JPS62178562A - Production of 1,2-quinonediazide compound - Google Patents
Production of 1,2-quinonediazide compoundInfo
- Publication number
- JPS62178562A JPS62178562A JP1689286A JP1689286A JPS62178562A JP S62178562 A JPS62178562 A JP S62178562A JP 1689286 A JP1689286 A JP 1689286A JP 1689286 A JP1689286 A JP 1689286A JP S62178562 A JPS62178562 A JP S62178562A
- Authority
- JP
- Japan
- Prior art keywords
- agent
- compound
- acid chloride
- acid
- quinone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 238000005917 acylation reaction Methods 0.000 claims abstract description 10
- 238000005694 sulfonylation reaction Methods 0.000 claims abstract description 9
- 230000010933 acylation Effects 0.000 claims abstract description 8
- 230000006103 sulfonylation Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 16
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 12
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 58
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 230000005855 radiation Effects 0.000 abstract description 7
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 abstract description 3
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012346 acetyl chloride Substances 0.000 abstract 1
- -1 quinonediazide compound Chemical class 0.000 description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 239000002245 particle Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 28
- 239000011342 resin composition Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 229940071221 dihydroxybenzoate Drugs 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 229940079877 pyrogallol Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 2
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 2
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- QHJGJOBIIBEJNN-UHFFFAOYSA-N 2-amino-7-methyl-1,5-dihydropteridine-4,6-dione Chemical compound N1C(N)=NC(=O)C2=C1N=C(C)C(=O)N2 QHJGJOBIIBEJNN-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- RTIXKCRFFJGDFG-UHFFFAOYSA-N chrysin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=CC=C1 RTIXKCRFFJGDFG-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- ZOEBOKASEORHKI-UHFFFAOYSA-N ethyl 3-chloro-2-methyl-3-oxopropanoate Chemical compound CCOC(=O)C(C)C(Cl)=O ZOEBOKASEORHKI-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- SFLOGVVDXPCWGR-UHFFFAOYSA-N leucopterin (keto form) Chemical compound N1C(=O)C(=O)NC2=C1C(=O)N=C(N)N2 SFLOGVVDXPCWGR-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- MBDIPBHBEVOYQB-UHFFFAOYSA-N nigerone Chemical compound O1C(C)=CC(=O)C2=C1C(C1=C3C(C(C=C(C)O3)=O)=C(O)C3=C(OC)C=C(C=C31)OC)=C1C=C(OC)C=C(OC)C1=C2O MBDIPBHBEVOYQB-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000007965 rubber solvent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- YTMCUIACOKRXQA-UHFFFAOYSA-N (2-aminoacetyl) 2-aminoacetate Chemical class NCC(=O)OC(=O)CN YTMCUIACOKRXQA-UHFFFAOYSA-N 0.000 description 1
- GRTWTVFDPBKQNU-MQQKCMAXSA-N (2e,4e)-hexa-2,4-dienoyl chloride Chemical compound C\C=C\C=C\C(Cl)=O GRTWTVFDPBKQNU-MQQKCMAXSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- FTVWIRXFELQLPI-ZDUSSCGKSA-N (S)-naringenin Chemical compound C1=CC(O)=CC=C1[C@H]1OC2=CC(O)=CC(O)=C2C(=O)C1 FTVWIRXFELQLPI-ZDUSSCGKSA-N 0.000 description 1
- XZTTZOAHFOFHRJ-HWKANZROSA-N (e)-2-ethylbut-2-enoyl chloride Chemical compound CC\C(=C/C)C(Cl)=O XZTTZOAHFOFHRJ-HWKANZROSA-N 0.000 description 1
- RJUIDDKTATZJFE-NSCUHMNNSA-N (e)-but-2-enoyl chloride Chemical compound C\C=C\C(Cl)=O RJUIDDKTATZJFE-NSCUHMNNSA-N 0.000 description 1
- OTTYFDRFBJPGRW-ONEGZZNKSA-N (e)-pent-2-enoyl chloride Chemical compound CC\C=C\C(Cl)=O OTTYFDRFBJPGRW-ONEGZZNKSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- TUNLYEHIVPWOHK-ARJAWSKDSA-N (z)-2-methylbut-2-enoyl chloride Chemical compound C\C=C(\C)C(Cl)=O TUNLYEHIVPWOHK-ARJAWSKDSA-N 0.000 description 1
- SIYWFCCUJXQAPG-UHFFFAOYSA-N 1,3-bis(2,4-dihydroxyphenyl)propane-1,3-dione Chemical compound OC1=CC(O)=CC=C1C(=O)CC(=O)C1=CC=C(O)C=C1O SIYWFCCUJXQAPG-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical class C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- UKDZROJJLPDLDO-UHFFFAOYSA-N 10h-pyrido[3,2-b][1,4]benzothiazine Chemical class C1=CN=C2NC3=CC=CC=C3SC2=C1 UKDZROJJLPDLDO-UHFFFAOYSA-N 0.000 description 1
- KGWYICAEPBCRBL-UHFFFAOYSA-N 1h-indene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C=CC2=C1 KGWYICAEPBCRBL-UHFFFAOYSA-N 0.000 description 1
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
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- 229940117954 naringenin Drugs 0.000 description 1
- WGEYAGZBLYNDFV-UHFFFAOYSA-N naringenin Natural products C1(=O)C2=C(O)C=C(O)C=C2OC(C1)C1=CC=C(CC1)O WGEYAGZBLYNDFV-UHFFFAOYSA-N 0.000 description 1
- 235000007625 naringenin Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- JKSIUSSQWDHHKM-UHFFFAOYSA-N penta-2,4-dienoyl chloride Chemical compound ClC(=O)C=CC=C JKSIUSSQWDHHKM-UHFFFAOYSA-N 0.000 description 1
- PWQOZRPSDQKNPW-UHFFFAOYSA-N pentane-1-sulfonyl chloride Chemical compound CCCCCS(Cl)(=O)=O PWQOZRPSDQKNPW-UHFFFAOYSA-N 0.000 description 1
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- HBZMQFJTPHSKNH-UHFFFAOYSA-N phenyl 3,4,5-trihydroxybenzoate Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C=CC=CC=2)=C1 HBZMQFJTPHSKNH-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- GZYRNGLILQCDRQ-UHFFFAOYSA-N prop-1-ene-1-sulfonyl chloride Chemical compound CC=CS(Cl)(=O)=O GZYRNGLILQCDRQ-UHFFFAOYSA-N 0.000 description 1
- VWQXLMJSFGLQIT-UHFFFAOYSA-N prop-2-enoyl bromide Chemical compound BrC(=O)C=C VWQXLMJSFGLQIT-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KPBSJEBFALFJTO-UHFFFAOYSA-N propane-1-sulfonyl chloride Chemical compound CCCS(Cl)(=O)=O KPBSJEBFALFJTO-UHFFFAOYSA-N 0.000 description 1
- RIBFXMJCUYXJDZ-UHFFFAOYSA-N propanoyl bromide Chemical compound CCC(Br)=O RIBFXMJCUYXJDZ-UHFFFAOYSA-N 0.000 description 1
- BXOLUNAZMVQZQN-UHFFFAOYSA-N propyl 2,3,4-trihydroxybenzoate Chemical compound CCCOC(=O)C1=CC=C(O)C(O)=C1O BXOLUNAZMVQZQN-UHFFFAOYSA-N 0.000 description 1
- QQKDTTWZXHEGAQ-UHFFFAOYSA-N propyl carbonochloridate Chemical compound CCCOC(Cl)=O QQKDTTWZXHEGAQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 235000005875 quercetin Nutrition 0.000 description 1
- 229960001285 quercetin Drugs 0.000 description 1
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 235000005493 rutin Nutrition 0.000 description 1
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 description 1
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 description 1
- 229960004555 rutoside Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Pyrane Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は1.2−キノンジアジド化合物の製造方法に関
し、さらに詳しくは1.2−キノンジアジド化合物とア
ルカリ可溶性樹脂とからなる、紫外線、遠紫外線、X線
、電子線、分子線、γ線、シンクロトロン放射線、プロ
トンビーム等の放射線に感応するポジ型レジストとして
好適な感放射線性樹脂組成物に使用されるのに適した特
定の1゜2−キノンジアジド化合物の製造方法に関する
。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a 1,2-quinonediazide compound, and more specifically, a method for producing a 1,2-quinonediazide compound and an alkali-soluble resin. A specific 1°2- The present invention relates to a method for producing a quinonediazide compound.
(従来の技術)
従来、集積回路を作製するために使用されるレジストと
しては、環化ゴムにビスアジド化合物を配合したネガ型
レジストと、アルカリ可溶性樹脂に1,2−キノンジア
ジド化合物を配合したポジ型レジストとが知られている
。ネガ型レジストは、紫外線照射によりビスアジド化合
物が窒素を脱離してナイトレンとなり、環化ゴムを三次
元架橋するため、環化ゴムの溶剤からなる現像液に対す
る紫外線照射部分と紫外線未照射部分の溶解性に差が生
じ、これによってバターニングされるが、架橋とはいっ
ても紫外線照射部分が完全に硬化するわけではないので
、環化ゴムの溶剤からなる現像液中でのレジストパター
ンの膨潤が大きく、レジストパターンの解像度が悪いと
いう欠点がある。(Prior art) Conventionally, resists used to fabricate integrated circuits include a negative resist made by blending a bisazide compound with cyclized rubber, and a positive resist made by blending a 1,2-quinonediazide compound into an alkali-soluble resin. It is known as resist. In negative resists, the bisazide compound desorbs nitrogen when exposed to ultraviolet rays and becomes nitrene, which three-dimensionally crosslinks the cyclized rubber. Therefore, the solubility of the ultraviolet irradiated areas and the non-UV irradiated areas in a developing solution consisting of a cyclized rubber solvent is important. This causes a difference in patterning, but even though it is crosslinked, the UV irradiated area is not completely cured, so the resist pattern swells significantly in a developer made of a cyclized rubber solvent. The drawback is that the resolution of the resist pattern is poor.
一方、ポジ型レジストは、アルカリ可溶性樹脂にアルカ
リ不溶性の1.2−キノンジアジド化合物を配合するた
め、アルカリ性水溶液からなる現像液に熔解しにくく、
はとんど膨潤もしないため、紫外線照射部分の1,2−
キノンジアジド化合物がインデンカルボン酸に変化し、
アルカリ性水溶液からなる現像液で現像されても、レジ
ストパターンとなる紫外線未照射部分の変化が極端に少
な(、パターンマスクのパターンに忠実で、かつ高い解
像度のレジストパターンが得られる。そこで、集積回路
の高集積度化が要求される近年は、このような解像度の
優れたポジ型レジストが多用されている。On the other hand, positive resists contain an alkali-insoluble 1,2-quinonediazide compound in an alkali-soluble resin, so they are difficult to dissolve in a developer consisting of an alkaline aqueous solution.
Because it hardly swells, the 1,2-
Quinonediazide compound changes to indene carboxylic acid,
Even when developed with a developer consisting of an alkaline aqueous solution, there is extremely little change in the unirradiated portions of the resist pattern that are not irradiated with ultraviolet rays (a resist pattern that is faithful to the pattern of the pattern mask and has high resolution can be obtained. In recent years, with the demand for higher integration, such positive resists with excellent resolution have come into widespread use.
しかしアルカリ可溶性樹脂と1.2−キノンジアジド化
合物を溶剤に溶解させてなるポジ型レジストを、例えば
孔径0.2μmのフィルタで濾過したのち保存してお(
と、異物が生成し、異物の生成したポジ型レジストをさ
らに長期にわたって保存すると、やがては沈殿物の発生
を見るに到る場合がある。このようなポジ型レジスト中
で発生する異物は粒径が0.5μm以上のものもある。However, a positive resist made by dissolving an alkali-soluble resin and a 1,2-quinonediazide compound in a solvent can be stored after being filtered, for example, through a filter with a pore size of 0.2 μm.
If the positive resist containing the foreign particles is stored for a longer period of time, the formation of precipitates may eventually occur. Some of the foreign particles generated in such a positive resist have a particle size of 0.5 μm or more.
このように大きい異物を含有するポジ型レジストを用い
てレジストパターンをシリコンウェーハ上に形成すると
、現像によりレジストが除去される部分に異物が残るた
め、解像度が低下し、さらに集積回路作製時の歩留りが
悪化する原因となる。When a resist pattern is formed on a silicon wafer using a positive resist that contains such large foreign particles, the foreign particles remain in the areas where the resist is removed during development, resulting in a decrease in resolution and a reduction in yield when manufacturing integrated circuits. causes deterioration.
(発明が解決しようとする問題点)
本発明の目的は、前記のようにアルカリ可溶性樹脂と1
.2−キノンジアジド化合物を溶剤に溶解させることに
より調製されるポジ型レジストとして好適な感放射線性
樹脂組成物(以下、単に「樹脂組成物」と称する)の溶
液中の異物の発生の問題点を解決し、レジストパターン
形成の際の解像性および集積回路作製時の歩留りを向上
させることができる1、2−キノンジアジド化合物の製
造方法を提供することにある。(Problems to be Solved by the Invention) The object of the present invention is to combine an alkali-soluble resin and a
.. Solving the problem of foreign matter occurring in a solution of a radiation-sensitive resin composition (hereinafter simply referred to as "resin composition") suitable for a positive resist prepared by dissolving a 2-quinonediazide compound in a solvent. Another object of the present invention is to provide a method for producing a 1,2-quinonediazide compound that can improve the resolution during resist pattern formation and the yield during integrated circuit production.
(問題点を解決するための手段)
本発明は、(1)(a)ポリヒドロキシ化合物の水酸基
の一部をアシル化剤および/またはスルホニル化剤と反
応させてアシル化および/またはスルホニル化した後、
さらにポリヒドロキシ化合物の残りの水酸基の一部また
は全部を1.2−キノンジアジド化剤と反応させて1.
2−キノンジアジド化するか、
(b)ポリヒドロキシ化合物の水酸基の一部または全部
にアシル化剤および/またはスルホニル化剤と1.2−
キノンジアジド化剤とを、反応させてアシル化および/
またはスルホニル化と同時に1.2−キノンジアジド化
するか、または(c)ポリヒドロキシ化合物の水酸基の
一部を1゜2−キノンジアジド化剤と反応させて1.2
−キノンジアジド化した後、さらにポリヒドロキシ化合
物の残りの水酸基の一部または全部をアシル化剤および
/またはスルホニル化剤と反応させてアシル化および/
またはスルホニル化する工程を含み、かつ、アシル化剤
、スルホニル化剤および1゜2−キノンジアジド化剤の
総使用量をポリヒドロキシ化合物の水酸基1グラム当量
に対して0.3モル以上とし、アシル化剤および/また
はスルホニル化剤〔A〕と1.2−キノンジアジド化剤
〔Q〕との使用割合を〔A〕 / 〔Q〕 =0.01
10.99〜0.710.3〔モル比〕とすることを特
徴とする1、2−キノンジアジド化合物の製造方法を提
供するものである。(Means for Solving the Problems) The present invention provides (1) (a) a part of the hydroxyl group of the polyhydroxy compound is acylated and/or sulfonylated by reacting with an acylating agent and/or a sulfonylating agent; rear,
Further, part or all of the remaining hydroxyl groups of the polyhydroxy compound are reacted with a 1.2-quinone diazidating agent to 1.
2-quinone diazidation, or (b) some or all of the hydroxyl groups of the polyhydroxy compound are treated with an acylating agent and/or a sulfonylating agent and 1.2-
acylation and/or reaction with a quinone diazidating agent.
Alternatively, 1.2-quinone diazidation is performed simultaneously with sulfonylation, or (c) a part of the hydroxyl group of the polyhydroxy compound is reacted with a 1.2-quinone diazidating agent to give 1.2-quinone diazidation.
- After the quinone diazidation, some or all of the remaining hydroxyl groups of the polyhydroxy compound are further reacted with an acylating agent and/or a sulfonylating agent to acylate and/or
or sulfonylation step, and the total amount of the acylating agent, sulfonylating agent, and 1゜2-quinone diazidating agent is 0.3 mol or more per 1 gram equivalent of hydroxyl group of the polyhydroxy compound, and the acylating The ratio of the agent and/or sulfonylating agent [A] and the 1,2-quinonediazide agent [Q] is [A] / [Q] = 0.01.
The present invention provides a method for producing a 1,2-quinonediazide compound, characterized in that the molar ratio is 10.99 to 0.710.3.
本発明で使用されるポリヒドロキシ化合物は、少なくと
も分子中に水酸基を2個以上含有するも−のであり、具
体的にはレゾルシノール、ピロガロール、フロログルシ
ノール等のポリヒドロキシベンゼンH12,4−ジヒド
ロキシフェニルプロピルケトン、2.4−ジヒドロキシ
フェニル−n −へキシルケトン、2.3.4−)ジヒ
ドロキシフェニル−n−へキシルケトン等のポリヒドロ
キシフェニルアルキルケトン類、2,4−ジヒドロキシ
ベンゾフェノン、2.3.4−)ジヒドロキシベンゾフ
ェノン、2,4.6−)リヒドロキシベンゾフエノン、
2.4.2’、4’−テトラヒドロキシベンゾフェノン
、2,3.4.4’−テトラヒドロキシベンゾフェノン
、2,3,4.2’。The polyhydroxy compound used in the present invention contains at least two or more hydroxyl groups in the molecule, and specifically includes polyhydroxybenzene H12,4-dihydroxyphenylpropyl such as resorcinol, pyrogallol, and phloroglucinol. Ketones, polyhydroxyphenylalkyl ketones such as 2.4-dihydroxyphenyl-n-hexylketone, 2.3.4-) dihydroxyphenyl-n-hexylketone, 2,4-dihydroxybenzophenone, 2.3.4- ) dihydroxybenzophenone, 2,4.6-) dihydroxybenzophenone,
2.4.2', 4'-tetrahydroxybenzophenone, 2,3.4.4'-tetrahydroxybenzophenone, 2,3,4.2'.
4′−ペンタヒドロキシベンゾフェノン、2,3゜4.
2’、6’−ペンタヒドロキシベンゾフェノン、2.3
.4.3’、4’、5’−へキサヒドロキシベンゾフェ
ノン、2,4.6.3’、4’。4'-pentahydroxybenzophenone, 2,3°4.
2',6'-pentahydroxybenzophenone, 2.3
.. 4.3',4',5'-hexahydroxybenzophenone, 2,4.6.3',4'.
5′−へキサヒドロキシベンゾフェノン、2,3゜4.
5.4”−ペンタヒドロキシベンゾフェノン、2、 3
. 4. 5. 3’、 4”、 5”−へブタヒ
ドロキシベンゾフヱノン、2,3.3″、4’、5’−
ペンタヒドロキシ−4−メトキシベンゾフェノン、2.
3,4.3“、4”、5’−へキサヒドロキシ−5−ク
ロロベンゾフェノン、2,3.4゜3’、4’、5’−
へキサヒドロキシ−5−ベンゾイルベンゾフェノン等の
ポリヒドロキシフェニルアリールケトン類、ビス(2,
4−ジヒドロキシフェニル)メタン、2.2−ビス(2
,4−ジヒドロキシフェニル)プロパン、2,2−ビス
(2,3,4−トリヒドロキシフェニル)プロパン等の
ビス(ポリヒドロキシフェニル)アルカン類、3.4.
5−)リヒドロキシ安患香酸プロピル、3.4.5−ト
リヒドロキシ安息香酸フェニル等のポリヒドロキシ安息
香酸アルキルエステル類またはポリヒドロキシ安息香酸
アリールエステル類、ビス(2,4−ジヒドロキシベン
ゾイル)メタンビ、2.(2,3,4−)ジヒドロキシ
ベンゾイル)メタン、ビス(2,4,6−)ジヒドロキ
シベンゾイル)メタン、2.2−ビス(2,3,4−)
ジヒドロキシフェニル)プロパン等のビス(ポリヒドロ
キシベンゾイル)アルカン類、p−ビス(2,5−ジヒ
ドロキシベンゾイル)ベンゼン、p−ビス(2,3,4
−1リヒドロキシベンゾイル)ベンゼン、p−ビス(2
,4,6−)ジヒドロキシベンゾイル)ベンゼン等のビ
ス(ポリヒドロキシベンゾイル)ベンゼン類、エチレン
グリコールジ(3,5−ジヒドロキシベンゾエート)、
エチレングリコールジ(3,4,5−トリヒドロキシベ
ンゾエート)、1.4−ブタンジオールジ(3,4,5
−1−ジヒドロキシベンゾエート)、1゜8−オクタン
ジオールジ(3,4,5−)ジヒドロキシベンゾエート
)等のアルカンジオールジ(ポリヒドロキシベンゾエー
ト)類、ジエチレングリコールジ(3,4,5−)ジヒ
ドロキシベンゾエート)、トリエチレングリコールジ(
3,4゜5−トリヒドロキシベンゾエート)等のポリエ
チレングリコールジ(ポリヒドロキシベンゾエート)類
、ヒスピジン、グルベルジン等の水酸基を有するα−ピ
ロン系天然色素類、クリシン、アビゲニン、ケルセチン
、ルチン、モリン、ナリンゲニン、ブルネチン等の水酸
基を有するγ−ピロン系天然色素類、ロイコプテリン、
エントロプテリン、クリソプテリン、イオジニン等の水
酸基を有するジアジン系天然色素類、アトロメンチン、
ムスカルフィン、ニゲロン、アリザリン、プルプリン、
スカイリン等の水酸基を有するキノン系天然色素類、お
よびポリ (ヒドロキシスチレン)、アルカリ可溶性ノ
ボラック樹脂、ピロガロール・アセトン縮合樹脂等の水
酸基を有する樹脂類を挙げることができる。これらのポ
リヒドロキシ化合物は単独でまたは2種以上組合わせて
用いられる。5'-hexahydroxybenzophenone, 2,3°4.
5.4”-pentahydroxybenzophenone, 2, 3
.. 4. 5. 3', 4'', 5''-hebutahydroxybenzophenone, 2,3.3'', 4', 5'-
Pentahydroxy-4-methoxybenzophenone, 2.
3,4.3",4",5'-hexahydroxy-5-chlorobenzophenone, 2,3.4°3',4',5'-
Polyhydroxyphenylarylketones such as hexahydroxy-5-benzoylbenzophenone, bis(2,
4-dihydroxyphenyl)methane, 2,2-bis(2
, 4-dihydroxyphenyl)propane, 2,2-bis(2,3,4-trihydroxyphenyl)propane and other bis(polyhydroxyphenyl)alkanes, 3.4.
5-) Polyhydroxybenzoic acid alkyl esters or polyhydroxybenzoic acid aryl esters such as propyl trihydroxybenzoate, phenyl 3.4.5-trihydroxybenzoate, bis(2,4-dihydroxybenzoyl)methane , 2. (2,3,4-)dihydroxybenzoyl)methane, bis(2,4,6-)dihydroxybenzoyl)methane, 2,2-bis(2,3,4-)
Bis(polyhydroxybenzoyl)alkanes such as dihydroxyphenyl)propane, p-bis(2,5-dihydroxybenzoyl)benzene, p-bis(2,3,4
-1 hydroxybenzoyl)benzene, p-bis(2
, 4,6-)dihydroxybenzoyl)benzene, etc., ethylene glycol di(3,5-dihydroxybenzoate),
Ethylene glycol di(3,4,5-trihydroxybenzoate), 1,4-butanediol di(3,4,5
-1-dihydroxybenzoate), alkanediol di(polyhydroxybenzoates) such as 1°8-octanediol di(3,4,5-) dihydroxybenzoate), diethylene glycol di(3,4,5-) dihydroxybenzoate) , triethylene glycol di(
polyethylene glycol di(polyhydroxybenzoate) such as 3,4゜5-trihydroxybenzoate), α-pyrone natural pigments having hydroxyl groups such as hispidin and gluterdine, chrysin, abigenin, quercetin, rutin, morin, naringenin, γ-pyrone natural pigments with hydroxyl groups such as brunetine, leucopterin,
Diazine natural pigments with hydroxyl groups such as entropterin, chrysopterin, and iodinine, atromentin,
muscarfine, nigerone, alizarin, purpurin,
Examples include quinone natural pigments having a hydroxyl group such as skyline, and resins having a hydroxyl group such as poly(hydroxystyrene), alkali-soluble novolak resin, and pyrogallol/acetone condensation resin. These polyhydroxy compounds may be used alone or in combination of two or more.
本発明でアシル化に使用するアシル化剤の具体例として
は、酢酸クロリド、酢酸プロミド、酢酸フルオリド、ク
ロル酢酸クロリド、ジクロル酢酸クロリド、トリクロル
酢酸クロリド、プロピオン酸クロリド、プロピオン酸プ
ロミド、α−クロロプロピオン酸クロリド、酪酸クロリ
ド、イソ酪酸クロリド、吉草酸クロリド、イソ吉草酸ク
ロリド、トリメチル酢酸クロリド等のアルカンカルボン
酸ハライド類、アクリル酸クロリド、アクリル酸ブロミ
ト、メタクリル酸クロリド、メタクリル酸プロミド、ク
ロトン酸クロリド、α−エチルアクリル酸クロリド、β
−メチルクロトン酸クロリド、アンゲリカ酸クロリド、
チグリン酸クロリド、α−エチルクロトン酸クロリド、
2−ペンテン酸クロリド等のアルケンカルボン酸ハライ
ド類、プロピオール酸りロリド、テトロール酸クロリド
、エチルプロピオール酸りロリド、ブチルプロピオール
酸りロリド等のアルキンカルボン酸ハライド類、2.4
−ペンタジェン酸クロリド、2.4−ヘキサジエン酸ク
ロリド等のアルカジエンカルボン酸ハライド類、安息香
酸クロリド、安息香酸プロミド、4−メチル安息香酸ク
ロリド、4−プロピル安息香酸クロリド、4−クロロ安
息香酸クロリド、3.4.5−1−リメトキシ安息香酸
クロリド、3゜4.5−1−リメトキシ安息香酸プロミ
ド等のアリールカルボン酸ハライド類、メトキシギ酸ク
ロリド、エトキシギ酸クロリド、プロポキシギ酸クロリ
ド、2−エトキシエトキシギ酸クロリド、メトキシ酢酸
クロリド、エトキシ酢酸クロリド、プロポキシ酢酸クロ
リド、3−メトキシプロピオン酸クロリド、3−エトキ
シプロピオン酸クロリド等のアルコキシアルカンカルボ
ン酸ハライド類、およびメトキシカルボニル酢酸クロリ
ド、エトキシカルボニルプロピオン酸クロリド、エトキ
シカルボニル酢酸クロリド、エトキシカルボニルプロピ
オン酸クロリド、メトキシカルボニル酪酸クロリド、エ
トキシカルボニル酪酸クロリド、メトキシカルボニル吉
草酸クロリド、エトキシカルボニル吉草酸クロリド等の
アルコキシカルボニルアルカンカルボン酸ハライド類を
挙げることができる。Specific examples of the acylating agent used for acylation in the present invention include acetic acid chloride, acetic acid bromide, acetic acid fluoride, chloroacetic acid chloride, dichloroacetic acid chloride, trichloroacetic acid chloride, propionic acid chloride, propionic acid bromide, α-chloropropion Alkanecarboxylic acid halides such as acid chloride, butyric acid chloride, isobutyric acid chloride, valeric acid chloride, isovaleric acid chloride, trimethylacetic acid chloride, acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride, methacrylic acid bromide, crotonic acid chloride, α-Ethyl acrylic acid chloride, β
-Methylcrotonic acid chloride, angelic acid chloride,
Tiglic acid chloride, α-ethyl crotonic acid chloride,
Alkene carboxylic acid halides such as 2-pentenoyl chloride, alkyne carboxylic acid halides such as propiol acid chloride, tetrolic acid chloride, ethylpropiol acid chloride, butylpropiol acid chloride, 2.4
- Alkadienecarboxylic acid halides such as pentadienoic acid chloride and 2,4-hexadienoic acid chloride, benzoic acid chloride, benzoic acid bromide, 4-methylbenzoic acid chloride, 4-propylbenzoic acid chloride, 4-chlorobenzoic acid chloride, 3.4.Arylcarboxylic acid halides such as 5-1-rimethoxybenzoic acid chloride, 3゜4.5-1-rimethoxybenzoic acid bromide, methoxyformic acid chloride, ethoxyformic acid chloride, propoxyformic acid chloride, 2-ethoxyethoxyformic acid Alkoxyalkane carboxylic acid halides such as chloride, methoxyacetic acid chloride, ethoxyacetic acid chloride, propoxyacetic acid chloride, 3-methoxypropionic acid chloride, 3-ethoxypropionic acid chloride, and methoxycarbonylacetic acid chloride, ethoxycarbonylpropionic acid chloride, ethoxycarbonyl Examples include alkoxycarbonylalkane carboxylic acid halides such as acetic acid chloride, ethoxycarbonylpropionic acid chloride, methoxycarbonylbutyric acid chloride, ethoxycarbonylbutyric acid chloride, methoxycarbonylvaleric acid chloride, and ethoxycarbonylvaleric acid chloride.
前記のアシル化剤としては主にカルボン酸ハライドを挙
げたが、アシル化反応の条件によってはカルボン酸また
はカルボン酸無水物であっても差し支えない。これらの
アシル化剤は単独でまたは2種以上組合わせて用いられ
る。Although carboxylic acid halides are mainly used as the above-mentioned acylating agent, carboxylic acids or carboxylic acid anhydrides may also be used depending on the conditions of the acylation reaction. These acylating agents may be used alone or in combination of two or more.
本発明でスルホニル化に使用するスルホニル化剤の具体
例としては、メタンスルホン酸クロリド、メタンスルホ
ン酸フルオリド、エタンスルホン酸クロリド、プロパン
スルホン酸クロリド、ブタンスルホン酸クロリド、ペン
タンスルホン酸クロリド、ヘキサンスルホン酸クロリド
等のアルカンスルホン酸ハライド類、エチレンスルホン
酸クロリド、1−プロペン−1−スルホン酸クロリド等
のアルケンスルホン酸ハライド類、およびベンゼンスル
ホン酸クロリド、ベンゼンスルホン酸フルオリド、p−
)ルエンスルホン酸クロリド、p−キシレンスルホン酸
クロリド等のアリールスルホン酸ハライド類を挙げるこ
とができる。これらのスルホニル化剤は単独でまたは2
種以上組合わせて用いられる。Specific examples of the sulfonylating agent used for sulfonylation in the present invention include methanesulfonic acid chloride, methanesulfonic acid fluoride, ethanesulfonic acid chloride, propanesulfonic acid chloride, butanesulfonic acid chloride, pentanesulfonic acid chloride, and hexanesulfonic acid chloride. Alkanesulfonic acid halides such as chloride, alkenesulfonic acid halides such as ethylenesulfonic acid chloride, 1-propene-1-sulfonic acid chloride, benzenesulfonic acid chloride, benzenesulfonic acid fluoride, p-
) Arylsulfonic acid halides such as luenesulfonic acid chloride and p-xylenesulfonic acid chloride can be mentioned. These sulfonylating agents alone or in combination
Used in combination of more than one species.
本発明で1,2−キノンジアジド化に使用する1、2−
キノンジアジド化剤の代表例としては、1.2−キノン
ジアジドスルホン酸ハライド、具体的には1,2−ナフ
トキノンジアジド−5−スルホン酸クロリド、1,2−
ナフトキノンジアジド−4−スルホン酸クロリド、1,
2−ベンゾキノンジアジド−4−スルホン酸クロリド等
が挙げられる。これらの1.2−キノンジアジド化剤は
単独でまたは2種以上組合せて用いられる。1,2- used in 1,2-quinone diazidation in the present invention
Typical examples of quinonediazidating agents include 1,2-quinonediazide sulfonic acid halide, specifically 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-
naphthoquinonediazide-4-sulfonic acid chloride, 1,
Examples include 2-benzoquinonediazide-4-sulfonic acid chloride. These 1,2-quinone diazidating agents may be used alone or in combination of two or more.
本発明の1.2−キノンジアジド化合物(以下、単にr
QD化合物」と称する)の製造方法の具体例としては、
下記(1)、(2)または(3)の方法を挙げることが
できる。The 1,2-quinonediazide compound of the present invention (hereinafter simply r
As a specific example of the method for producing QD compound (referred to as "QD compound"),
The following methods (1), (2), or (3) can be mentioned.
(1)ポリヒドロキシ化合物をア七トン、ジオキサン、
テトラヒドロフラン、メチルエチルケトン等の溶媒に溶
解後、ポリヒドロキシ化合物の水酸基の一部をアシル化
および/またはスルホニル化する量のアシル化剤および
/またはスルホニル化剤を、好ましくはポリヒドロキシ
化合物の水酸基1グラム当量に対して0.01〜0.8
モル添加し、反応させた後、さらにポリヒドロキシ化合
物の残りの水酸基の一部または全部を1,2−キノンジ
アジド化する量の1,2−キノンジアジド化剤を添加し
て反応させ、反応終了後、生成した塩酸塩を濾過するか
、または水を添加して塩酸塩を熔解させた後、大量の希
塩酸水、希硫酸水のような酸性水で再沈1ffl$i製
した後、乾燥する方法。(1) The polyhydroxy compound is a7tone, dioxane,
After dissolving in a solvent such as tetrahydrofuran or methyl ethyl ketone, add an amount of acylating agent and/or sulfonylating agent to acylate and/or sulfonylate a portion of the hydroxyl groups of the polyhydroxy compound, preferably 1 gram equivalent of the hydroxyl groups of the polyhydroxy compound. 0.01-0.8 for
After adding molar amount and reacting, further add a 1,2-quinonediazidizing agent in an amount to convert some or all of the remaining hydroxyl groups of the polyhydroxy compound into 1,2-quinonediazide and react, and after the reaction is completed, A method of filtering the generated hydrochloride or adding water to dissolve the hydrochloride, reprecipitating with a large amount of acidic water such as dilute hydrochloric acid or dilute sulfuric acid, and then drying.
(2)ポリヒドロキシ化合物を前記と同様の溶媒に溶解
後、アシル化剤および/またはスルホニル他剤と1.2
−キノンジアジド化剤とを添加し、反応させ、反応終了
後、生成した塩酸塩を濾過するか、または水を添加して
塩酸塩を溶解させた後、大量の希塩酸水、希硫酸水のよ
うな酸性水で再沈殿精製した後、乾燥する方法。(2) After dissolving the polyhydroxy compound in the same solvent as above, add acylating agent and/or sulfonyl other agent to 1.2
- Add a quinone diazidating agent and react with it, and after the reaction is complete, filter the generated hydrochloride, or add water to dissolve the hydrochloride, and then add a large amount of dilute hydrochloric acid water, dilute sulfuric acid water, etc. A method in which the product is purified by reprecipitation with acidic water and then dried.
(3)ポリヒドロキシ化合物を前記と同様の溶媒に溶解
後、ポリヒドロキシ化合物の水酸基の一部を1.2−キ
ノンジアジド化する量の1,2−キノンジアジド化剤を
、好ましくはポリヒドロキシ化合物の水酸基1グラム当
量に対して0.3〜0.99モル添加し反応させた後、
さらにポリヒドロキシ化合物の残りの水酸基の一部もし
くは全部をアシル化および/またはスルホニル化する量
のアシル化剤および/またはスルホニル化剤を添加し、
反応させ、反応終了後、生成した塩酸塩を濾過するか、
または水を添加して塩酸塩を溶解させた後、大量の希塩
酸水、希硫酸水のような酸性水で再沈殿精製した後、乾
燥する方法。(3) After dissolving the polyhydroxy compound in the same solvent as above, add a 1,2-quinone diazidating agent in an amount to convert a part of the hydroxyl groups of the polyhydroxy compound into 1,2-quinone diazide, preferably the hydroxyl groups of the polyhydroxy compound. After adding 0.3 to 0.99 mol per 1 gram equivalent and reacting,
Further, adding an acylating agent and/or a sulfonylating agent in an amount to acylate and/or sulfonylate some or all of the remaining hydroxyl groups of the polyhydroxy compound,
React, and after the reaction is complete, filter the generated hydrochloride, or
Alternatively, after adding water to dissolve the hydrochloride, purifying it by reprecipitation with a large amount of acidic water such as diluted hydrochloric acid or diluted sulfuric acid, followed by drying.
本発明で使用されるアシル化剤、スルホニル化剤および
1.2−キノンジアジド化剤の総使用量は、ポリヒドロ
キシ化合物の水酸基1グラム当量に対して0.3モル以
上、好ましくは0.4モル以上、特に好ましくは0.5
モル以上で、通常は1.2モル以下である。これが0.
3モル未満の場合は、樹脂組成物の特性である感度やこ
れをポジ型レジストとして使用する際の残膜率のバラン
スがくずれ、さらには解像性にも問題が生じる。The total amount of the acylating agent, sulfonylating agent, and 1,2-quinone diazidizing agent used in the present invention is 0.3 mol or more, preferably 0.4 mol, per gram equivalent of hydroxyl group of the polyhydroxy compound. or more, particularly preferably 0.5
It is more than 1 mole, and usually less than 1.2 mole. This is 0.
If the amount is less than 3 moles, the sensitivity, which is a characteristic of the resin composition, and the residual film rate when used as a positive resist will be unbalanced, and furthermore, problems will arise in resolution.
アシル化剤および/またはスルホニル化剤〔A〕と1.
2−キノンジアジド化剤(Ql との使用割合は〔A〕
/ 〔Q〕 =0.0110.99〜0.710.3
〔モル比)、好ましくは〔A〕/ 〔Q〕=0゜011
0.99〜0.610.4Cモル比)、特に好ましくは
〔A〕 / 〔Q〕 = 0.110.9〜0.6 /
0.4〔モル比〕である。使用割合〔A〕/ 〔Q〕
が0゜0110.99Cモル比〕未満であると、ポリヒ
ドロキシ化合物の水酸基のアシル化および/またはスル
ホニル化される割合が1.2−キノンジアジド化される
割合に対して少ないため、樹脂組成物として溶液で保管
する時に異物の発生を止めることができない。一方、使
用割合〔A〕/ 〔Q〕が0.710.3[モル比〕を
超えると、ポリヒドロキシ化合物の水酸基の1,2−キ
ノンジアジド化される割合がアシル化および/またはス
ルホニル化される割合に対して少ないため、樹脂組成物
の特性である感度やこれをポジ型レジストとして使用す
る際の残膜率のバランスがくずれ、さらには解像性にも
問題が生じる。Acylating agent and/or sulfonylating agent [A] and 1.
2-quinone diazidating agent (Using ratio with Ql is [A]
/ [Q] =0.0110.99~0.710.3
[Molar ratio), preferably [A]/[Q]=0°011
0.99-0.610.4C molar ratio), particularly preferably [A] / [Q] = 0.110.9-0.6 /
The molar ratio is 0.4. Usage ratio [A] / [Q]
is less than 0゜0110.99C molar ratio], the proportion of acylated and/or sulfonylated hydroxyl groups of the polyhydroxy compound is smaller than the proportion of 1,2-quinone diazidation, and therefore the resin composition is It is not possible to stop the generation of foreign substances when storing in solution. On the other hand, when the usage ratio [A]/[Q] exceeds 0.710.3 [molar ratio], the proportion of 1,2-quinone diazidation of the hydroxyl groups of the polyhydroxy compound is acylated and/or sulfonylated. Since the ratio is small, the sensitivity, which is a characteristic of the resin composition, and the residual film rate when used as a positive resist are unbalanced, and furthermore, problems arise in resolution.
前記1.2−キノンジアジド化反応において、塩基性試
剤を用いることが必要である。In the 1,2-quinone diazidation reaction, it is necessary to use a basic reagent.
前記塩基性試剤としては、例えば水酸化ナトリウム、水
酸化カリウム、炭酸ナトリウム等の無機アルカリ類、ト
リエチルアミン、トリプロピルアミン、ピリジン、アニ
リン等の有機アミン類を挙げることができる。これらの
塩基性試剤の使用量は、1.2−キノンジアジド他剤1
モルに対して通常、0.8〜2モル、好ましくは1〜1
.5モルである。Examples of the basic reagent include inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and organic amines such as triethylamine, tripropylamine, pyridine, and aniline. The amount of these basic reagents used is 1,2-quinonediazide and other agents.
Usually 0.8 to 2 mol, preferably 1 to 1 mol
.. It is 5 moles.
また、アシル化および/またはスルホニル化反応におい
て、前記カルボン酸ハライドおよび/またはスルホン酸
ハライドを用いる場合にも塩基号1試剤を用いることが
必要であり、その使用量は、カルボン酸ハライドおよび
スルホン酸ハライドの総量1モルに対して、通常、0.
8〜2モル、好ましくは1〜1.5である。In addition, in the acylation and/or sulfonylation reaction, when using the carboxylic acid halide and/or sulfonic acid halide, it is necessary to use the base No. 1 reagent, and the amount used is Usually 0.00% per mole of halide.
8 to 2 mol, preferably 1 to 1.5 mol.
なお、アシル化反応において、前記カルボン酸無水物を
使用する場合には、特に前記塩基性試剤は必要ではなく
、また前記カルボン酸を使用する場合には、反応系に前
記塩基性試剤が存在しないようにすることが必要である
。In addition, in the acylation reaction, when the carboxylic acid anhydride is used, the basic reagent is not particularly required, and when the carboxylic acid is used, the basic reagent is not present in the reaction system. It is necessary to do so.
また、上記(1)、(2)および(3)の方法における
反応温度は、通常、−20〜60℃、好ましくは0〜4
0℃である。Further, the reaction temperature in the above methods (1), (2) and (3) is usually -20 to 60°C, preferably 0 to 4°C.
It is 0°C.
前記のようにして合成される本発明によるQD化合物は
、樹脂組成物として使用する際に単独でまたは2種以上
混合してアルカリ可溶性樹脂に配合して使用されるが、
その配合量はアルカリ可溶性樹脂100重量部に対して
好ましくは5〜100重量部、特に好ましくは10〜5
0重量部である。QD化合物の配合量が少なすぎると、
QD化合物が放射線を吸収して生成するカルボン@量が
少ないので、樹脂組成物をポジ型レジストとして使用す
る際にパターニングが困難となり、また配合量が多すぎ
ると、短時間の放射線照射では加えたQD化合物のすべ
てを分解することができず、アルカリ性水溶液からなる
現像液による現像が困難となる。The QD compound according to the present invention synthesized as described above can be used alone or as a mixture of two or more in an alkali-soluble resin when used as a resin composition.
The blending amount is preferably 5 to 100 parts by weight, particularly preferably 10 to 5 parts by weight, per 100 parts by weight of the alkali-soluble resin.
It is 0 parts by weight. If the amount of QD compound is too small,
Since the QD compound absorbs radiation and produces a small amount of carvone, patterning becomes difficult when the resin composition is used as a positive resist. All of the QD compounds cannot be decomposed, making development with a developer consisting of an alkaline aqueous solution difficult.
本発明の製造方法により得られるQD化合物を含有する
樹脂組成物に用いられるアルカリ可溶性樹脂としては、
例えばアルカリ可溶性ノボラック樹脂(以下、単に「ノ
ボラック樹脂」と称する)が挙げられる。ノボラック樹
脂は、フェノール類とアルデヒド類とを酸触媒の存在下
に付加縮合して合成されるものである。The alkali-soluble resin used in the resin composition containing the QD compound obtained by the production method of the present invention includes:
For example, an alkali-soluble novolak resin (hereinafter simply referred to as "novolak resin") can be mentioned. Novolac resins are synthesized by addition condensation of phenols and aldehydes in the presence of an acid catalyst.
この際使用されるフェノール類としては、例えばフェノ
ール、0−クレゾール、m−クレゾール、p−クレゾー
ル、0−エチルフェノール、m−エチルフェノール、p
−エチルフェノール、0−ブチルフェノール、m−ブチ
ルフェノール、p−ブチルフェノール、2.3−キシレ
ノール、2.4−キシレノール、2.5−キシレノール
、3.4−キシレノール、3.5−キシレノール、2,
3゜5−トリメチルフェノール、p−フェニルフェノー
ル、ヒドロキノン、カテコール、レゾルシノール、2−
メチルレゾルシノール、ピロガロール、α−ナフトール
、ビスフェノールA1ジヒドロキシ安息香酸エステル、
没食子酸エステル等が挙げられる。これらのフェノール
類は、単独でまたは2種以上組合わせて用いられる。The phenols used at this time include, for example, phenol, 0-cresol, m-cresol, p-cresol, 0-ethylphenol, m-ethylphenol, p-cresol,
-Ethylphenol, 0-butylphenol, m-butylphenol, p-butylphenol, 2.3-xylenol, 2.4-xylenol, 2.5-xylenol, 3.4-xylenol, 3.5-xylenol, 2,
3゜5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-
Methylresorcinol, pyrogallol, α-naphthol, bisphenol A1 dihydroxybenzoate,
Examples include gallic acid ester. These phenols may be used alone or in combination of two or more.
また前記アルデヒド類としては、例えばホルムアルデヒ
ド、パラホルムアルデヒド、アセトアルデヒド、プロピ
ルアルデヒド、ベンズアルデヒド、フェニルアセトアル
デヒド、α−フェニルプロピルアルデヒド、β−フェニ
ルプロピルアルデヒド、0−ヒドロキシベンズアルデヒ
ド、m−ヒドロキシベンズアルデヒド、p−ヒドロキシ
ベンズアルデヒド、0−クロロベンズアルデヒド、m−
クロロベンズアルデヒド、p−クロロベンズアルデヒド
、0−ニトロベンズアルデヒド、m−ニトロベンズアル
デヒド、p−ニトロベンズアルデヒド、O−メチルベン
ズアルデヒド、m−メチルベンズアルデヒド、p−メチ
ルベンズアルデヒド、p−エチルベンズアルデヒド、p
−n−ブチルベンズアルデヒド等が挙げられる。これら
のアルデヒド類は、単独でまたは2種以上組合わせて用
いられる。アルデヒド類の使用量は、フェノール類1モ
ル当たり、通常、0.7〜3モルである。Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, 0-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, 0-chlorobenzaldehyde, m-
Chlorobenzaldehyde, p-chlorobenzaldehyde, 0-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, O-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p
-n-butylbenzaldehyde and the like. These aldehydes may be used alone or in combination of two or more. The amount of aldehydes used is usually 0.7 to 3 moles per mole of phenols.
前記酸触媒としては、塩酸、硝酸、硫酸等の無ta酸、
または蟻酸、蓚酸、酢酸等の有機酸が用いられる。これ
らの酸触媒の使用量は、フェノール類1モル当たり、好
ましくは1×10″″4〜5×10−1モルである。The acid catalyst includes non-ta acids such as hydrochloric acid, nitric acid, and sulfuric acid;
Alternatively, organic acids such as formic acid, oxalic acid, and acetic acid are used. The amount of these acid catalysts used is preferably 1 x 10''4 to 5 x 10-1 mol per mol of phenol.
ノボラック樹脂を合成する際の縮合反応においては、通
常、反応媒質として水を用いるが、縮合反応において使
用するフェノール類がアルデヒド類の水溶液に溶解せず
、反応初期から不均一系になる場合には、反応媒質とし
て親水性溶媒を使用することもできる。この際用いられ
る親水性溶媒としては、例えばメタノール、エタノール
、プロパツール、ブタノール等のアルコール類、または
テトラヒドロフラン、ジオキサン等の環状エーテル類が
挙げられる。これらの反応媒質の使用量は、通常、反応
原料100重量部当たり、20〜1000重量部である
。Water is usually used as a reaction medium in the condensation reaction when synthesizing novolac resins, but if the phenols used in the condensation reaction do not dissolve in the aqueous solution of aldehydes and the reaction becomes a heterogeneous system from the early stage, , it is also possible to use hydrophilic solvents as reaction medium. Examples of the hydrophilic solvent used in this case include alcohols such as methanol, ethanol, propatool, and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw materials.
縮合反応の反応温度は、反応原料に応じて適宜調整する
ことができるが、通常、10〜200℃である。The reaction temperature of the condensation reaction can be adjusted as appropriate depending on the reaction raw materials, but is usually 10 to 200°C.
縮合反応終了後、系内に存在する未反応原料、酸触媒お
よび反応媒質を除去するため、減圧下に揮発分を留去し
、次いで溶融したノボラック樹脂をスチール製ベルト等
の上に流源して回収する。After the condensation reaction is complete, in order to remove the unreacted raw materials, acid catalyst, and reaction medium present in the system, volatile components are distilled off under reduced pressure, and then the molten novolac resin is poured onto a steel belt, etc. and collect it.
前記ノボラック樹脂以外のアルカリ可溶性樹脂としては
、例えばポリヒドロキシスチレンもしくはその誘導体、
スチレン−無水マレイン酸共重合体、ポリビニルヒドロ
キシベンゾエート、カルボキシル基含有(メタ)アクリ
ル系樹脂等が挙げられる。これらのアルカリ可溶性樹脂
は単独でまたは2種以上組合わせて用いられる。Examples of alkali-soluble resins other than the novolak resin include polyhydroxystyrene or derivatives thereof,
Examples include styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and carboxyl group-containing (meth)acrylic resin. These alkali-soluble resins may be used alone or in combination of two or more.
本発明の製造方法により得られるQD化合物を含有する
樹脂組成物を基板に塗布するに際しては、該組成物を、
例えば濃度が5〜50重量%となるように適当な溶剤に
溶解し、これを回転塗布、流し塗布、ロール塗布等によ
りシリコンウェーハ等の基板に塗布する。この際に用い
られる溶剤としては、例えばエチレングリコールモノメ
チルエーテル、エチレングリコールモノエチルエーテル
等のグリコールエーテル類、メチルセロソルブアセテー
ト、エチルセロソルブアセテート等のセロソルブエステ
ル類、2−オキシプロピオン酸エチル、2−オキシプロ
ピオン酸エチル等のモノオキシモノカルボン酸エステル
類、トルエン、キシレン等の芳香族炭化水素類、メチル
エチルケトン、シクロヘキサノン等のケトン類、または
酢酸エチル、酢酸ブチル等のエステル類が挙げられる。When applying a resin composition containing a QD compound obtained by the production method of the present invention to a substrate, the composition is
For example, it is dissolved in a suitable solvent to a concentration of 5 to 50% by weight, and applied to a substrate such as a silicon wafer by spin coating, flow coating, roll coating, or the like. Examples of solvents used in this case include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, ethyl 2-oxypropionate, and 2-oxypropion. Examples include monooxymonocarboxylic acid esters such as ethyl acid, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate.
これらの溶剤は単独でまたは2種以上組合わせて用いら
れる。また必要に応じ、ベンジルエチルエーテル、ジヘ
キシルエーテル等のエーテル類、ジエチレングリコール
七ツメチルエーテル、ジエチレングリコールモノエチル
エーテル等のグリコールエーテル類、アセトニルアセト
ン、イソホロン等のケトン類、カプロン酸、カプリル酸
等の脂肪酸類、1−オクタツール、1−ノナノール、ベ
ンジルアルコール等のアルコール類、または酢酸ベンジ
ル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジ
エチル、γ−ブチロラクトン、炭酸エチレン、・炭酸エ
チレン、フェニルセロソルブアセテート等のエステル類
のような高沸点溶剤を添加することもできる。These solvents may be used alone or in combination of two or more. In addition, if necessary, ethers such as benzyl ethyl ether and dihexyl ether, glycol ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, ketones such as acetonyl acetone and isophorone, and fatty acids such as caproic acid and caprylic acid are added. , 1-octatool, 1-nonanol, alcohols such as benzyl alcohol, or esters such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, ethylene carbonate, phenyl cellosolve acetate, etc. It is also possible to add high boiling point solvents such as.
本発明の製造方法により得られるQD化合物を含有する
樹脂組成物には、感度を向上させるために増感剤を配合
することができる。この増感剤としては、例えば2H−
ピリド(3,2−b)−1゜4−オキサジン−3〔4H
)オン類、l0H−ピリド(3,2−b)(1,4)−
ベンゾチアジン類、ウラゾール類、ヒダントイン類、バ
ルビッール酸類、グリシン無水物類、1−ヒドロキシベ
ンゾトリアゾール類、アロキサン類、マレイミド類、さ
らには特公昭4B−12242号公報、特公昭48−3
5402号公報、特開昭58−37641号公報、特開
昭58−149042号公報等に記載されている増感剤
が挙げられる。これらの増感剤の配合量は、QD化合物
100重量部に対し、通常、100重量部以下である。A sensitizer can be added to the resin composition containing the QD compound obtained by the production method of the present invention in order to improve sensitivity. As this sensitizer, for example, 2H-
Pyrido(3,2-b)-1゜4-oxazine-3[4H
) ons, 10H-pyrido(3,2-b)(1,4)-
Benzothiazines, urazoles, hydantoins, barbylic acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides, as well as Japanese Patent Publication No. 4B-12242, Japanese Patent Publication No. 48-3
Examples include sensitizers described in JP-A No. 5402, JP-A-58-37641, JP-A-58-149042, and the like. The blending amount of these sensitizers is usually 100 parts by weight or less per 100 parts by weight of the QD compound.
さらに本発明の製造方法により得られるQD化合物を含
有する樹脂組成物には、塗布性、例えばス) IJエニ
ーョンや乾燥塗膜形成後の放射線照射部の現像性を改良
するため、界面活性剤等を配合することができる。界面
活性剤等としては、例えばポリオキシエチレンラウリル
エーテル、ポリオキシエチレンステアリルエーテル、ポ
リオキシエチレンオレイルエーテル等のポリオキシエチ
レンアルキルエーテル類、ポリオキシエチレンオクチル
フェニルエーテル、ポリオキシエチレンノニルフェニル
エーテル等のポリオキシエチレンアルキルフェニルエー
テル類、ポリエチレングリコールジラウレート、ポリエ
チレングリコールジステアレート等のポリエチレングリ
コールジアルキルエーテル類のノニオン系界面活性剤、
エフトップEF301、EF303、EF352(新秋
田化成(株)製)、メガファックF171、F173
(大日本インキ(株)製)、特開昭57−178242
号公報に例示されるフッ化アルキル基またはパーフルオ
ロアルキル基を有する直鎮状のフッ素系界面活性剤、フ
ロラードFC430、FC431(住友スリーエム(株
)製)、アサヒガードAG710、サーフロンS−38
2,5C101,5C102,5C103,5C104
,5CIO5,5C106(旭硝子(株)製)等のフッ
素系界面活性剤、オルガノシロキサンポリマーKP34
1(信越化学工業(株)製)、アクリル酸系またはメタ
クリル酸系(共)重合体ポリフロー隘75、l1h95
(共栄社油脂化学工業(株)製)等が挙げられる。これ
らの界面活性剤等の配合量は、本発明の製造方法により
得られるQD化合物を含有する樹脂組成物の固形分10
0重量部当たり、通常、2重量部以下である。Furthermore, the resin composition containing the QD compound obtained by the production method of the present invention may contain surfactants, etc. in order to improve the coating properties, for example, the developability of the IJ any and the radiation irradiated area after forming the dry coating film. can be blended. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. Nonionic surfactants of polyethylene glycol dialkyl ethers such as oxyethylene alkyl phenyl ethers, polyethylene glycol dilaurate, and polyethylene glycol distearate;
F-TOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173
(manufactured by Dainippon Ink Co., Ltd.), JP-A-57-178242
Straight fluorine-based surfactants having a fluorinated alkyl group or perfluoroalkyl group as exemplified in the above publication, Florard FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-38
2, 5C101, 5C102, 5C103, 5C104
, 5CIO5, 5C106 (manufactured by Asahi Glass Co., Ltd.), fluorine-based surfactants, organosiloxane polymer KP34
1 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co)polymer Polyflow 75, l1h95
(manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). The blending amount of these surfactants, etc. is based on the solid content of the resin composition containing the QD compound obtained by the production method of the present invention.
It is usually 2 parts by weight or less per 0 parts by weight.
また本発明の製造方法により得られるQD化合物を含有
する樹脂組成物には、放射線照射部の潜増を可視化させ
たり、放射線照射時のハレーションの影響を少なくする
ために着色剤を、また接着性を改良するために接着助剤
を配合することもできる。In addition, the resin composition containing the QD compound obtained by the production method of the present invention is coated with a coloring agent in order to visualize the latent increase in the radiation irradiated area and to reduce the effect of halation during radiation irradiation. Adhesion aids can also be added to improve the properties.
さらに、本発明の製造方法により得られるQD化合物を
含有する樹脂組成物には、必要に応じて保存安定剤、消
泡剤等も配合することができる。Furthermore, the resin composition containing the QD compound obtained by the production method of the present invention may also contain a storage stabilizer, an antifoaming agent, etc., if necessary.
本発明の製造方法により得られるQD化合物を含有する
樹脂組成物は、溶剤にアルカリ可溶性樹脂、QD化合物
および各種配合剤を所定量ずつ熔解させ、例えば孔径0
.2μm程度のフィルタで濾過することにより、調製さ
れる。A resin composition containing a QD compound obtained by the production method of the present invention is prepared by dissolving a predetermined amount of an alkali-soluble resin, a QD compound, and various compounding agents in a solvent.
.. It is prepared by filtering through a filter of about 2 μm.
本発明の製造方法により得られるQD化合物を含有する
樹脂組成物の現像液としては、例えば水酸化ナトリウム
、水酸化カリウム、炭酸ナトリウム、珪酸ナトリウム、
メタ珪酸ナトリウム、アンモニア水等の無機アルカリ類
、エチルアミン、n−プロピルアミン等の第1級アミン
類、ジエチルアミン、ジ−n−プロピルアミン等の第2
級アミン類、トリエチルアミン、メチルジエチルアミン
等の第3級アミン類、ジメチルエタノールアミン、トリ
エタノールアミン等のアルコールアミン類、テトラメチ
ルアンモニウムヒドロキシド、テトラエチルアンモニウ
ムヒドロキシド等の第4級アンモニウム塩、またはビロ
ール、ピペリジン、1゜8−ジアザビシクロ(5,4,
0) −7−ウンデセン、1.5−ジアザビシクロ(4
,3,0)−5−ノナン等の環状アミン類を熔解してな
るアルカリ性水溶液が使用される。Examples of the developer for the resin composition containing the QD compound obtained by the production method of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate,
Inorganic alkalis such as sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and secondary amines such as diethylamine and di-n-propylamine.
amines, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, or virol, Piperidine, 1°8-diazabicyclo(5,4,
0) -7-undecene, 1,5-diazabicyclo(4
An alkaline aqueous solution prepared by dissolving a cyclic amine such as ,3,0)-5-nonane is used.
また前記現像液に水溶性有機溶媒、例えばメタノール、
エタノール等のアルコール類や界面活性剤を適量添加し
た水溶液を現像液として使用することもできる。Further, the developer may contain a water-soluble organic solvent, such as methanol,
An aqueous solution containing an appropriate amount of an alcohol such as ethanol or a surfactant can also be used as the developer.
次に、実施例を挙げて本発明をさらに具体的に説明する
が、本発明はこれらの実施例によって何ら制約されるも
のではない。Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited in any way by these Examples.
実施例1
(1)攪拌器、滴下ロートおよび温度針付きの5Q Q
m 12セパラブルフラスコに、遮光下にポリヒドロ
キシ化合物としてエチレングリコールージ(3,4,5
−)リヒドロキシベンゾエート) (H)8.9g、
1.2−キノンジアジド化剤として1゜2−ナフトキノ
ンジアジド−5−スルホン酸クロリド〔Q〕 32.6
g (〔Q〕 / (H) =5 Cモル比〕)、ア
シル化剤としてプロピオン酸クロリド〔A〕 2.3
g (〔A〕 / 〔Q〕 =0.1710.83〔モ
ル比〕)および溶媒としてジオキサン240gを仕込み
、攪拌しながら溶解した。さらに滴下ロートに16.2
gのトリエチルアミンを仕込んだ。Example 1 (1) 5Q Q with stirrer, dropping funnel and temperature needle
Into a 12 separable flask, add ethylene glycol di(3,4,5
-) hydroxybenzoate) (H) 8.9 g,
1.2-Naphthoquinonediazide-5-sulfonic acid chloride [Q] 32.6 as a 2-quinonediazide agent
g ([Q] / (H) = 5 C molar ratio]), propionic acid chloride [A] as acylating agent 2.3
g ([A] / [Q] = 0.1710.83 [molar ratio]) and 240 g of dioxane as a solvent were charged and dissolved with stirring. Further add 16.2 to the dropping funnel.
g of triethylamine was charged.
セパラブルフラスコを30℃にコントロールされた水浴
に浸し、内温か30℃一定となった時点でこの溶液にト
リエチルアミンを内温か35℃を超えないようにゆっく
りと滴下した。その後、析出したトリエチルアミン塩酸
塩を濾過して除き、濾液を大量の希塩酸中に注ぎこんで
、QD化合物を析出させた。析出物を回収し、40℃に
コントロールされた加熱真空乾燥器で一昼夜乾燥した。The separable flask was immersed in a water bath controlled at 30°C, and when the internal temperature became constant at 30°C, triethylamine was slowly added dropwise to this solution so that the internal temperature did not exceed 35°C. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of diluted hydrochloric acid to precipitate the QD compound. The precipitate was collected and dried in a heated vacuum dryer controlled at 40° C. all day and night.
得られたQD化合物の収率は98%であった。The yield of the QD compound obtained was 98%.
(2)攪拌器付きの2βセパラブルフラスコに、遮光下
、m−クレゾール336g、p−クレゾール224g、
37重量%、ホルムアルデヒド水溶液400gおよびシ
ュウ酸0.24 gを仕込み、100℃で3時間線合重
合させた後加熱処理して得られるノボラック樹脂260
g、(1)で得られたQD化合物39g1エチルセロソ
ルブアセテート720gおよびγ−ブチロラクトン18
0gを加え、室温でよく攪拌して熔解した。溶解後、孔
径0.2μmのメンブランフィルタで濾過し、組成物の
溶液を調製した。調製直後の溶液の異物の数を自動微粒
子計測器で測定したところ、0.5μm以上の異物の数
は10(llil/mI2であった。次に溶液を40℃
にコントロールされた恒温槽に入れ1ケ月間保存したと
ころ、自動微粒子計測器で測定した0、 5μm以上の
異物の数は15個/mβとほとんど増加しなかった。ま
た、レジストとしての性能評価を実施したところ、40
℃での保存安定性テストを始める前のものと、後のもの
での感度および残膜率に変化がなく、保存安定性が高い
ことがわかった。(2) In a 2β separable flask equipped with a stirrer, 336 g of m-cresol, 224 g of p-cresol,
37% by weight, 400 g of formaldehyde aqueous solution and 0.24 g of oxalic acid were prepared, linear polymerization was carried out at 100°C for 3 hours, and then heat treatment was performed to obtain Novolac resin 260.
g, 39 g of the QD compound obtained in (1), 720 g of ethyl cellosolve acetate and 18 g of γ-butyrolactone.
0 g was added and stirred thoroughly at room temperature to dissolve. After dissolution, it was filtered through a membrane filter with a pore size of 0.2 μm to prepare a solution of the composition. When the number of foreign particles in the solution immediately after preparation was measured using an automatic particle counter, the number of foreign particles larger than 0.5 μm was 10 (llil/mI2).Then, the solution was heated at 40°C.
When stored for one month in a thermostatically controlled oven, the number of foreign particles larger than 0.5 μm measured using an automatic particulate counter was 15 particles/mβ, which showed almost no increase. In addition, when we conducted a performance evaluation as a resist, we found that 40
There was no change in the sensitivity or residual film rate between the sample before and after the storage stability test at ℃, indicating that the sample had high storage stability.
比較例1
攪拌器、滴下ロートおよび温度計付きの500mβセパ
ラブルフラスコに、遮光下にエチレングリコールージ(
3,4,5−トリヒドロキシヘンシェード)(H)9.
7g、1.2−ナフトキノンジアジド−5−スルポン酸
りロリド(Q335.6g (〔Q〕 / (H) =
5 (モル比))およびジオキサン240gを仕込み、
攪拌しながら溶解した。Comparative Example 1 Into a 500 m β separable flask equipped with a stirrer, dropping funnel, and thermometer, ethylene glycol rouge (
3,4,5-trihydroxyhenshade) (H)9.
7g, 1.2-naphthoquinonediazide-5-sulfonic acid chloride (Q335.6g ([Q] / (H) =
5 (molar ratio)) and 240 g of dioxane,
Dissolved with stirring.
さらに滴下ロートに14.7gのトリエチルアミンを仕
込んだ。実施例1 (1)と同様にトリエチルアミンを
滴下しながら反応させた後、生成物を回収し、乾燥して
アシル化されていないQD化合物を得た。Furthermore, 14.7 g of triethylamine was charged into the dropping funnel. Example 1 After reacting while dropping triethylamine in the same manner as in (1), the product was collected and dried to obtain a non-acylated QD compound.
次に実施例1 (2)で使用したQD化合物に替え、前
記のQD化合物を使用した他は実施例1 (2)と同様
にして組成物の溶液を調製した。調製直後の溶液の異物
の数を自動微粒子計測器で測定したところ、0.5μm
以上の異物の数は15個/mlであった。次に溶液を4
0℃にコントロールされた恒温槽に入れ1ケ月間保存し
たところ、自動微粒子計測器で測定した0、5μm以上
の異物の数は1200個/ m lと増加していた。Next, a solution of the composition was prepared in the same manner as in Example 1 (2) except that the QD compound described above was used instead of the QD compound used in Example 1 (2). When the number of foreign particles in the solution immediately after preparation was measured using an automatic particle counter, it was found to be 0.5 μm.
The number of foreign substances was 15/ml. Then add the solution to 4
When stored in a constant temperature bath controlled at 0°C for one month, the number of foreign particles larger than 0.5 μm measured using an automatic particle counter increased to 1200 pieces/ml.
実施例2〜lO
実施例1 (1)でアシル化剤として使用したプロピオ
ン酸クロリドに替えて、〔A〕/ 〔Q〕=0.171
0.83〔モル比〕となる条件で第1表に示すアシル化
剤またはスルホニル化剤〔A〕を使用した他は実施例1
(1)と同様にしてQD化合物を得た。次にこれらQ
D化合物を用い、それぞれ実施例1 (2)と同様にし
て組成物の溶液を調製した。ti!l!直後と40℃で
1ケ月間恒温槽中で保存した各々の溶液につき、0.5
μm以上の異物の数を自動微粒子計測器で測定したとこ
ろ、いずれの溶液にも異物の増加は認められなかった。Examples 2 to 1O Example 1 In place of the propionic acid chloride used as the acylating agent in (1), [A]/[Q]=0.171
Example 1 except that the acylating agent or sulfonylating agent [A] shown in Table 1 was used under conditions such that the molar ratio was 0.83 [molar ratio].
A QD compound was obtained in the same manner as in (1). Next, these Q
Using Compound D, solutions of the compositions were prepared in the same manner as in Example 1 (2). Ti! l! 0.5 for each solution immediately and stored in a constant temperature bath at 40°C for 1 month.
When the number of foreign particles of μm or larger was measured using an automatic particle counter, no increase in foreign particles was observed in any of the solutions.
結果を第1表に示す。The results are shown in Table 1.
以下余白
第 1 表
廻
ニ]」
実施例11〜18
ポリヒドロキシ化合物(H)として第2表に示す化合物
を選び、その他は実施例1 (1)と同様にしてQD化
合物を得た。次にこれらのQD化合物を使用し、それぞ
れ実施例1 (2)と同様にして組成物の溶液を調製し
た。調製直後と40℃で1ケ月間恒温槽中で保存した各
々の溶液につき、0、5μm以上の異物の数を自動微粒
子計測器で測定したところ、いずれの溶液にも異物の数
の増加は認められなかった。結果を第2表に示す。Examples 11 to 18 QD compounds were obtained in the same manner as in Example 1 (1) except that the compounds shown in Table 2 were selected as polyhydroxy compounds (H). Next, using these QD compounds, composition solutions were prepared in the same manner as in Example 1 (2). When the number of foreign particles of 0.5 μm or larger was measured using an automatic particle counter for each solution immediately after preparation and stored in a constant temperature bath at 40°C for one month, no increase in the number of foreign particles was observed in any of the solutions. I couldn't. The results are shown in Table 2.
以下余白
実施例19
攪拌器、滴下ロートおよび温度針付きの500m1セパ
ラブルフラスコに、遮光下にポリヒドロキシ化合物とし
てエチレングリコールージ(3゜4.5−)リヒドロキ
シベンゾエート)(H)8゜9g1アシル化剤としてプ
ロピオン酸クロリド〔A)2.3gおよびジオキサン1
00gを仕込み、攪拌しながら溶解した。さらに滴下ロ
ートに16゜2gのトリエチルアミンを仕込んだ。実施
例1 (1)と同様にトリエチルアミンを滴下しながら
反応させた後、反応溶液を30分攪拌した。さらに滴下
ロートに1,2−キノンジアジド化剤として1.2−ナ
フトキノンジアジド−5−スルホン酸クロリド32.6
g (〔Q〕/ (H)=5 Cモル比〕、〔A〕 /
〔Q〕 =0.1 ’I10.83 (モル比〕)お
よびジオキサン140gから調製した溶液を仕込んだ。Example 19 In a 500 ml separable flask equipped with a stirrer, a dropping funnel and a temperature needle, 8°9 g of ethylene glycol di(3°4.5-)lihydroxybenzoate) (H) (1 acyl) was added as a polyhydroxy compound under the cover of light. 2.3 g of propionic acid chloride [A] and 1 dioxane as a curing agent.
00g was charged and dissolved while stirring. Furthermore, 16.2 g of triethylamine was charged into the dropping funnel. Example 1 After reacting while dropping triethylamine in the same manner as in (1), the reaction solution was stirred for 30 minutes. Furthermore, 32.6 liters of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was added to the dropping funnel as a 1,2-quinonediazide agent.
g ([Q]/(H)=5C molar ratio], [A]/
A solution prepared from [Q]=0.1'I10.83 (molar ratio) and 140 g of dioxane was charged.
セパラブルフラスコを30℃にコントロールされた水浴
に浸し、内温か30℃一定となった時点でこの反応溶液
に前記調製溶液を内温か35℃を超えないようにゆっく
りと滴下しながら反応させた後、生成物を回収し、乾燥
してQD化合物を得た。得られたQD化合物の収率は9
7%であった。The separable flask was immersed in a water bath controlled at 30°C, and when the internal temperature became constant at 30°C, the prepared solution was slowly added dropwise to the reaction solution so that the internal temperature did not exceed 35°C. , the product was collected and dried to obtain the QD compound. The yield of the QD compound obtained was 9
It was 7%.
次に前記QD化合物を用い、実施例1 (2)と同様に
して組成物の溶液を開裂した。調製直後の溶液の異物の
数を自動微粒子計測器で測定したところ、0.5μm以
上の異物の数は13個/mlであった。次に溶液を40
℃にコントロールされた恒温槽に入れ1ケ月間保存した
ところ、自動微粒子計測器で測定した0、5μm以上の
異物の数は21(固/m1と異物の増加はほとんど認め
られなかった。Next, the solution of the composition was cleaved using the QD compound in the same manner as in Example 1 (2). When the number of foreign substances in the solution immediately after preparation was measured using an automatic particle counter, the number of foreign substances with a diameter of 0.5 μm or more was 13 pieces/ml. Then add 40% of the solution
When stored in a constant temperature bath controlled at ℃ for one month, the number of foreign particles of 0.5 μm or more was measured with an automatic particle counter to 21 (hard/m1, and almost no increase in the number of foreign particles was observed.
実施例20
攪拌器、滴下ロートおよび温度計付きの500m1lセ
パラブルフラスコに、遮光下にポリヒドロキシ化合物と
してエチレングリコールージ(3゜4.5−1−リヒド
ロキシベンゾエート)(H)8゜9g、1.2−キノン
ジアジド化剤として1,2−ナフトキノンジアジド−5
−スルホン酸クロリド〔Q〕 32.6 g (〔Q〕
/ (H) =5 Cモル比〕)およびジオキサン2
40gを仕込み、攪拌しながら溶解した。さらに滴下ロ
ートに16.2 gのトリエチルアミンを仕込んだ。実
施例1 (1)と同様にトリエチルアミンを滴下しなが
ら反応させた後、反応溶液を30分攪拌した。さらに滴
下ロートにアシル化剤としてプロピオン酸クロリド〔A
) 2.3 g (〔A〕 / 〔Q〕 =0.171
0.83 (モル比〕)を仕込んだ。セパラブルフラ
スコを30℃にコントロールされた水浴に浸し、内温か
30℃一定となった時点でこの反応溶液に前記アシル化
剤を内温か35℃を超えないようにゆっくりと滴下しな
がら反応させた後、生成物を回収し、乾燥してQD化合
物を得た。得られたQD化合物の収率は98%であった
。Example 20 Into a 500ml separable flask equipped with a stirrer, a dropping funnel and a thermometer, 8°9 g of ethylene glycoluge (3°4.5-1-lyhydroxybenzoate) (H) as a polyhydroxy compound was added under protection from light. .1,2-naphthoquinonediazide-5 as a 2-quinonediazidating agent
-Sulfonic acid chloride [Q] 32.6 g ([Q]
/ (H) = 5 C molar ratio]) and dioxane 2
40g was charged and dissolved while stirring. Furthermore, 16.2 g of triethylamine was charged into the dropping funnel. Example 1 After reacting while dropping triethylamine in the same manner as in (1), the reaction solution was stirred for 30 minutes. Furthermore, propionic acid chloride [A] was added to the dropping funnel as an acylating agent.
) 2.3 g ([A] / [Q] =0.171
0.83 (molar ratio) was charged. The separable flask was immersed in a water bath controlled at 30°C, and when the internal temperature became constant at 30°C, the acylating agent was slowly added dropwise to the reaction solution so that the internal temperature did not exceed 35°C. After that, the product was collected and dried to obtain a QD compound. The yield of the QD compound obtained was 98%.
次に前記QD化合物を用い、実施例1 (2)と同様に
して組成物の溶液をm製した。調製直後の溶液の異物の
数を自動微粒子計測器で測定したところ、0.5μm以
上の異物の数は12個/ m lであった。次に溶液を
40℃にコントロールされた恒温槽に入れ1ケ月間保存
したところ、自動微粒子計測器で測定した0、 5μm
以上の異物の数は15個/ m lと異物の増加はほと
んど認められなかった。Next, using the QD compound, a solution of the composition was prepared in the same manner as in Example 1 (2). When the number of foreign particles in the solution immediately after preparation was measured using an automatic particle counter, the number of foreign particles with a diameter of 0.5 μm or more was 12 pieces/ml. Next, the solution was stored in a constant temperature bath controlled at 40°C for one month, and the particle size was 0.5 μm as measured with an automatic particle counter.
The number of foreign substances was 15 pieces/ml, and almost no increase in foreign substances was observed.
(発明の効果)
本発明の製造方法により得られる特定の1,2−キノン
ジアジド化合物は、これとアルカリ可溶性樹脂を使用す
ることにより、異物の発生が極めて少なく、かつレジス
トパターン形成の際の解像性および集積回路作製時の歩
留りを向上させることができるポジ型レジストとして好
適な感放射線性樹脂組成物を得ることができる。(Effects of the Invention) By using the specific 1,2-quinonediazide compound obtained by the production method of the present invention and an alkali-soluble resin, the generation of foreign matter is extremely small, and the resolution during resist pattern formation is improved. It is possible to obtain a radiation-sensitive resin composition suitable as a positive resist that can improve the properties and yield during the production of integrated circuits.
Claims (1)
シル化剤および/またはスルホニル化剤と反応させてア
シル化および/またはスルホニル化した後、さらにポリ
ヒドロキシ化合物の残りの水酸基の一部または全部を1
,2−キノンジアジド化剤と反応させて1,2−キノン
ジアジド化するか、 (b)ポリヒドロキシ化合物の水酸基の一部または全部
にアシル化剤および/またはスルホニル化剤と1,2−
キノンジアジド化剤とを、反応させてアシル化および/
またはスルホニル化と同時に1,2−キノンジアジド化
するか、または (c)ポリヒドロキシ化合物の水酸基の一部を1,2−
キノンジアジド化剤と反応させて1,2−キノンジアジ
ド化した後、さらにポリヒドロキシ化合物の残りの水酸
基の一部または全部をアシル化剤および/またはスルホ
ニル化剤と反応させてアシル化および/またはスルホニ
ル化する工程を含み、かつ、アシル化剤、スルホニル化
剤および1,2−キノンジアジド化剤の総使用量をポリ
ヒドロキシ化合物の水酸基1グラム当量に対して0.3
モル以上とし、アシル化剤および/またはスルホニル化
剤〔A〕と1,2−キノンジアジド化剤〔Q〕との使用
割合を〔A〕/〔Q〕=0.01/0.99〜0.7/
0.3〔モル比〕とすることを特徴とする1,2−キノ
ンジアジド化合物の製造方法。(1) (a) After reacting a part of the hydroxyl group of the polyhydroxy compound with an acylating agent and/or a sulfonylating agent to acylate and/or sulfonylate it, further part of the remaining hydroxyl group of the polyhydroxy compound or all 1
, 2-quinonediazidating agent to form 1,2-quinonediazide, or (b) some or all of the hydroxyl groups of the polyhydroxy compound are reacted with an acylating agent and/or a sulfonylating agent to form 1,2-quinonediazide.
acylation and/or reaction with a quinone diazidating agent.
or 1,2-quinonediazide at the same time as sulfonylation, or (c) some of the hydroxyl groups of the polyhydroxy compound are 1,2-
After reacting with a quinone diazidating agent to form 1,2-quinone diazidation, some or all of the remaining hydroxyl groups of the polyhydroxy compound are further reacted with an acylating agent and/or a sulfonylating agent to form acylation and/or sulfonylation. and the total amount of the acylating agent, sulfonylating agent, and 1,2-quinone diazidizing agent is 0.3 per gram equivalent of hydroxyl group of the polyhydroxy compound.
The ratio of the acylating agent and/or sulfonylating agent [A] and the 1,2-quinonediazidating agent [Q] is set to be at least 1 mol [A]/[Q]=0.01/0.99 to 0. 7/
A method for producing a 1,2-quinonediazide compound, characterized in that the molar ratio is 0.3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1689286A JPS62178562A (en) | 1986-01-30 | 1986-01-30 | Production of 1,2-quinonediazide compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1689286A JPS62178562A (en) | 1986-01-30 | 1986-01-30 | Production of 1,2-quinonediazide compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62178562A true JPS62178562A (en) | 1987-08-05 |
JPH0583543B2 JPH0583543B2 (en) | 1993-11-26 |
Family
ID=11928808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1689286A Granted JPS62178562A (en) | 1986-01-30 | 1986-01-30 | Production of 1,2-quinonediazide compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62178562A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63110446A (en) * | 1986-10-29 | 1988-05-14 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JPH01156738A (en) * | 1987-12-15 | 1989-06-20 | Japan Synthetic Rubber Co Ltd | Radiation sensitive resin composition |
EP0565006A2 (en) | 1992-04-06 | 1993-10-13 | Fuji Photo Film Co., Ltd. | Method for preparing PS plate |
EP0710886A1 (en) | 1994-10-31 | 1996-05-08 | Fuji Photo Film Co., Ltd. | Positive photoresist composition |
JP2018154625A (en) * | 2008-07-21 | 2018-10-04 | ユニゲン・インコーポレーテッド | Series of skin whitening (lightening) compounds |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4407926A (en) * | 1980-11-21 | 1983-10-04 | Hoechst Aktiengesellschaft | Light-sensitive mixture comprising O-naphthoquinone-diazides and light sensitive copying material prepared therefrom |
US4409314A (en) * | 1980-10-24 | 1983-10-11 | Hoechst Aktiengesellschaft | Light-sensitive compounds, light-sensitive mixture, and light-sensitive copying material prepared therefrom |
EP0167778A1 (en) * | 1984-06-08 | 1986-01-15 | Hoechst Aktiengesellschaft | Derivatives of 1,2-naphthoquinone diazide containing perfluoralkyl groups, and reproduction material containing these compounds |
-
1986
- 1986-01-30 JP JP1689286A patent/JPS62178562A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4409314A (en) * | 1980-10-24 | 1983-10-11 | Hoechst Aktiengesellschaft | Light-sensitive compounds, light-sensitive mixture, and light-sensitive copying material prepared therefrom |
US4407926A (en) * | 1980-11-21 | 1983-10-04 | Hoechst Aktiengesellschaft | Light-sensitive mixture comprising O-naphthoquinone-diazides and light sensitive copying material prepared therefrom |
EP0167778A1 (en) * | 1984-06-08 | 1986-01-15 | Hoechst Aktiengesellschaft | Derivatives of 1,2-naphthoquinone diazide containing perfluoralkyl groups, and reproduction material containing these compounds |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63110446A (en) * | 1986-10-29 | 1988-05-14 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JPH01156738A (en) * | 1987-12-15 | 1989-06-20 | Japan Synthetic Rubber Co Ltd | Radiation sensitive resin composition |
EP0565006A2 (en) | 1992-04-06 | 1993-10-13 | Fuji Photo Film Co., Ltd. | Method for preparing PS plate |
EP0710886A1 (en) | 1994-10-31 | 1996-05-08 | Fuji Photo Film Co., Ltd. | Positive photoresist composition |
JP2018154625A (en) * | 2008-07-21 | 2018-10-04 | ユニゲン・インコーポレーテッド | Series of skin whitening (lightening) compounds |
Also Published As
Publication number | Publication date |
---|---|
JPH0583543B2 (en) | 1993-11-26 |
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