a nitrogen atmosphere, dichloromethylsilane (873 g) was added dropwise, and the mixture was stirred at -10°C for 1 hour. Ammonia (510 L) was blown in, and the mixture was stirred for 12 hours while returning to 25°C. After filtration, di-n-butyl ether (1,000 g) was added to the filtrate. Pyridine in the liquid was distilled off under reduced pressure while azeotroping di-n-butyl ether, and di-n-butyl ether (1,000 g) was further added when the distillate reached 4,000 g. Subsequently, pyridine and di-n-butyl ether were azeotropically distilled under reduced pressure to obtain a di-n-butyl ether solution of methylhydropolysilazane. The weight average molecular weight of this methylhydropolysilazane was 1,200. Thereafter, di-n-butyl ether was added so that the amount of polysilazane was 20 parts by mass when the total solution was 100 parts by mass. In the following examples and comparative examples, this solution was assumed to contain 20 parts by mass of methylhydropolysilazane as component (A-2) and 80 parts by mass of di-n-butyl ether as component (B).
（Ｂ）有機溶剤
（Ｂ－１）ジ－ｎ－ブチルエーテル（関東化学製）
(B) organic solvent (B-1) di-n-butyl ether (manufactured by Kanto Kagaku)
（Ｃ）光塩基発生剤
（Ｃ－１）Ｎ，Ｎ－ジシクロヘキシルカルバミン酸９－アントリルメチル（富士フィルム和光純薬製）
（Ｃ－２）Ｎ，Ｎ－ジエチルカルバミン酸９－アントリルメチル（富士フィルム和光純薬製）
(C) Photobase generator (C-1) 9-anthrylmethyl N,N-dicyclohexylcarbamate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
(C-2) 9-anthrylmethyl N,N-diethylcarbamate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
なお、（Ｃ－１）成分、（Ｃ－２）成分のいずれも、２５℃における（Ｂ）ジ－ｎ－ブチルエーテル１ｇへの溶解度が１ｍｇ以上であった。 Both of component (C-1) and component (C-2) had a solubility of 1 mg or more in 1 g of (B) di-n-butyl ether at 25°C.
［実施例１～１４、比較例１～３］
（１）溶液外観の評価
表１、２に示す割合で、前記合成例で調製した（Ａ－１）成分、（Ａ－１）’成分、（Ａ－２）成分、および（Ｂ）成分を混合した溶液に、場合により（Ｃ）成分を加えて、超音波洗浄機を用いて超音波（３８ｋＨｚ）を当てながら５分間撹拌することでポリシラザン含有組成物の調製を行った。得られたポリシラザン含有組成物の外観を目視にて観察したとき、透明だったものは〇、沈殿が生じていたものは×を表１、２に示した。
[Examples 1 to 14, Comparative Examples 1 to 3]
(1) Evaluation of solution appearance In proportions shown in Tables 1 and 2, the components (A-1), (A-1)', (A-2), and (B) prepared in the Synthesis Example were added. The component (C) was optionally added to the mixed solution, and the mixture was stirred for 5 minutes while applying ultrasonic waves (38 kHz) using an ultrasonic cleaner to prepare a polysilazane-containing composition. When the appearance of the resulting polysilazane-containing composition was visually observed, ◯ indicates that the composition was transparent, and X indicates that there was precipitation.
（２）パターニング性の評価
（ｉ）塗布工程
（１）の評価が○だったポリシラザン含有組成物を、Ｓｉウエハーにスピンコート（回転速度１０００ｒｐｍ、回転時間３０秒）した。
(2) Evaluation of patterning properties
(i) The polysilazane-containing composition evaluated as ◯ in the coating step (1) was spin-coated onto a Si wafer (rotation speed: 1000 rpm, rotation time: 30 seconds).
（ｉｉ）露光工程
上記工程（ｉ）で作製した塗膜上にフォトマスク（露光部は線幅１００μｍかつ線間隔５００μｍ）を載せ、メタルハライドランプ（アイグラフィックス製）を用いて、波長３６５ｎｍの光線について照射エネルギーが８００ｍＪ／ｃｍ２となるように光線照射した。
(ii) Exposure step A photomask (exposed portion has a line width of 100 μm and a line spacing of 500 μm) is placed on the coating film prepared in the above step (i), and a metal halide lamp (manufactured by Eye Graphics) is used to emit light with a wavelength of 365 nm. was irradiated so that the irradiation energy was 800 mJ/cm 2 .
（ｉｉｉ）仮硬化工程
上記工程（ｉｉ）で露光した塗膜について、フォトマスクを除去した後、１００℃の乾燥機で１０分間加熱することで、塗膜を仮硬化した。
(iii) Temporary curing step After removing the photomask, the coating film exposed in the above step (ii) was heated in a drier at 100°C for 10 minutes to temporarily cure the coating film.
（ｉｖ）現像工程
上記工程（ｉｉｉ）で加熱した塗膜を、トルエン２０ｍＬを用いてリンスした。
(iv) Development step The coated film heated in the above step (iii) was rinsed with 20 mL of toluene.
（ｖ）本硬化工程
上記工程（ｉｖ）で現像した仮硬化膜を、１５０℃の乾燥機で３時間加熱することでＳｉウエハー上にパターニングされた硬化膜を作製した。
(v) Main curing step The temporary cured film developed in the above step (iv) was heated in a dryer at 150°C for 3 hours to prepare a patterned cured film on a Si wafer.
上記（ｉ）～（ｖ）の工程を経て作製した、硬化膜のパターンをデジタルマイクロスコープ（ＫＥＹＥＮＣＥ製ＶＨＸ－７０００）を用いて観察し、線幅１００μｍかつ線間隔５００μｍのパターンが作製できたものは〇、未露光部が洗浄しきれていない、または、露光部が過剰に溶解したためにパターンが途切れたものは×を表１、２に示した。 The pattern of the cured film produced through the above steps (i) to (v) was observed using a digital microscope (VHX-7000 manufactured by KEYENCE), and a pattern with a line width of 100 μm and a line spacing of 500 μm was produced. Tables 1 and 2 show ◯ when the unexposed area was not completely washed or the pattern was interrupted due to excessive dissolution of the exposed area.
（３）膜厚の評価
顕微分光膜厚計（大塚電子製ＯＰＴＭ－Ａ１）を用いて、上記（２）の評価にて作製したパターン膜の膜厚を測定し、その値を表１、２に示した。
(3) Evaluation of film thickness Using a microscopic spectroscopic film thickness meter (Otsuka Electronics OPTM-A1), the film thickness of the pattern film prepared in the evaluation of (2) above was measured, and the values are shown in Tables 1 and 2. It was shown to.
実施例１～５は（Ｃ）成分を含まないものの、パターニング性は良好であり、膜厚も十分であった。実施例１～１４の中で、（Ａ－１）成分と（Ａ－２）成分の配合量がそれぞれ同じでも（Ｃ）成分を含有している実施例６～１４（例えば、実施例１と実施例６を比較）は、有機塩基によって露光部の塗膜の硬化が促進されたために、現像時の硬化物の膜減りが低減され、得られたパターンの膜厚が大きくなった。また、（Ｃ）成分を含まない実施例１～５は当然に酸を発生せず、（Ｃ）成分を含む実施例６～１４は酸を発生しない光塩基発生剤を使用したため、実施例１～１４において、硬化時に酸が発生することはない。 Although Examples 1 to 5 did not contain the component (C), the patterning property was good and the film thickness was sufficient. Among Examples 1 to 14, Examples 6 to 14 (for example, Example 1 and In comparison with Example 6), since the curing of the coating film in the exposed area was accelerated by the organic base, the film loss of the cured product during development was reduced, and the film thickness of the resulting pattern was increased. In addition, Examples 1 to 5 containing no component (C) naturally did not generate acid, and Examples 6 to 14 containing component (C) used photobase generators that did not generate acid. In ~14, no acid is generated during curing.
一方、比較例１および２は、本発明における（Ａ－１）成分と（Ａ－２）成分の合計に対する（Ａ－１）成分の配合量が本発明の範囲を逸脱しているために、硬化膜のパターニングができなかった。比較例２は実施例１～１４と比較して、（Ａ－１）成分と（Ａ－２）成分の合計に対する（Ａ－１）成分の配合量が本発明の範囲より少ないために、塗膜の硬化が遅く、加熱時の成分揮発量と現像時の塗膜溶解量が多かった。その結果、硬化膜の膜厚が小さくなった。比較例３は実施例１～１４と比較して、ｗ1＞２ｗ2を満たしていないために、現像工程時に溶出する（Ａ－１）成分が増加した。その結果、硬化膜の膜厚が小さくなった。 On the other hand, in Comparative Examples 1 and 2, since the blending amount of component (A-1) with respect to the sum of component (A-1) and component (A-2) in the present invention is outside the scope of the present invention, The cured film could not be patterned. In Comparative Example 2, compared with Examples 1 to 14, the amount of component (A-1) with respect to the total of components (A-1) and (A-2) is less than the range of the present invention. Curing of the film was slow, and the amount of components volatilized during heating and the amount of coating dissolved during development were large. As a result, the film thickness of the cured film was reduced. Compared to Examples 1 to 14, Comparative Example 3 did not satisfy w 1 >2w 2 , so the component (A-1) eluted during the development step increased. As a result, the film thickness of the cured film was reduced.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 In addition, this invention is not limited to the said embodiment. The above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of
［産業上の利用可能性］
本発明のポリシラザン含有組成物は、光線照射を含む工程を経て作製される硬化膜のパターニング性に優れることから、基材上の所望の微細箇所上にガラス質硬化膜を形成できる。これを利用して、例えば、微小な電子部品の電気的、力学的性能を損なうことなく、長期使用時の信頼性を向上させる保護コーティングとして有用である。
[Industrial applicability]
The polysilazane-containing composition of the present invention is excellent in patterning properties of a cured film produced through a process including irradiation with light, so that a vitreous cured film can be formed on desired minute locations on a substrate. Utilizing this, for example, it is useful as a protective coating that improves reliability in long-term use without impairing the electrical and mechanical performance of minute electronic parts.
Claims (9)
（Ｂ）有機溶剤、
を含むポリシラザン含有組成物であって、
前記（Ａ－１）成分の配合量が、前記（Ａ－１）成分と前記（Ａ－２）成分の合計１００質量部に対して、３０～９５質量部であり、
ゲルパーミエーションクロマトグラフィによって求められる、前記（Ａ－１）成分の重量平均分子量をｗ１、前記（Ａ－２）成分の重量平均分子量をｗ２としたとき、ｗ１＞２ｗ２、
となるものであることを特徴とするポリシラザン含有組成物。 (A-1) a perhydropolysilazane represented by the following formula (a-1),
(B) an organic solvent,
A polysilazane-containing composition comprising
The blending amount of the component (A-1) is 30 to 95 parts by mass with respect to a total of 100 parts by mass of the component (A-1) and the component (A-2),
Where w 1 is the weight average molecular weight of component (A-1) and w 2 is the weight average molecular weight of component (A-2), w 1 >2w 2 , determined by gel permeation chromatography.
A polysilazane-containing composition characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022004341A JP2023103684A (en) | 2022-01-14 | 2022-01-14 | Polysilazane-containing composition, cured film, and article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022004341A JP2023103684A (en) | 2022-01-14 | 2022-01-14 | Polysilazane-containing composition, cured film, and article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2023103684A true JP2023103684A (en) | 2023-07-27 |
Family
ID=87378474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022004341A Pending JP2023103684A (en) | 2022-01-14 | 2022-01-14 | Polysilazane-containing composition, cured film, and article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2023103684A (en) |
-
2022
- 2022-01-14 JP JP2022004341A patent/JP2023103684A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS63502780A (en) | Method for developing poly(methacrylic anhydride) resist | |
| US20090181224A1 (en) | Negative-type photosensitive resin composition, pattern forming method and electronic parts | |
| JP5644339B2 (en) | Resist underlayer film forming composition, resist underlayer film and pattern forming method | |
| WO2006006581A1 (en) | Photosensitive insulating resin composition, cured product thereof and use thereof | |
| KR102395936B1 (en) | Silicon-rich silsesquioxane resin | |
| JP5109471B2 (en) | Negative photosensitive resin composition, pattern manufacturing method, and electronic component | |
| JP2024032869A (en) | Method for manufacturing cured film and use of the same | |
| JP7183939B2 (en) | Polysiloxane skeleton-containing polymer, photosensitive resin composition, pattern forming method, and method for manufacturing optical semiconductor element | |
| TW201944175A (en) | Negative photosensitive resin composition and method for producing cured relief pattern capable of obtaining a relatively high imidization rate and chemical resistance in low-temperature curing | |
| TW201816516A (en) | Negative-type photosensitive resin composition and use thereof | |
| JP7147500B2 (en) | Photosensitive resin composition, pattern forming method, and antireflection film | |
| JP2023103684A (en) | Polysilazane-containing composition, cured film, and article | |
| JPH08160623A (en) | Positivee type resist material | |
| JP3414708B2 (en) | Method of forming patterned polysilazane film | |
| TW201321907A (en) | Method for treating resist pattern and method for producing resist pattern using thereof, and composition for forming cover layer used in the same | |
| TW200404049A (en) | Photosensitive composition for interlayer insulating film and forming method of patterned interlayer insulating film | |
| KR100455652B1 (en) | A positive photoresist composition and a method for preparing photoresist layer using the same | |
| TWI813852B (en) | Photocurable resin composition, film containing the composition, cured material obtained by curing the composition or the film, wiring structure, electronic component and semiconductor device | |
| EP3656803B1 (en) | Polysiloxane skeleton polymer, photosensitive resin composition, pattern forming process, and fabrication of opto-semiconductor device | |
| JPH08160621A (en) | Positive type resist material | |
| TW202010772A (en) | Photosensitive resin composition and pattern forming process | |
| JP3856237B1 (en) | Silicon-containing photosensitive composition, method for producing thin film pattern using the same, protective film for electronic device | |
| JP6838369B2 (en) | Negative photosensitive resin composition, curing pattern manufacturing method, cured product and electronic device | |
| JPH04212160A (en) | Photosensitive resin composition | |
| JP7440224B2 (en) | Positive photosensitive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20231221 |