JP6328350B2 - Novolac resin and resist material - Google Patents
Novolac resin and resist material Download PDFInfo
- Publication number
- JP6328350B2 JP6328350B2 JP2017541403A JP2017541403A JP6328350B2 JP 6328350 B2 JP6328350 B2 JP 6328350B2 JP 2017541403 A JP2017541403 A JP 2017541403A JP 2017541403 A JP2017541403 A JP 2017541403A JP 6328350 B2 JP6328350 B2 JP 6328350B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- novolak
- compound
- group
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920003986 novolac Polymers 0.000 title claims description 113
- 239000000463 material Substances 0.000 title claims description 14
- 229920005989 resin Polymers 0.000 claims description 136
- 239000011347 resin Substances 0.000 claims description 136
- -1 aldehyde compound Chemical class 0.000 claims description 114
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 90
- 239000000203 mixture Substances 0.000 claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 58
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 39
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 35
- 238000004519 manufacturing process Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- 150000002989 phenols Chemical class 0.000 description 21
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 17
- 229930003836 cresol Natural products 0.000 description 17
- 238000003860 storage Methods 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 14
- 229920000647 polyepoxide Polymers 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- 239000003513 alkali Substances 0.000 description 12
- 230000007774 longterm Effects 0.000 description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 238000000206 photolithography Methods 0.000 description 6
- 230000036211 photosensitivity Effects 0.000 description 6
- 229960001755 resorcinol Drugs 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229940100630 metacresol Drugs 0.000 description 4
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 150000003739 xylenols Chemical class 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 3
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 2
- XGQJGMGAMHFMAO-UHFFFAOYSA-N 1,3,4,6-tetrakis(methoxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound COCN1C(=O)N(COC)C2C1N(COC)C(=O)N2COC XGQJGMGAMHFMAO-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 2
- BOGFHOWTVGAYFK-UHFFFAOYSA-N 1-[2-(2-propoxyethoxy)ethoxy]propane Chemical compound CCCOCCOCCOCCC BOGFHOWTVGAYFK-UHFFFAOYSA-N 0.000 description 2
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- CPEXFJVZFNYXGU-UHFFFAOYSA-N 2,4,6-trihydroxybenzophenone Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC=CC=C1 CPEXFJVZFNYXGU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- GXYCPGOCXLHIAT-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxyphenyl)-(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=C(C2CCCCC2)C=CC=1)O)C1=CC=CC(C2CCCCC2)=C1O GXYCPGOCXLHIAT-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 2
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical group OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-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
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- 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
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
-
- 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
- G03F7/20—Exposure; Apparatus therefor
Description
本発明は、耐熱性が非常に高く、様々な温度条件での長期保存安定性にも優れるノボラック型樹脂、これを含有する感光性組成物、硬化性組成物、及びレジスト材料に関する。 The present invention relates to a novolac resin having very high heat resistance and excellent long-term storage stability under various temperature conditions, a photosensitive composition containing the same, a curable composition, and a resist material.
ノボラック型樹脂等のフェノール性水酸基含有樹脂は、接着剤、成形材料、塗料、フォトレジスト材料、エポキシ樹脂原料、エポキシ樹脂用硬化剤等に用いられている他、硬化物における耐熱性や耐湿性などに優れることから、フェノール性水酸基含有樹脂自体を主剤とする硬化性組成物として、或いは、エポキシ樹脂等の硬化剤として、半導体封止材やプリント配線板用絶縁材料等の電気・電子分野で幅広く用いられている。 Phenolic hydroxyl group-containing resins such as novolak resins are used in adhesives, molding materials, paints, photoresist materials, epoxy resin raw materials, epoxy resin curing agents, etc., as well as heat resistance and moisture resistance in cured products As a curable composition mainly composed of a phenolic hydroxyl group-containing resin itself, or as a curing agent such as an epoxy resin, it is widely used in the electrical and electronic fields such as semiconductor sealing materials and insulating materials for printed wiring boards. It is used.
このうちフォトレジストの分野では、用途や機能に応じて細分化された多種多様なレジストパターン形成方法が次々に開発されており、それに伴い、レジスト用樹脂材料に対する要求性能も高度化かつ多様化している。例えば、高集積化された半導体に微細なパターンを正確かつ高い生産効率で形成するための高い現像性はもちろんのこと、厚膜形成する場合には硬化物が柔軟で割れにくい等の性能が必要であり、レジスト下層膜に用いる場合にはドライエッチング耐性や耐熱性等が要求され、また、レジスト永久膜に用いる場合には耐熱性に加え、基材追従性等の靱性が要求される。更に、品質信頼性の観点から、世界各国の様々な環境下での長期保存安定性も重要な性能の一つである。 Among these, in the field of photoresists, a wide variety of resist pattern formation methods that have been subdivided according to applications and functions have been developed one after another, and as a result, the required performance for resist resin materials has become more sophisticated and diversified. Yes. For example, in addition to high developability to form fine patterns accurately and with high production efficiency on highly integrated semiconductors, it is necessary to have properties such as cured products that are flexible and resistant to cracking when forming thick films. When used as a resist underlayer film, dry etching resistance and heat resistance are required, and when used as a resist permanent film, toughness such as substrate followability is required in addition to heat resistance. Furthermore, from the viewpoint of quality and reliability, long-term storage stability in various environments around the world is one of the important performances.
現像性や耐熱性に優れるレジスト用樹脂材料として、例えば、クレゾールやキシレノール等のアルキルフェノールと、ジヒドロキシベンゼンとからなるノボラック型樹脂が知られている(下記特許文献1、2参照)。これらのノボラック型樹脂はアルカリ溶解性及び光感度が高く、解像度の高いレジストパターンが得られる点で優れる樹脂材料であるが、耐熱性が低く、また、比較的高い温度条件下での長期保存安定性も十分なものではなかったため、これらの性能を兼備する樹脂材料の開発が求められていた。 As a resist resin material excellent in developability and heat resistance, for example, a novolak resin composed of alkylphenol such as cresol and xylenol and dihydroxybenzene is known (see Patent Documents 1 and 2 below). These novolak resins are excellent in terms of alkali solubility and photosensitivity, and are excellent in terms of obtaining resist patterns with high resolution, but they have low heat resistance and long-term storage stability under relatively high temperature conditions. Since the properties were not sufficient, development of a resin material having these performances was required.
したがって、本発明が解決しようとする課題は、現像性や光感度に優れるのみならず、耐熱性が非常に高く、様々な温度条件での長期保存安定性にも優れるノボラック型樹脂、これを含有する感光性組成物、硬化性組成物、及びレジスト材料を提供することにある。 Therefore, the problem to be solved by the present invention is a novolak resin that not only has excellent developability and photosensitivity, but also has extremely high heat resistance and excellent long-term storage stability under various temperature conditions, and contains this The present invention provides a photosensitive composition, a curable composition, and a resist material.
本発明者らは上記課題を解決するため鋭意検討を行った結果、フェノールとポリヒドロキシベンゼンとを反応原料とするノボラック型樹脂は、耐熱性が非常に高く、また、様々な温度条件での長期保存安定性にも優れることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that novolac resins using phenol and polyhydroxybenzene as reaction raw materials have extremely high heat resistance, and have long-term performance under various temperature conditions. The inventors have found that the storage stability is excellent, and have completed the present invention.
即ち、本発明は、フェノール、ポリヒドロキシベンゼン化合物(A)、及びアルデヒド化合物(B)を必須の反応原料とすることを特徴とするノボラック型樹脂に関する。 That is, the present invention relates to a novolac resin characterized by using phenol, polyhydroxybenzene compound (A), and aldehyde compound (B) as essential reaction raw materials.
本発明は更に、前記ノボラック型樹脂と感光剤とを含有する感光性組成物に関する。 The present invention further relates to a photosensitive composition containing the novolac resin and a photosensitive agent.
本発明は更に、前記感光性組成物からなるレジスト材料に関する。 The present invention further relates to a resist material comprising the photosensitive composition.
本発明は更に、前記ノボラック型樹脂と硬化剤とを含有する硬化性組成物に関する。 The present invention further relates to a curable composition containing the novolac resin and a curing agent.
本発明は更に、前記硬化性組成物の硬化物に関する。 The present invention further relates to a cured product of the curable composition.
本発明は更に、前記硬化性組成物からなるレジスト材料に関する。 The present invention further relates to a resist material comprising the curable composition.
本発明によれば、耐熱性が非常に高く、様々な温度条件での長期保存安定性にも優れるノボラック型樹脂、これを含有する感光性組成物、硬化性組成物、及びレジスト材料を提供することができる。 According to the present invention, there are provided a novolac resin having very high heat resistance and excellent long-term storage stability under various temperature conditions, a photosensitive composition containing the same, a curable composition, and a resist material. be able to.
本発明のノボラック型樹脂は、フェノール、ポリヒドロキシベンゼン化合物(A)、及びアルデヒド化合物(B)を必須の反応原料とすることを特徴とする。 The novolak type resin of the present invention is characterized by using phenol, polyhydroxybenzene compound (A), and aldehyde compound (B) as essential reaction raw materials.
前記ポリヒドロキシベンゼン化合物(A)は、ベンゼン環上にフェノール性水酸基を複数有する化合物であれば何れの化合物でもよく、フェノール性水酸基の置換位置や、その他の置換基の有無等は特に限定されない。また、ポリヒドロキシベンゼン化合物(A)は一種類を単独で用いてもよいし、2種類以上を併用して用いてもよい。ポリヒドロキシベンゼン化合物(A)の具体例としては、例えば、下記構造式(2) The polyhydroxybenzene compound (A) may be any compound as long as it has a plurality of phenolic hydroxyl groups on the benzene ring, and the substitution position of the phenolic hydroxyl group and the presence or absence of other substituents are not particularly limited. Moreover, a polyhydroxybenzene compound (A) may be used individually by 1 type, and may be used in combination of 2 or more types. Specific examples of the polyhydroxybenzene compound (A) include, for example, the following structural formula (2)
で表される分子構造を有する化合物等が挙げられる。
The compound etc. which have the molecular structure represented by these are mentioned.
前記構造式(2)中のR2は、脂肪族炭化水素基、アルコキシ基、アリール基の何れかである。前記脂肪族炭化水素基は、直鎖型でも分岐型であってもよく、構造中に不飽和結合を有していてもよい。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、t−ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、ノニル基のアルキル基やシクロへキシル基等のシクロアルキル基等が挙げられる。前記アルコキシ基は、例えば、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、t−ブトキシ基等が挙げられる。前記アリール基は、例えば、フェニル基、トリル基、キシリル基、ナフチル基、アントリル基、及びこれらの芳香核上にアルキル基やアルコキシ基、ハロゲン原子等が置換した構造部位等が挙げられる。中でも、耐熱性に優れるノボラック型樹脂となることから、R2は炭素原子数1〜6のアルキル基であることが好ましく、nが0であるものがより好ましい。R 2 in the structural formula (2) is an aliphatic hydrocarbon group, an alkoxy group, or an aryl group. The aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond in the structure. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group alkyl group, cyclohexyl group, etc. A cycloalkyl group etc. are mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a t-butoxy group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, and a structural site in which an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on the aromatic nucleus. Especially, since it becomes a novolak-type resin excellent in heat resistance, R 2 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably n is 0.
前記構造式(2)中のmは2又は3である。中でも、耐熱性と長期保存安定性とに優れるノボラック型樹脂となることから、mが2であるジヒドロキシベンゼン化合物が好ましい。前記構造式(2)中の水酸基の置換位置は特に限定されない。mが2である場合には、例えば、水酸基の置換位置が1,2−位、1,3−位、1,4−位の何れかであるものが挙げられ、何れの置換位置であっても良い。中でも、耐熱性と長期保存安定性とに優れるノボラック型樹脂となることから、水酸基を1,3−位に有するレゾルシノール型の化合物であることが好ましい。 M in the structural formula (2) is 2 or 3. Especially, since it becomes a novolak-type resin excellent in heat resistance and long-term storage stability, the dihydroxybenzene compound whose m is 2 is preferable. The substitution position of the hydroxyl group in the structural formula (2) is not particularly limited. In the case where m is 2, for example, a hydroxyl group can be substituted at any one of the 1,2-position, 1,3-position, and 1,4-position. Also good. Among these, a resorcinol-type compound having a hydroxyl group at the 1,3-position is preferable because it becomes a novolak-type resin excellent in heat resistance and long-term storage stability.
本発明のノボラック型樹脂は、前記ポリヒドロキシベンゼン化合物(A)と、フェノールとを必須の原料とするが、これらと併せてその他のフェノール性水酸基含有化合物を用いても良い。その他のフェノール性水酸基含有化合物は、例えば、クレゾール、キシレノール、エチルフェノール、プロピルフェノール、イソプロピルフェノール、ブチルフェノール、t−ブチルフェノール、ペンチルフェノール、オクチルフェノール、ノニルフェノール、クミルフェノール等のアルキルフェノール;フルオロフェノール、クロロフェノール、ブロモフェノール、ヨードフェノール等のハロゲン化フェノール;フェニルフェノール等のアリールフェノール;アミノフェノール、ニトロフェノール、ジニトロフェノール、トリニトロフェノール等の官能基を有するフェノール;ナフトール、アントラセノール等の縮合多環式化合物;ジヒドロキシナフタレン、ビフェノール、ビスフェノール等のポリヒドロキシ化合物等が挙げられる。これらはそれぞれ単独で用いても良いし、2種以上を併用しても良い。 The novolak type resin of the present invention uses the polyhydroxybenzene compound (A) and phenol as essential raw materials, but other phenolic hydroxyl group-containing compounds may be used in combination with these. Other phenolic hydroxyl group-containing compounds include, for example, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, butylphenol, t-butylphenol, pentylphenol, octylphenol, nonylphenol, cumylphenol, and other alkylphenols; fluorophenol, chlorophenol, Halogenated phenols such as bromophenol and iodophenol; arylphenols such as phenylphenol; phenols having functional groups such as aminophenol, nitrophenol, dinitrophenol, and trinitrophenol; condensed polycyclic compounds such as naphthol and anthracenol And polyhydroxy compounds such as dihydroxynaphthalene, biphenol and bisphenol. These may be used alone or in combination of two or more.
これらその他のフェノール性水酸基含有化合物を用いる場合、その使用量は、耐熱性と長期保存安定性とに優れるノボラック型樹脂となることから、フェノール、前記ポリヒドロキシベンゼン化合物(A)及びその他のフェノール性水酸基含有化合物の合計、即ち、本発明のノボラック型樹脂を構成するフェノール性水酸基含有化合物の合計モル数に対し、フェノールと前記ポリヒドロキシベンゼン化合物(A)とを合計で50モル%以上用いることが好ましく、80モル%以上用いることがより好ましく、90モル%以上用いることが特に好ましい。 When these other phenolic hydroxyl group-containing compounds are used, the amount used is a novolak resin excellent in heat resistance and long-term storage stability. Therefore, phenol, the polyhydroxybenzene compound (A) and other phenolic compounds are used. Phenol and the polyhydroxybenzene compound (A) may be used in a total of 50 mol% or more based on the total number of hydroxyl group-containing compounds, that is, the total number of moles of the phenolic hydroxyl group-containing compound constituting the novolak resin of the present invention. Preferably, 80 mol% or more is used, more preferably 90 mol% or more is used.
また、ノボラック型樹脂を構成するフェノール性水酸基含有化合物の全モル数に対するフェノールの割合は、耐熱性と長期保存安定性とに優れるノボラック型樹脂となることから、50〜99モル%の範囲であることが好ましく、80〜98モル%の範囲であることがより好ましい。 In addition, the ratio of phenol to the total number of moles of the phenolic hydroxyl group-containing compound constituting the novolak type resin is in the range of 50 to 99 mol% because the novolak type resin is excellent in heat resistance and long-term storage stability. It is preferable that it is in the range of 80 to 98 mol%.
ノボラック型樹脂を構成するフェノール性水酸基含有化合物の全モル数に対する前記ポリヒドロキシベンゼン化合物(A)の割合は、耐熱性と長期保存安定性とに優れるノボラック型樹脂となることから、1〜33モル%の範囲であることが好ましく、2〜20モル%の範囲であることがより好ましい。 The ratio of the polyhydroxybenzene compound (A) with respect to the total number of moles of the phenolic hydroxyl group-containing compound constituting the novolak type resin is from 1 to 33 mol because it becomes a novolak type resin excellent in heat resistance and long-term storage stability. % Is preferable, and a range of 2 to 20 mol% is more preferable.
前記アルデヒド化合物(B)は、フェノールや前記ポリヒドロキシベンゼン化合物(A)等のフェノール水酸基含有化合物と縮合反応を生じてノボラック型樹脂を形成し得るものであればよく、例えば、ホルムアルデヒド、トリオキサン、アセトアルデヒド、プロピオンアルデヒド、テトラオキシメチレン、ポリオキシメチレン、クロラール、ヘキサメチレンテトラミン、フルフラール、グリオキザール、n−ブチルアルデヒド、カプロアルデヒド、アリルアルデヒド、ベンズアルデヒド、フェニルアセトアルデヒド、o−トルアルデヒド、サリチルアルデヒド、クロトンアルデヒド、アクロレイン等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。中でも、反応性に優れることからホルムアルデヒドを用いることが好ましい。ホルムアルデヒドは水溶液の状態であるホルマリンとして用いても、固形の状態であるパラホルムアルデヒドとして用いても、どちらでも良い。また、ホルムアルデヒドとその他のアルデヒド化合物とを併用する場合には、ホルムアルデヒド1モルに対して、その他のアルデヒド化合物を0.05〜1モルの割合で用いることが好ましい。 The aldehyde compound (B) is not particularly limited as long as it can form a novolac resin by causing a condensation reaction with a phenol hydroxyl group-containing compound such as phenol or the polyhydroxybenzene compound (A), for example, formaldehyde, trioxane, acetaldehyde. , Propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, crotonaldehyde, Examples include acrolein. These may be used alone or in combination of two or more. Among them, it is preferable to use formaldehyde because of excellent reactivity. Formaldehyde may be used either as formalin in an aqueous solution or as paraformaldehyde in a solid state. Moreover, when using together formaldehyde and another aldehyde compound, it is preferable to use another aldehyde compound in the ratio of 0.05-1 mol with respect to 1 mol of formaldehyde.
本発明のノボラック型樹脂の具体構造は特に限定されず、樹脂構造中にフェノール由来の構造部位と、前記ポリヒドロキシベンゼン化合物(A)由来の構造部位とが含まれていれば、各構造部位がどのような順序で配列していてもよい。つまり、本発明のノボラック型樹脂は、フェノール、前記ポリヒドロキシベンゼン化合物(A)、及び前記アルデヒド化合物(B)を必須の反応原料とするものであれば、どのような方法で製造されたものでもよく、具体的な製法の例としては、例えば、下記方法1〜3のような方法が挙げられる。 The specific structure of the novolak-type resin of the present invention is not particularly limited, and if the resin structure contains a structural part derived from phenol and a structural part derived from the polyhydroxybenzene compound (A), each structural part is They may be arranged in any order. That is, the novolak resin of the present invention can be produced by any method as long as it uses phenol, the polyhydroxybenzene compound (A), and the aldehyde compound (B) as essential reaction raw materials. Well, examples of specific production methods include methods such as the following methods 1 to 3.
(方法1)フェノール、前記ポリヒドロキシベンゼン化合物(A)及び必要に応じて用いるその他のフェノール性水酸基含有化合物を一括して用い、これと前記アルデヒド化合物(B)とを反応させてノボラック型樹脂を製造する方法。
(方法2)フェノール、前記ポリヒドロキシベンゼン化合物(A)及び必要に応じて用いるその他のフェノール性水酸基含有化合物をそれぞれ単独でアルデヒド化合物(B)と反応させてノボラック型樹脂中間体を製造した後、得られた各種のノボラック型樹脂中間体とアルデヒド化合物(B)とを反応させてブロック型のノボラック型樹脂を製造する方法。
(方法3)フェノール、前記ポリヒドロキシベンゼン化合物(A)及び必要に応じて用いるその他のフェノール性水酸基含有化合物のうちの一種乃至複数種と前記アルデヒド化合物(B)とを反応させてノボラック型樹脂中間体を製造し、得られたノボラック型樹脂中間体と、フェノール、前記ポリヒドロキシベンゼン化合物(A)及び必要に応じて用いるその他のフェノール性水酸基含有化合物のうち一種乃至複数種と、前記アルデヒド化合物(B)とを反応させてノボラック型樹脂を製造する方法。(Method 1) Phenol, the polyhydroxybenzene compound (A), and other phenolic hydroxyl group-containing compounds used as necessary are collectively used, and this is reacted with the aldehyde compound (B) to obtain a novolak resin. How to manufacture.
(Method 2) After the phenol, the polyhydroxybenzene compound (A) and the other phenolic hydroxyl group-containing compound used as needed are reacted with the aldehyde compound (B) alone to produce a novolak-type resin intermediate, A method of producing a block type novolak resin by reacting the obtained various novolak resin intermediates with the aldehyde compound (B).
(Method 3) Reaction of one or more of phenol, the polyhydroxybenzene compound (A) and other phenolic hydroxyl group-containing compounds used as necessary with the aldehyde compound (B) to produce a novolak resin intermediate A novolak-type resin intermediate obtained, and one or more of phenol, the polyhydroxybenzene compound (A) and other phenolic hydroxyl group-containing compounds used as necessary, and the aldehyde compound ( A method for producing a novolac resin by reacting with B).
これら様々な製造方法の中でも、耐熱性と長期保存安定性とに優れるノボラック型樹脂となることから、前記方法3にて製造されるノボラック型樹脂が好ましい。中でも、フェノールと、必要に応じて用いるその他のフェノール性水酸基含有化合物と、前記アルデヒド化合物(B)とを反応させてノボラック型樹脂中間体を製造し、得られたノボラック型樹脂中間体と、前記ポリヒドロキシベンゼン化合物(A)と、前記アルデヒド化合物(B)とを反応させる方法(以下「方法3−1」と略記する)にて得られるノボラック型樹脂が特に好ましい。 Among these various production methods, the novolak type resin produced by the method 3 is preferable because the novolak type resin is excellent in heat resistance and long-term storage stability. Among them, a novolac resin intermediate is produced by reacting phenol, other phenolic hydroxyl group-containing compound used as necessary, and the aldehyde compound (B), and the obtained novolac resin intermediate, A novolak resin obtained by a method of reacting the polyhydroxybenzene compound (A) with the aldehyde compound (B) (hereinafter abbreviated as “Method 3-1”) is particularly preferable.
前記方法1〜3について、何れの製造方法においても、各種のフェノール性水酸基含有化合物と前記アルデヒド化合物(B)との反応は、一般的なフェノールノボラック型樹脂の製造方法と同様にして行うことができる。具体的には、各種フェノール性水酸基含有化合物の合計1モルに対し、前記アルデヒド化合物(B)を0.5〜1.2モルの範囲で用い、酸触媒の存在下、50〜200℃の温度条件下で反応させる方法が挙げられる。 About said methods 1-3, in any manufacturing method, reaction with various phenolic hydroxyl group containing compounds and said aldehyde compound (B) is performed like the manufacturing method of a general phenol novolak-type resin. it can. Specifically, the aldehyde compound (B) is used in a range of 0.5 to 1.2 mol with respect to a total of 1 mol of various phenolic hydroxyl group-containing compounds, and the temperature is 50 to 200 ° C. in the presence of an acid catalyst. The method of making it react on conditions is mentioned.
前記酸触媒は、例えば、塩酸、硫酸、リン酸などの無機酸、メタンスルホン酸、パラトルエンスルホン酸、シュウ酸などの有機酸、三フッ化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸などが挙げられる。これらはそれぞれ単独で用いてもよいし、2種類以上を併用してもよい。 Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Is mentioned. These may be used alone or in combination of two or more.
各種のフェノール性水酸基含有化合物と前記アルデヒド化合物(B)との反応は、必要に応じて溶媒中で行っても良い。ここで用いる溶媒は、例えば、水;メタノール、エタノール、プロパノール、乳酸エチル、エチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,7−ヘプタンジオール、1,8−オクタンジオール、1,9−ノナンジオール、トリメチレングリコール、ジエチレングリコール、ポリエチレングリコール、グリセリン、2−エトキシエタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノペンチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールエチルメチルエーテル、エチレングリコールモノフェニルエーテル、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテル、1,3−ジオキサン、1,4−ジオキサン、テトラヒドロフラン、エチレングリコールアセテート、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、N−メチルピロリドン、ジメチルホルムアミド、ジメチルスルホキシド等が挙げられる。これらの溶媒は、それぞれ単独で用いても良いし、2種類以上の混合溶媒として用いても良い。中でも、得られるノボラック型樹脂が保存安定性の高いものとなることからプロトン性溶媒を用いることが好ましい。 You may perform reaction with various phenolic hydroxyl group containing compounds and the said aldehyde compound (B) in a solvent as needed. The solvent used here is, for example, water; methanol, ethanol, propanol, ethyl lactate, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl Tyl ether, ethylene glycol monophenyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, ethylene glycol acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone , Dimethylformamide, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more kinds. Among these, it is preferable to use a protic solvent because the resulting novolac resin has high storage stability.
反応終了後は、必要に応じて未反応原料や溶媒等を留去する工程、水洗或いは再沈殿等にて精製する工程等を行っても良い。 After completion of the reaction, a step of distilling off unreacted raw materials and solvents, a step of purification by washing with water, reprecipitation, or the like may be performed as necessary.
前記方法3−1について詳述する。まず、フェノールと、必要に応じて用いるその他のフェノール性水酸基含有化合物と、前記アルデヒド化合物(B)とを反応させてノボラック型樹脂中間体を製造する工程は、前述した一般的なフェノールノボラック型樹脂の製造方法と同様にして行うことができる。 The method 3-1 will be described in detail. First, the step of producing a novolak-type resin intermediate by reacting phenol, other phenolic hydroxyl group-containing compound used as necessary, and the aldehyde compound (B) is the same as the above-described general phenol novolak-type resin. It can carry out similarly to the manufacturing method of.
得られるノボラック型樹脂中間体は、耐熱性が高く、現像性にも優れるノボラック型樹脂となることから、その重量平均分子量(Mw)が1,000〜10,000の範囲であることが好ましく、1,000〜5,000の範囲であることがより好ましい。多分散度(Mw/Mn)は1.2〜10の範囲であることが好ましく、1.5〜5の範囲であることがより好ましい。 The obtained novolac resin intermediate is a novolak resin having high heat resistance and excellent developability, and therefore, its weight average molecular weight (Mw) is preferably in the range of 1,000 to 10,000. More preferably, it is in the range of 1,000 to 5,000. The polydispersity (Mw / Mn) is preferably in the range of 1.2 to 10, more preferably in the range of 1.5 to 5.
なお、本発明において重量平均分子量(Mw)及び多分散度(Mw/Mn)は、下記条件のGPCにて測定される値である。
[GPCの測定条件]
測定装置:東ソー株式会社製「HLC−8220 GPC」
カラム:昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF803」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF804」(8.0mmФ×300mm)
カラム温度:40℃
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC−8020モデルIIバージョン4.30」
展開溶媒:テトラヒドロフラン
流速:1.0mL/分
試料:樹脂固形分換算で0.5質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
標準試料:下記単分散ポリスチレン
(標準試料:単分散ポリスチレン)
東ソー株式会社製「A−500」
東ソー株式会社製「A−2500」
東ソー株式会社製「A−5000」
東ソー株式会社製「F−1」
東ソー株式会社製「F−2」
東ソー株式会社製「F−4」
東ソー株式会社製「F−10」
東ソー株式会社製「F−20」In the present invention, the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) are values measured by GPC under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: Filtered 0.5% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
次いで、得られたノボラック型樹脂中間体と、前記ポリヒドロキシベンゼン化合物(A)と、前記アルデヒド化合物(B)とを反応させる工程は、前記ノボラック型樹脂中間体を得る工程同様、前述した一般的なフェノールノボラック型樹脂の製造方法と同様にして行うことができる。より好ましい反応条件としては、前記ポリヒドロキシベンゼン化合物(A)1モルに対し、前記アルデヒド化合物(B)を0.5〜1.2モルの範囲で用いることが好ましい。また、反応速度や分子量の制御が容易となることから、100℃以下の比較的低温条件で反応させることが好ましく、溶媒中で反応させることが好ましい。 Next, the step of reacting the obtained novolak type resin intermediate, the polyhydroxybenzene compound (A), and the aldehyde compound (B) is the same as the above-described general step similar to the step of obtaining the novolak type resin intermediate. It can carry out similarly to the manufacturing method of a novel phenol novolak-type resin. As more preferable reaction conditions, it is preferable to use the aldehyde compound (B) in a range of 0.5 to 1.2 mol with respect to 1 mol of the polyhydroxybenzene compound (A). Moreover, since it becomes easy to control the reaction rate and the molecular weight, the reaction is preferably carried out under a relatively low temperature condition of 100 ° C. or less, and preferably in a solvent.
前記方法3−1のような方法にて本発明のノボラック型樹脂を製造した場合、得られるノボラック型樹脂は、分子末端に下記構造式(1) When the novolak resin of the present invention is produced by a method such as Method 3-1, the resulting novolak resin has the following structural formula (1) at the molecular end.
で表される構造部位(I)を有するものとなる。該構造部位(I)を分子末端に有するノボラック型樹脂は反応性が著しく高く、例えば、硬化剤と配合して硬化性組成物とした場合の硬化物における耐熱性が非常に高いものとなる。
It has a structural site (I) represented by The novolak type resin having the structural site (I) at the molecular end is extremely high in reactivity, and for example, the heat resistance in the cured product when it is blended with a curing agent to form a curable composition is very high.
本発明のノボラック型樹脂は、耐熱性が高く、現像性にも優れるノボラック型樹脂となることから、その重量平均分子量(Mw)が5,000〜30,000の範囲であることが好ましく、10,000〜30,000の範囲であることがより好ましい。多分散度(Mw/Mn)は2〜15の範囲であることが好ましく、3〜10の範囲であることがより好ましい。 Since the novolak resin of the present invention is a novolak resin having high heat resistance and excellent developability, its weight average molecular weight (Mw) is preferably in the range of 5,000 to 30,000. More preferably, it is in the range of 3,000 to 30,000. The polydispersity (Mw / Mn) is preferably in the range of 2 to 15, and more preferably in the range of 3 to 10.
以上詳述した本発明のノボラック型樹脂は耐熱性が非常に高い特徴を有することから、フォトレジストや、液晶配向膜、プリント配線基板等の各種の電気・電子部材用途の他、接着剤や塗料等にも好適に用いることが出来る。また、本発明のノボラック型樹脂はアルカリ溶解性や光感度にも優れることから、特にレジスト用途に適しており、一般的な層間絶縁膜の他、レジスト下層膜、レジスト永久膜等の様々なレジスト部材に用いることができる。 The novolac resin of the present invention described in detail above has a very high heat resistance, so that it can be used for various electrical and electronic members such as photoresists, liquid crystal alignment films, and printed wiring boards, as well as adhesives and paints. It can be suitably used for the above. In addition, the novolac resin of the present invention is particularly suitable for resist applications because it is excellent in alkali solubility and photosensitivity, and various resists such as a resist underlayer film and a resist permanent film in addition to a general interlayer insulating film. It can be used as a member.
本発明の感光性組成物は、前記本発明のノボラック型樹脂と感光剤とを必須の成分として含有する。本発明の感光性組成物は、前記本発明のノボラック型樹脂以外に、その他の樹脂(C)を併用しても良い。その他の樹脂(C)は、アルカリ現像液に可溶なもの、或いは、酸発生剤等の添加剤と組み合わせて用いることによりアルカリ現像液へ溶解するものであれば何れのものも用いることができる。 The photosensitive composition of the present invention contains the novolak resin of the present invention and a photosensitizer as essential components. The photosensitive composition of the present invention may be used in combination with other resin (C) in addition to the novolak resin of the present invention. As the other resin (C), any resin can be used as long as it is soluble in an alkali developer or can be dissolved in an alkali developer by using it in combination with an additive such as an acid generator. .
前記その他の樹脂(C)は、例えば、前記本発明のノボラック型樹脂以外のその他のフェノール樹脂(C−1)、p−ヒドロキシスチレンやp−(1,1,1,3,3,3−ヘキサフルオロ−2−ヒドロキシプロピル)スチレン等のヒドロキシ基含有スチレン化合物の単独重合体あるいは共重合体(C−2)、前記(C−1)又は(C−2)の水酸基をt−ブトキシカルボニル基やベンジルオキシカルボニル基等の酸分解性基で変性したもの(C−3)、(メタ)アクリル酸の単独重合体あるいは共重合体(C−4)、ノルボルネン化合物やテトラシクロドデセン化合物等の脂環式重合性単量体と無水マレイン酸或いはマレイミドとの交互重合体(C−5)等が挙げられる。 Examples of the other resin (C) include other phenol resins (C-1) other than the novolak resin of the present invention, p-hydroxystyrene, and p- (1,1,1,3,3,3- A homopolymer or copolymer (C-2) of a hydroxy group-containing styrene compound such as hexafluoro-2-hydroxypropyl) styrene, and the hydroxyl group of the above (C-1) or (C-2) is a t-butoxycarbonyl group Modified with an acid-decomposable group such as benzyloxycarbonyl group (C-3), homopolymer or copolymer (C-4) of (meth) acrylic acid, norbornene compound, tetracyclododecene compound, etc. Examples thereof include an alternating polymer (C-5) of an alicyclic polymerizable monomer and maleic anhydride or maleimide.
前記その他のフェノール樹脂(C−1)は、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂(ザイロック樹脂)、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ビフェニル変性フェノール樹脂(ビスメチレン基でフェノール核が連結された多価フェノール化合物)、ビフェニル変性ナフトール樹脂(ビスメチレン基でフェノール核が連結された多価ナフトール化合物)、アミノトリアジン変性フェノール樹脂(メラミン、ベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物)やアルコキシ基含有芳香環変性ノボラック樹脂(ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物)等のフェノール樹脂が挙げられる。 Examples of the other phenol resin (C-1) include phenol novolak resin, cresol novolak resin, naphthol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylock resin). ), Naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenolic resin (polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl modified naphthol resin (phenol nucleus linked by bismethylene group) Polyhydric naphthol compounds), aminotriazine-modified phenolic resins (polyhydric phenol compounds with phenolic nuclei linked by melamine, benzoguanamine, etc.) and alkoxy groups Aromatic ring-modified novolac resins (polyvalent phenolic compounds phenol nucleus and an alkoxy group-containing aromatic ring are connected by formaldehyde) and phenol resins.
前記他のフェノール樹脂(C)の中でも、感度が高く、耐熱性にも優れる感光性樹脂組成物となることから、クレゾールノボラック樹脂又はクレゾールと他のフェノール性化合物との共縮ノボラック樹脂が好ましい。クレゾールノボラック樹脂又はクレゾールと他のフェノール性化合物との共縮ノボラック樹脂は、具体的には、o−クレゾール、m−クレゾール及びp−クレゾールからなる群から選ばれる少なくとも1つのクレゾールとアルデヒド化合物とを必須原料とし、適宜その他のフェノール性化合物を併用して得られるノボラック樹脂である。 Among the other phenol resins (C), a cresol novolak resin or a co-condensed novolak resin of cresol and another phenolic compound is preferable because it is a photosensitive resin composition having high sensitivity and excellent heat resistance. The cresol novolac resin or the co-condensed novolak resin of cresol and other phenolic compound specifically includes at least one cresol selected from the group consisting of o-cresol, m-cresol and p-cresol and an aldehyde compound. It is a novolak resin obtained as an essential raw material and appropriately used in combination with other phenolic compounds.
前記クレゾール以外のその他のフェノール性化合物は、例えば、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、2,6−キシレノール、3,4−キシレノール、3,5−キシレノール等のキシレノール;o−エチルフェノール、m−エチルフェノール、p−エチルフェノール等のエチルフェノール;イソプロピルフェノール、ブチルフェノール、p−t−ブチルフェノール等のブチルフェノール;p−ペンチルフェノール、p−オクチルフェノール、p−ノニルフェノール、p−クミルフェノール等のアルキルフェノール;フルオロフェノール、クロロフェノール、ブロモフェノール、ヨードフェノール等のハロゲン化フェノール;p−フェニルフェノール、アミノフェノール、ニトロフェノール、ジニトロフェノール、トリニトロフェノール等の1置換フェノール;1−ナフトール、2−ナフトール等の縮合多環式フェノール;レゾルシン、アルキルレゾルシン、ピロガロール、カテコール、アルキルカテコール、ハイドロキノン、アルキルハイドロキノン、フロログルシン、ビスフェノールA、ビスフェノールF、ビスフェノールS、ジヒドロキシナフタリン等の多価フェノール等が挙げられる。これらその他のフェノール性化合物は、それぞれ単独で用いても良いし、2種以上を併用しても良い。これらその他のフェノール性化合物を用いる場合、その使用量は、クレゾール原料の合計1モルに対し、その他のフェノール性化合物が0.05〜1モルの範囲となる割合であることが好ましい。 Other phenolic compounds other than the cresol include, for example, phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Xylenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol, etc .; butylphenol such as isopropylphenol, butylphenol, pt-butylphenol; p-pentylphenol, p-octylphenol, p-nonylphenol, alkylphenols such as p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol and iodophenol; p-phenylphenol, aminophenol, nitrophenol, di 1-substituted phenols such as trophenol and trinitrophenol; condensed polycyclic phenols such as 1-naphthol and 2-naphthol; resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol And polyhydric phenols such as F, bisphenol S, and dihydroxynaphthalene. These other phenolic compounds may be used alone or in combination of two or more. When these other phenolic compounds are used, the amount used is preferably such that the other phenolic compound is in the range of 0.05 to 1 mol with respect to a total of 1 mol of the cresol raw material.
また、前記アルデヒド化合物は、例えば、ホルムアルデヒド、パラホルムアルデヒド、トリオキサン、アセトアルデヒド、プロピオンアルデヒド、ポリオキシメチレン、クロラール、ヘキサメチレンテトラミン、フルフラール、グリオキザール、n−ブチルアルデヒド、カプロアルデヒド、アリルアルデヒド、ベンズアルデヒド、クロトンアルデヒド、アクロレイン、テトラオキシメチレン、フェニルアセトアルデヒド、o−トルアルデヒド、サリチルアルデヒド等が挙げられ、それぞれ単独で用いても良いし、2種以上を併用しても良い。中でも、反応性に優れることからホルムアルデヒドが好ましく、ホルムアルデヒドとその他のアルデヒド化合物を併用しても構わない。ホルムアルデヒドとその他のアルデヒド化合物を併用する場合、その他のアルデヒド化合物の使用量は、ホルムアルデヒド1モルに対して、0.05〜1モルの範囲とすることが好ましい。 Examples of the aldehyde compound include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, and croton. Examples include aldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, and the like. These may be used alone or in combination of two or more. Among these, formaldehyde is preferable because of its excellent reactivity, and formaldehyde and other aldehyde compounds may be used in combination. When formaldehyde and another aldehyde compound are used in combination, the amount of the other aldehyde compound used is preferably in the range of 0.05 to 1 mol with respect to 1 mol of formaldehyde.
ノボラック樹脂を製造する際のフェノール性化合物とアルデヒド化合物との反応比率は、感度と耐熱性に優れる感光性樹脂組成物が得られることから、フェノール性化合物1モルに対しアルデヒド化合物が0.3〜1.6モルの範囲であることが好ましく、0.5〜1.3の範囲であることがより好ましい。 The reaction ratio between the phenolic compound and the aldehyde compound in producing the novolak resin is such that a photosensitive resin composition having excellent sensitivity and heat resistance is obtained, so that the aldehyde compound is 0.3 to 1 mol per mol of the phenolic compound. The range is preferably 1.6 mol, and more preferably 0.5 to 1.3.
前記フェノール性化合物とアルデヒド化合物との反応は、酸触媒存在下60〜140℃の温度条件で行い、次いで減圧条件下にて水や残存モノマーを除去する方法が挙げられる。ここで用いる酸触媒は、例えば、シュウ酸、硫酸、塩酸、フェノールスルホン酸、パラトルエンスルホン酸、酢酸亜鉛、酢酸マンガン等が挙げられ、それぞれ単独で用いても良いし、2種類以上を併用しても良い。中でも、触媒活性に優れる点からシュウ酸が好ましい。 The reaction between the phenolic compound and the aldehyde compound is carried out under a temperature condition of 60 to 140 ° C. in the presence of an acid catalyst, and then water and residual monomers are removed under a reduced pressure condition. Examples of the acid catalyst used here include oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, etc., each of which may be used alone or in combination of two or more. May be. Of these, oxalic acid is preferred because of its excellent catalytic activity.
以上詳述したクレゾールノボラック樹脂、又はクレゾールと他のフェノール性化合物との共縮ノボラック樹脂の中でも、メタクレゾールを単独で用いたクレゾールノボラック樹脂、または、メタクレゾールとパラクレゾールとを併用したクレゾールノボラック樹脂であることが好ましい。また、後者においてメタクレゾールとパラクレゾールとの反応モル比[メタクレゾール/パラクレゾール]は、感度と耐熱性とのバランスに優れる感光性樹脂組成物となることから、10/0〜2/8の範囲が好ましく、7/3〜2/8の範囲がより好ましい。 Among the cresol novolak resins detailed above or co-condensed novolak resins of cresol and other phenolic compounds, cresol novolak resins using metacresol alone or cresol novolak resins using metacresol and paracresol in combination It is preferable that In the latter case, the reaction molar ratio of metacresol to paracresol [metacresol / paracresol] is a photosensitive resin composition having an excellent balance between sensitivity and heat resistance. The range is preferable, and the range of 7/3 to 2/8 is more preferable.
前記その他の樹脂(C)を用いる場合、本発明のノボラック型樹脂とその他の樹脂(C)との配合割合は所望の用途により任意に調整することが出来る。例えば、本発明のノボラック型樹脂は耐熱性に優れ、かつ、アルカリ溶解性や光感度にも優れることから、これを主成分とする感光性組成物はレジスト用途に最適である。このとき、樹脂成分の合計における本発明のノボラック型樹脂の割合は、60質量%以上であることが好ましく、80質量%以上であることがより好ましい。 When using the said other resin (C), the compounding ratio of the novolak-type resin of this invention and other resin (C) can be arbitrarily adjusted with a desired use. For example, since the novolac resin of the present invention is excellent in heat resistance and also in alkali solubility and photosensitivity, a photosensitive composition containing this as a main component is optimal for resist applications. At this time, the ratio of the novolak resin of the present invention in the total resin component is preferably 60% by mass or more, and more preferably 80% by mass or more.
また、本発明のノボラック型樹脂が有する高い耐熱性はこれまでにない突出したレベルのものであるから、その他の樹脂(C)を主成分とする感光性組成物の耐熱性を一層向上させるために、本願発明のノボラック型樹脂を一部添加して用いても良い。この場合、本発明のノボラック型樹脂とその他の樹脂(C)との配合割合は、前記その他の樹脂(C)100質量部に対し、本発明のノボラック型樹脂が3〜80質量部の範囲であることが好ましい。 Moreover, since the high heat resistance which the novolak-type resin of the present invention has is an unprecedented level, in order to further improve the heat resistance of the photosensitive composition containing the other resin (C) as a main component. In addition, a part of the novolac resin of the present invention may be added. In this case, the blending ratio of the novolac resin of the present invention and the other resin (C) is such that the novolac resin of the present invention is in the range of 3 to 80 parts by mass with respect to 100 parts by mass of the other resin (C). Preferably there is.
前記感光剤は、例えば、キノンジアジド基を有する化合物が挙げられる。キノンジアジド基を有する化合物の具体例としては、例えば、芳香族(ポリ)ヒドロキシ化合物と、ナフトキノン−1,2−ジアジド−5−スルホン酸、ナフトキノン−1,2−ジアジド−4−スルホン酸、オルトアントラキノンジアジドスルホン酸等のキノンジアジド基を有するスルホン酸との完全エステル化合物、部分エステル化合物、アミド化物又は部分アミド化物などが挙げられる。 Examples of the photosensitive agent include compounds having a quinonediazide group. Specific examples of the compound having a quinonediazide group include, for example, an aromatic (poly) hydroxy compound, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthra Examples thereof include complete ester compounds, partial ester compounds, amidated products, and partially amidated products with sulfonic acids having a quinonediazide group such as quinonediazidesulfonic acid.
ここで用いる前記芳香族(ポリ)ヒドロキシ化合物は、例えば、2,3,4−トリヒドロキシベンゾフェノン、2,4,4’−トリヒドロキシベンゾフェノン、2,4,6−トリヒドロキシベンゾフェノン、2,3,6−トリヒドロキシベンゾフェノン、2,3,4−トリヒドロキシ−2’−メチルベンゾフェノン、2,3,4,4’−テトラヒドロキシベンゾフェノン、2,2’,4,4’−テトラヒドロキシベンゾフェノン、2,3’,4,4’,6−ペンタヒドロキシベンゾフェノン、2,2’,3,4,4’−ペンタヒドロキシベンゾフェノン、2,2’,3,4,5−ペンタヒドロキシベンゾフェノン、2,3’,4,4’,5’,6−ヘキサヒドロキシベンゾフェノン、2,3,3’,4,4’,5’−ヘキサヒドロキシベンゾフェノン等のポリヒドロキシベンゾフェノン化合物; Examples of the aromatic (poly) hydroxy compound used here include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3, 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2, 3 ′, 4,4 ′, 6-pentahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′, 4,4 ′, 5 ′, 6-hexahydroxybenzophenone, 2,3,3 ′, 4,4 ′, 5′-hexahydroxybenzo Polyhydroxy benzophenone compounds such Enon;
ビス(2,4−ジヒドロキシフェニル)メタン、ビス(2,3,4−トリヒドロキシフェニル)メタン、2−(4−ヒドロキシフェニル)−2−(4’−ヒドロキシフェニル)プロパン、2−(2,4−ジヒドロキシフェニル)−2−(2’,4’−ジヒドロキシフェニル)プロパン、2−(2,3,4−トリヒドロキシフェニル)−2−(2’,3’,4’−トリヒドロキシフェニル)プロパン、4,4’−{1−[4−〔2−(4−ヒドロキシフェニル)−2−プロピル〕フェニル]エチリデン}ビスフェノール,3,3’−ジメチル−{1−[4−〔2−(3−メチル−4−ヒドロキシフェニル)−2−プロピル〕フェニル]エチリデン}ビスフェノール等のビス[(ポリ)ヒドロキシフェニル]アルカン化合物; Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) Propane, 4,4 ′-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, 3,3′-dimethyl- {1- [4- [2- ( Bis [(poly) hydroxyphenyl] alkane compounds such as 3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol;
トリス(4−ヒドロキシフェニル)メタン、ビス(4−ヒドロキシ−3、5−ジメチルフェニル)−4−ヒドロキシフェニルメタン、ビス(4−ヒドロキシ−2,5−ジメチルフェニル)−4−ヒドロキシフェニルメタン、ビス(4−ヒドロキシ−3,5−ジメチルフェニル)−2−ヒドロキシフェニルメタン、ビス(4−ヒドロキシ−2,5−ジメチルフェニル)−2−ヒドロキシフェニルメタン、ビス(4−ヒドロキシ−2,5−ジメチルフェニル)−3,4−ジヒドロキシフェニルメタン、ビス(4−ヒドロキシ−3,5−ジメチルフェニル)−3,4−ジヒドロキシフェニルメタン等のトリス(ヒドロキシフェニル)メタン化合物又はそのメチル置換体; Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethyl) Phenyl) -3,4-dihydroxyphenylmethane, tris (hydroxyphenyl) methane compounds such as bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane or methyl-substituted products thereof;
ビス(3−シクロヘキシル−4−ヒドロキシフェニル)−3−ヒドロキシフェニルメタン,ビス(3−シクロヘキシル−4−ヒドロキシフェニル)−2−ヒドロキシフェニルメタン,ビス(3−シクロヘキシル−4−ヒドロキシフェニル)−4−ヒドロキシフェニルメタン,ビス(5−シクロヘキシル−4−ヒドロキシ−2−メチルフェニル)−2−ヒドロキシフェニルメタン,ビス(5−シクロヘキシル−4−ヒドロキシ−2−メチルフェニル)−3−ヒドロキシフェニルメタン、ビス(5−シクロヘキシル−4−ヒドロキシ−2−メチルフェニル)−4−ヒドロキシフェニルメタン、ビス(3−シクロヘキシル−2−ヒドロキシフェニル)−3−ヒドロキシフェニルメタン、ビス(5−シクロヘキシル−4−ヒドロキシ−3−メチルフェニル)−4−ヒドロキシフェニルメタン、ビス(5−シクロヘキシル−4−ヒドロキシ−3−メチルフェニル)−3−ヒドロキシフェニルメタン、ビス(5−シクロヘキシル−4−ヒドロキシ−3−メチルフェニル)−2−ヒドロキシフェニルメタン、ビス(3−シクロヘキシル−2−ヒドロキシフェニル)−4−ヒドロキシフェニルメタン、ビス(3−シクロヘキシル−2−ヒドロキシフェニル)−2−ヒドロキシフェニルメタン、ビス(5−シクロヘキシル−2−ヒドロキシ−4−メチルフェニル)−2−ヒドロキシフェニルメタン、ビス(5−シクロヘキシル−2−ヒドロキシ−4−メチルフェニル)−4−ヒドロキシフェニルメタンなどの、ビス(シクロヘキシルヒドロキシフェニル)(ヒドロキシフェニル)メタン化合物又はそのメチル置換体等が挙げられる。これらの感光剤はそれぞれ単独で用いても良いし、2種類以上を併用しても良い。 Bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4- Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis ( 5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3- Methylfe ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxy Phenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4) -Methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane and the like bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane compounds or their Chill substituents and the like. These photosensitizers may be used alone or in combination of two or more.
本発明の感光性組成物における前記感光剤の配合量は、光感度に優れる感光性組成物となることから、感光性組成物の樹脂固形分の合計100質量部に対し、5〜50質量部となる割合であることが好ましい。 Since the compounding amount of the photosensitive agent in the photosensitive composition of the present invention is a photosensitive composition having excellent photosensitivity, it is 5 to 50 parts by mass with respect to 100 parts by mass of the resin solids in the photosensitive composition. It is preferable that the ratio is
本発明の感光性組成物は、レジスト用途に用いた場合の製膜性やパターンの密着性の向上、現像欠陥を低減するなどの目的で界面活性剤を含有していても良い。ここで用いる界面活性剤は、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セチルエーテル、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化合物、ポリオキシエチレンオクチルフェノールエーテル、ポリオキシエチレンノニルフェノールエーテル等のポリオキシエチレンアルキルアリルエーテル化合物、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル化合物、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテ−ト、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル化合物等のノニオン系界面活性剤;フルオロ脂肪族基を有する重合性単量体と[ポリ(オキシアルキレン)](メタ)アクリレートとの共重合体など分子構造中にフッ素原子を有するフッ素系界面活性剤;分子構造中にシリコーン構造部位を有するシリコーン系界面活性剤等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。 The photosensitive composition of the present invention may contain a surfactant for the purpose of improving the film-forming property and pattern adhesion when used for resist applications, and reducing development defects. Examples of the surfactant used here include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ether compounds such as ethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, poly Nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester compounds such as xylethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; fluoro fat Fluorosurfactants having a fluorine atom in the molecular structure such as a copolymer of a polymerizable monomer having a group and [poly (oxyalkylene)] (meth) acrylate; having a silicone structure site in the molecular structure Examples thereof include silicone surfactants. These may be used alone or in combination of two or more.
これらの界面活性剤の配合量は、本発明の感光性組成物中の樹脂固形分の合計100質量部に対し0.001〜2質量部の範囲で用いることが好ましい。 The amount of these surfactants to be used is preferably in the range of 0.001 to 2 parts by mass with respect to 100 parts by mass of the total resin solids in the photosensitive composition of the present invention.
本発明の感光性組成物をフォトレジスト用途に用いる場合には、本発明のノボラック型樹脂、感光剤の他、更に必要に応じてその他の樹脂(C)や界面活性剤、染料、充填材、架橋剤、溶解促進剤など各種の添加剤を加え、有機溶剤に溶解することによりレジスト用組成物とすることができる。これをそのままポジ型レジスト溶液と用いても良いし、或いは、該レジスト用組成物をフィルム状に塗布して脱溶剤させたものをポジ型レジストフィルムとして用いても良い。レジストフィルムとして用いる際の支持フィルムは、ポリエチレン、ポリプロピレン、ポリカーボネート、ポリエチレンテレフタレート等の合成樹脂フィルムが挙げられ、単層フィルムでも複数の積層フィルムでも良い。また、該支持フィルムの表面はコロナ処理されたものや剥離剤が塗布されたものでも良い。 When the photosensitive composition of the present invention is used for photoresist applications, in addition to the novolak type resin and photosensitive agent of the present invention, if necessary, other resins (C), surfactants, dyes, fillers, By adding various additives such as a crosslinking agent and a dissolution accelerator and dissolving in an organic solvent, a resist composition can be obtained. This may be used as it is as a positive resist solution, or may be used as a positive resist film obtained by removing the solvent by applying the resist composition in a film form. Examples of the support film used as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, and may be a single layer film or a plurality of laminated films. The surface of the support film may be a corona-treated one or a release agent.
本発明の感光性組成物に用いる有機溶剤は特に限定されないが、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル等のアルキレングリコールモノアルキルエーテル;ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル等のジアルキレングリコールジアルキルエーテル;エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のアルキレングリコールアルキルエーテルアセテート;アセトン、メチルエチルケトン、シクロヘキサノン、メチルアミルケトン等のケトン化合物;ジオキサン等の環式エーテル;2−ヒドロキシプロピオン酸メチル、2−ヒドロキシプロピオン酸エチル、2−ヒドロキシ−2−メチルプロピオン酸エチル、エトキシ酢酸エチル、オキシ酢酸エチル、2−ヒドロキシ−3−メチルブタン酸メチル、3−メトキシブチルアセテート、3−メチル−3−メトキシブチルアセテート、蟻酸エチル、酢酸エチル、酢酸ブチル、アセト酢酸メチル、アセト酢酸エチル、乳酸エチル等のエステル化合物が挙げられる、これらはそれぞれ単独でも地いても良いし、2種類以上を併用しても良い。 The organic solvent used in the photosensitive composition of the present invention is not particularly limited, and examples thereof include alkylene glycol monomethyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Alkyl ethers; Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene glycols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Alkyl ether acetate; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate , Ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, acetoacetic acid Examples thereof include ester compounds such as ethyl and ethyl lactate, which may be used alone or in combination of two or more.
本発明の感光性組成物は上記各成分を配合し、攪拌機等を用いて混合することにより製造することができる。また、感光性組成物が充填材や顔料を含有する場合には、ディゾルバー、ホモジナイザー、3本ロールミル等の分散装置を用いて分散或いは混合して製造することが出来る。 The photosensitive composition of this invention can be manufactured by mix | blending said each component and mixing using a stirrer etc. Further, when the photosensitive composition contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.
本発明の感光性組成物を用いたフォトリソグラフィーの方法は、例えば、シリコン基板フォトリソグラフィーを行う対象物上に感光性組成物を塗布し、60〜150℃の温度条件でプリベークする。このときの塗布方法は、スピンコート、ロールコート、フローコート、ディップコート、スプレーコート、ドクターブレードコート等の何れの方法でも良い。次にレジストパターンの作成であるが、本発明の感光性組成物はポジ型であることから、目的とするレジストパターンを所定のマスクを通じて露光し、露光した箇所をアルカリ現像液にて溶解することにより、レジストパターンを形成する。本発明の感光性組成物は、露光部のアルカリ溶解性と、非露光部の耐アルカリ溶解性とが共に高いことから、解像度に優れるレジストパターンの形成が可能となる。 In the photolithography method using the photosensitive composition of the present invention, for example, the photosensitive composition is applied onto an object to be subjected to silicon substrate photolithography, and prebaked at a temperature of 60 to 150 ° C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like. Next, a resist pattern is prepared. Since the photosensitive composition of the present invention is a positive type, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkaline developer. Thus, a resist pattern is formed. Since the photosensitive composition of the present invention has both high alkali solubility in the exposed area and high alkali resistance in the non-exposed area, it is possible to form a resist pattern with excellent resolution.
本発明の硬化性組成物は、前記本発明のノボラック型樹脂と、硬化剤とを必須の成分として含有する。本発明の硬化性組成物は、前記本発明のノボラック型樹脂以外に、その他の樹脂(D)を含有しても良い。ここで用いるその他の樹脂(D)は、例えば、各種のノボラック樹脂、ジシクロペンタジエン等の脂環式ジエン化合物とフェノール化合物との付加重合樹脂、フェノール性水酸基含有化合物とアルコキシ基含有芳香族化合物との変性ノボラック樹脂、フェノールアラルキル樹脂(ザイロック樹脂)、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ビフェニル変性フェノール樹脂、ビフェニル変性ナフトール樹脂、アミノトリアジン変性フェノール樹脂、及び各種のビニル重合体等が挙げられる。 The curable composition of the present invention contains the novolac resin of the present invention and a curing agent as essential components. The curable composition of the present invention may contain other resin (D) in addition to the novolac resin of the present invention. Other resins (D) used here include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, Modified novolak resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenol resin, and various vinyl polymers Etc.
前記各種のノボラック樹脂は、より具体的には、フェノール、クレゾールやキシレノール等のアルキルフェノール、フェニルフェノール、レゾルシノール、ビフェニル、ビスフェノールAやビスフェノールF等のビスフェノール、ナフトール、ジヒドロキシナフタレン等のフェノール性水酸基含有化合物と、アルデヒド化合物とを酸触媒条件下で反応させて得られる重合体が挙げられる。 More specifically, the various novolak resins include phenols, alkylphenols such as cresol and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F, and phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene. And a polymer obtained by reacting an aldehyde compound with an acid catalyst.
前記各種のビニル重合体は、ポリヒドロキシスチレン、ポリスチレン、ポリビニルナフタレン、ポリビニルアントラセン、ポリビニルカルバゾール、ポリインデン、ポリアセナフチレン、ポリノルボルネン、ポリシクロデセン、ポリテトラシクロドデセン、ポリノルトリシクレン、ポリ(メタ)アクリレート等のビニル化合物の単独重合体或いはこれらの共重合体が挙げられる。 The various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinyl carbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly ( A homopolymer of a vinyl compound such as (meth) acrylate or a copolymer thereof may be mentioned.
これらその他の樹脂を用いる場合、本発明のノボラック型樹脂とその他の樹脂(D)との配合割合は、用途に応じて任意に設定することが出来るが、本発明が奏する耐熱性に優れる効果がより顕著に発現することから、本発明のノボラック型樹脂100質量部に対し、その他の樹脂(D)が0.5〜100質量部となる割合であることが好ましい。 When these other resins are used, the blending ratio of the novolak resin of the present invention and the other resin (D) can be arbitrarily set according to the use, but the effect of the present invention in terms of heat resistance is excellent. It is preferable that the ratio of the other resin (D) to be 0.5 to 100 parts by mass with respect to 100 parts by mass of the novolac resin of the present invention because it is more remarkably expressed.
本発明で用いる前記硬化剤は、例えば、メチロール基、アルコキシメチル基、アシロキシメチル基から選ばれる少なくとも一つの基で置換されたメラミン化合物、グアナミン化合物、グリコールウリル化合物、ウレア化合物、レゾール樹脂、エポキシ化合物、イソシアネート化合物、アジド化合物、アルケニルエーテル基等の2重結合を含む化合物、酸無水物、オキサゾリン化合物等が挙げられる。 The curing agent used in the present invention is, for example, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resole resin, an epoxy substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Compound, isocyanate compound, azide compound, compound containing double bond such as alkenyl ether group, acid anhydride, oxazoline compound and the like.
前記メラミン化合物は、例えば、ヘキサメチロールメラミン、ヘキサメトキシメチルメラミン、ヘキサメチロールメラミンの1〜6個のメチロール基がメトキシメチル化した化合物、ヘキサメトキシエチルメラミン、ヘキサアシロキシメチルメラミン、ヘキサメチロールメラミンのメチロール基の1〜6個がアシロキシメチル化した化合物等が挙げられる。 Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and hexamethylol melamine methylol. Examples include compounds in which 1 to 6 of the groups are acyloxymethylated.
前記グアナミン化合物は、例えば、テトラメチロールグアナミン、テトラメトキシメチルグアナミン、テトラメトキシメチルベンゾグアナミン、テトラメチロールグアナミンの1〜4個のメチロール基がメトキシメチル化した化合物、テトラメトキシエチルグアナミン、テトラアシロキシグアナミン、テトラメチロールグアナミンの1〜4個のメチロール基がアシロキシメチル化した化合物等が挙げられる。 Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, tetra Examples thereof include compounds in which 1 to 4 methylol groups of methylolguanamine are acyloxymethylated.
前記グリコールウリル化合物は、例えば、1,3,4,6−テトラキス(メトキシメチル)グリコールウリル、1,3,4,6−テトラキス(ブトキシメチル)グリコールウリル、1,3,4,6−テトラキス(ヒドロキシメチル)グリコールウリル等が挙げられる。 Examples of the glycoluril compound include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis ( Hydroxymethyl) glycoluril and the like.
前記ウレア化合物は、例えば、1,3−ビス(ヒドロキシメチル)尿素、1,1,3,3−テトラキス(ブトキシメチル)尿素及び1,1,3,3−テトラキス(メトキシメチル)尿素等が挙げられる。 Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea. It is done.
前記レゾール樹脂は、例えば、フェノール、クレゾールやキシレノール等のアルキルフェノール、フェニルフェノール、レゾルシノール、ビフェニル、ビスフェノールAやビスフェノールF等のビスフェノール、ナフトール、ジヒドロキシナフタレン等のフェノール性水酸基含有化合物と、アルデヒド化合物とをアルカリ性触媒条件下で反応させて得られる重合体が挙げられる。 The resole resin may be, for example, an alkylphenol such as phenol, cresol or xylenol, a bisphenol such as phenylphenol, resorcinol, biphenyl, bisphenol A or bisphenol F, a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene, and an aldehyde compound. Examples include polymers obtained by reacting under catalytic conditions.
前記エポキシ化合物は、例えば、ジグリシジルオキシナフタレン、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、1,1−ビス(2,7−ジグリシジルオキシ−1−ナフチル)アルカン、ナフチレンエーテル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂、リン原子含有エポキシ樹脂、フェノール性水酸基含有化合物とアルコキシ基含有芳香族化合物との共縮合物のポリグリシジルエーテル等が挙げられる。 Examples of the epoxy compound include diglycidyloxynaphthalene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene- Examples include phenol addition reaction type epoxy resins, phosphorus atom-containing epoxy resins, polyglycidyl ethers of cocondensates of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, and the like. .
前記イソシアネート化合物は、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、シクロヘキサンジイソシアネート等が挙げられる。 Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.
前記アジド化合物は、例えば、1,1’−ビフェニル−4,4’−ビスアジド、4,4’−メチリデンビスアジド、4,4’−オキシビスアジド等が挙げられる。 Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, 4,4'-oxybisazide, and the like.
前記アルケニルエーテル基等の2重結合を含む化合物は、例えば、エチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、1,2−プロパンジオールジビニルエーテル、1,4−ブタンジオールジビニルエーテル、テトラメチレングリコールジビニルエーテル、ネオペンチルグリコールジビニルエーテル、トリメチロールプロパントリビニルエーテル、ヘキサンジオールジビニルエーテル、1,4−シクロヘキサンジオールジビニルエーテル、ペンタエリスリトールトリビニルエーテル、ペンタエリスリトールテトラビニルエーテル、ソルビトールテトラビニルエーテル、ソルビトールペンタビニルエーテル、トリメチロールプロパントリビニルエーテル等が挙げられる。 Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether. , Neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether Etc.
前記酸無水物は例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物、4,4’−(イソプロピリデン)ジフタル酸無水物、4,4’−(ヘキサフルオロイソプロピリデン)ジフタル酸無水物等の芳香族酸無水物;無水テトラヒドロフタル酸、無水メチルテトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルヘキサヒドロフタル酸、無水エンドメチレンテトラヒドロフタル酸無水ドデセニルコハク酸、無水トリアルキルテトラヒドロフタル酸等の脂環式カルボン酸無水物等が挙げられる。 Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4 Aromatic acid anhydrides such as '-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride And alicyclic carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.
これらの中でも、硬化性や硬化物における耐熱性に優れる硬化性組成物となることから、グリコールウリル化合物、ウレア化合物、レゾール樹脂が好ましく、グリコールウリル化合物が特に好ましい。 Among these, a glycoluril compound, a urea compound, and a resole resin are preferable, and a glycoluril compound is particularly preferable because it becomes a curable composition having excellent curability and heat resistance in a cured product.
本発明の硬化性組成物における前記硬化剤の配合量は、硬化性に優れる組成物となることから、本発明のノボラック型樹脂とその他の樹脂(D)との合計100質量部に対し、0.5〜50質量部となる割合であることが好ましい。 Since the compounding amount of the curing agent in the curable composition of the present invention is a composition having excellent curability, it is 0 with respect to 100 parts by mass in total of the novolac resin of the present invention and the other resin (D). It is preferable that it is the ratio used as 5-50 mass parts.
本発明の硬化性組成物をレジスト下層膜(BARC膜)用途に用いる場合には、本発明のノボラック型樹脂、硬化剤の他、更に必要に応じてその他の樹脂(D)、界面活性剤や染料、充填材、架橋剤、溶解促進剤など各種の添加剤を加え、有機溶剤に溶解することによりレジスト下層膜用組成物とすることができる。 When the curable composition of the present invention is used for a resist underlayer film (BARC film), in addition to the novolac resin and the curing agent of the present invention, other resins (D), surfactants, By adding various additives such as dyes, fillers, cross-linking agents and dissolution accelerators and dissolving them in an organic solvent, a resist underlayer film composition can be obtained.
レジスト下層膜用組成物に用いる有機溶剤は、特に限定されないが、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル等のアルキレングリコールモノアルキルエーテル;ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル等のジアルキレングリコールジアルキルエーテル;エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のアルキレングリコールアルキルエーテルアセテート;アセトン、メチルエチルケトン、シクロヘキサノン、メチルアミルケトン等のケトン化合物;ジオキサン等の環式エーテル;2−ヒドロキシプロピオン酸メチル、2−ヒドロキシプロピオン酸エチル、2−ヒドロキシ−2−メチルプロピオン酸エチル、エトキシ酢酸エチル、オキシ酢酸エチル、2−ヒドロキシ−3−メチルブタン酸メチル、3−メトキシブチルアセテート、3−メチル−3−メトキシブチルアセテート、蟻酸エチル、酢酸エチル、酢酸ブチル、アセト酢酸メチル、アセト酢酸エチル、乳酸エチル等のエステル化合物が挙げられる、これらはそれぞれ単独でも地いても良いし、2種類以上を併用しても良い。 The organic solvent used in the resist underlayer film composition is not particularly limited, and examples thereof include alkylene glycol monomethyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Alkyl ethers; Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene groups such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Cole alkyl ether acetate; Ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; Cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, Ethyl 2-hydroxy-2-methylpropionate , Ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, acetoacetic acid Examples thereof include ester compounds such as ethyl and ethyl lactate, which may be used alone or in combination of two or more.
前記レジスト下層膜用組成物は上記各成分を配合し、攪拌機等を用いて混合することにより製造することができる。また、レジスト下層膜用組成物が充填材や顔料を含有する場合には、ディゾルバー、ホモジナイザー、3本ロールミル等の分散装置を用いて分散或いは混合して製造することができる。 The resist underlayer film composition can be produced by blending the above components and mixing them using a stirrer or the like. When the resist underlayer film composition contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.
前記レジスト下層膜用組成物からレジスト下層膜を作成するには、例えば、前記レジスト下層膜用組成物を、シリコン基板などフォトリソグラフィーを行う対象物上に塗布し、100〜200℃の温度条件下で乾燥させた後、更に250〜400℃の温度条件下で加熱硬化させるなどの方法によりレジスト下層膜を形成する。次いで、この下層膜上で通常のフォトリソグラフィー操作を行ってレジストパターンを形成し、ハロゲン系プラズマガス等でドライエッチング処理することにより、多層レジスト法によるレジストパターンを形成することが出来る。 In order to create a resist underlayer film from the resist underlayer film composition, for example, the resist underlayer film composition is applied onto an object to be subjected to photolithography such as a silicon substrate, and is subjected to a temperature condition of 100 to 200 ° C. Then, a resist underlayer film is formed by a method such as heat curing under a temperature condition of 250 to 400 ° C. Next, a resist pattern is formed on this lower layer film by performing a normal photolithography operation, and a resist pattern by a multilayer resist method can be formed by performing a dry etching process with a halogen-based plasma gas or the like.
本発明の硬化性組成物をレジスト永久膜用途に用いる場合には、本発明のノボラック型樹脂、硬化剤の他、更に必要に応じてその他の樹脂(D)、界面活性剤や染料、充填材、架橋剤、溶解促進剤など各種の添加剤を加え、有機溶剤に溶解することによりレジスト永久膜用組成物とすることができる。ここで用いる有機溶剤は、レジスト下層膜用組成物で用いる有機溶剤と同様のものが挙げられる。 When the curable composition of the present invention is used for resist permanent film applications, in addition to the novolak type resin and the curing agent of the present invention, other resins (D), surfactants, dyes, and fillers as necessary. The composition for a resist permanent film can be obtained by adding various additives such as a crosslinking agent and a dissolution accelerator and dissolving in an organic solvent. The organic solvent used here is the same as the organic solvent used in the resist underlayer film composition.
前記レジスト永久膜用組成物を用いたフォトリソグラフィーの方法は、例えば、有機溶剤に樹脂成分及び添加剤成分を溶解・分散させ、シリコン基板フォトリソグラフィーを行う対象物上に塗布し、60〜150℃の温度条件でプリベークする。このときの塗布方法は、スピンコート、ロールコート、フローコート、ディップコート、スプレーコート、ドクターブレードコート等の何れの方法でもよい。次にレジストパターンの作成であるが、当該レジスト永久膜用組成物がポジ型の場合には、目的とするレジストパターンを所定のマスクを通じて露光し、露光した箇所をアルカリ現像液にて溶解することにより、レジストパターンを形成する。 A photolithography method using the resist permanent film composition may be, for example, dissolving and dispersing a resin component and an additive component in an organic solvent, and applying the solution on an object to be subjected to silicon substrate photolithography at 60 to 150 ° C. Pre-bake under the following temperature conditions. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like. Next, when creating the resist pattern, if the resist permanent film composition is positive, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkali developer. Thus, a resist pattern is formed.
前記レジスト永久膜用組成物からなる永久膜は、例えば、半導体デバイス関係ではソルダーレジスト、パッケージ材、アンダーフィル材、回路素子等のパッケージ接着層や集積回路素子と回路基板の接着層、LCD、OELDに代表される薄型ディスプレイ関係では薄膜トランジスタ保護膜、液晶カラーフィルター保護膜、ブラックマトリックス、スペーサーなどに好適に用いることができる。 The permanent film made of the resist permanent film composition is, for example, a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an integrated circuit element-circuit board adhesive layer, an LCD, or an OELD for semiconductor devices. Can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers and the like.
以下に具体的な例を挙げて、本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with specific examples.
本実施例において数平均分子量(Mn)、重量平均分子量(Mw)、及び多分散度(Mw/Mn)は、下記のGPCの測定条件で測定したものである。
[GPCの測定条件]
測定装置:東ソー株式会社製「HLC−8220 GPC」
カラム:昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF802」(8.0mmФ×300mm)
+昭和電工株式会社製「Shodex KF803」(8.0mmФ×300mm)+昭和電工株式会社製「Shodex KF804」(8.0mmФ×300mm)
カラム温度:40℃
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC−8020モデルIIバージョン4.30」
展開溶媒:テトラヒドロフラン
流速:1.0mL/分
試料:樹脂固形分換算で0.5質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの
注入量:0.1mL
標準試料:下記単分散ポリスチレン
(標準試料:単分散ポリスチレン)
東ソー株式会社製「A−500」
東ソー株式会社製「A−2500」
東ソー株式会社製「A−5000」
東ソー株式会社製「F−1」
東ソー株式会社製「F−2」
東ソー株式会社製「F−4」
東ソー株式会社製「F−10」
東ソー株式会社製「F−20」In this example, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the polydispersity (Mw / Mn) are measured under the following GPC measurement conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: 0.5% by mass tetrahydrofuran solution filtered with a microfilter in terms of resin solids Injection volume: 0.1 mL
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
製造例1 ノボラック型樹脂中間体(1)の製造
冷却管を設置した2000ml4口フラスコにフェノール1000質量部、41.5%ホルマリン600質量部、シュウ酸1質量部を仕込み、撹拌しながら99℃まで2時間かけて昇温した後、乾留しながら3時間撹拌を継続した。脱水回路に切り替えて、脱水しながら180℃まで3時間かけて昇温した。180℃を保持しながら残存するフェノールを留去し、淡赤色のノボラック型樹脂中間体(1)580gを得た。得られたノボラック型樹脂中間体(1)の数平均分子量(Mn)は966、重量平均分子量(Mw)は2,126、多分散度(Mw/Mn)は2.20であった。Production Example 1 Production of Novolac Type Resin Intermediate (1) 1000 parts by mass of phenol, 600 parts by mass of 41.5% formalin, and 1 part by mass of oxalic acid were placed in a 2000 ml four-necked flask equipped with a cooling tube, and stirred up to 99 ° C. After raising the temperature over 2 hours, stirring was continued for 3 hours while dry distillation. It switched to the dehydration circuit and heated up to 180 degreeC over 3 hours, dehydrating. The remaining phenol was distilled off while maintaining 180 ° C. to obtain 580 g of a light red novolac resin intermediate (1). The obtained novolak type resin intermediate (1) had a number average molecular weight (Mn) of 966, a weight average molecular weight (Mw) of 2,126, and a polydispersity (Mw / Mn) of 2.20.
実施例1 ノボラック型樹脂(1)の製造
冷却管を設置した2,000ml4口フラスコに、製造例1で得たノボラック型樹脂中間体(1)450質量部、レゾルシノール50質量部、91.5%パラホルムアルデヒド10質量部を仕込み、メタノール900質量部に溶解させた。室温で98%硫酸5質量部を仕込んだ後、60℃まで1時間かけて昇温し、20時間撹拌を継続した。60℃を保持しながら減圧条件下でメタノールを600質量部留去し、撹拌しながら水1,000質量部を滴下して、反応生成物を再沈殿させた。分離した水溶性の上澄み液を吸引除去し、メタノール300質量部を加えて残渣の反応生成物を溶解させた。再度水1000質量部を加えて反応生成物を再沈殿させ、上澄み液を除去した。プロピレングリコールモノエチルエーテルアセテート1,000質量部を加えて反応生成物を溶解させ、減圧条件下で脱水し、ノボラック型樹脂(1)溶液(樹脂分30質量%)793質量部を得た。得られたノボラック型樹脂(1)の数平均分子量(Mn)は3,144、重量平均分子量(Mw)は15,760、多分散度(Mw/Mn)は5.01であった。ノボラック型樹脂(1)のGPCチャートを図1に示す。Example 1 Production of Novolak Type Resin (1) In a 2,000 ml four-necked flask equipped with a cooling tube, 450 parts by mass of novolac type resin intermediate (1) obtained in Production Example 1 and 50 parts by mass of resorcinol, 91.5% 10 parts by mass of paraformaldehyde was charged and dissolved in 900 parts by mass of methanol. After charging 5 parts by mass of 98% sulfuric acid at room temperature, the temperature was raised to 60 ° C. over 1 hour, and stirring was continued for 20 hours. While maintaining 60 ° C., 600 parts by mass of methanol was distilled off under reduced pressure, and 1,000 parts by mass of water was added dropwise with stirring to reprecipitate the reaction product. The separated water-soluble supernatant was removed by suction, and 300 parts by mass of methanol was added to dissolve the residual reaction product. 1000 parts by mass of water was added again to reprecipitate the reaction product, and the supernatant was removed. The reaction product was dissolved by adding 1,000 parts by mass of propylene glycol monoethyl ether acetate and dehydrated under reduced pressure to obtain 793 parts by mass of a novolac resin (1) solution (resin content: 30% by mass). The novolak resin (1) obtained had a number average molecular weight (Mn) of 3,144, a weight average molecular weight (Mw) of 15,760, and a polydispersity (Mw / Mn) of 5.01. A GPC chart of the novolac resin (1) is shown in FIG.
実施例2 ノボラック型樹脂(2)の製造
ノボラック型樹脂中間体(1)を475質量部に、レゾルシノールを25質量部に、91.5%パラホルムアルデヒドを5質量部に変更した以外は実施例1と同様の操作を行い、ノボラック型樹脂(2)溶液(樹脂分30質量%)788質量部を得た。得られたノボラック型樹脂(2)の数平均分子量(Mn)は3,483、重量平均分子量(Mw)は16,112、多分散度(Mw/Mn)は4.63であった。Example 2 Production of novolak type resin (2) Example 1 except that novolak type resin intermediate (1) was changed to 475 parts by mass, resorcinol to 25 parts by mass, and 91.5% paraformaldehyde to 5 parts by mass. The same operation was carried out to obtain 788 parts by mass of a novolac resin (2) solution (resin content: 30% by mass). The novolak resin (2) obtained had a number average molecular weight (Mn) of 3,483, a weight average molecular weight (Mw) of 16,112, and a polydispersity (Mw / Mn) of 4.63.
比較製造例1 ノボラック型樹脂(1’)の製造
冷却管を設置した2,000ml4口フラスコにオルソクレゾール900質量部、レゾルシノール90質量部、41.5%ホルマリン600質量部、シュウ酸1質量部を仕込み撹拌しながら99℃まで2時間かけて昇温した後、乾留しながら3時間撹拌を継続した。脱水回路に切り替えて、脱水しながら180℃まで3時間かけて昇温した。180℃を保持しながら残存するオルソクレゾールを留去し、淡赤色のノボラック型樹脂(1‘)530gを得た。得られたノボラック型樹脂(1’)の数平均分子量(Mn)は1,032、重量平均分子量(Mw)は2,234、多分散度(Mw/Mn)は2.16であった。Comparative Production Example 1 Production of Novolac Type Resin (1 ′) In a 2,000 ml four-necked flask equipped with a cooling tube, 900 parts by mass of orthocresol, 90 parts by mass of resorcinol, 600 parts by mass of 41.5% formalin, and 1 part by mass of oxalic acid The temperature was raised to 99 ° C. over 2 hours with stirring, and stirring was continued for 3 hours while dry distillation. It switched to the dehydration circuit and heated up to 180 degreeC over 3 hours, dehydrating. The remaining ortho-cresol was distilled off while maintaining 180 ° C. to obtain 530 g of a pale red novolac resin (1 ′). The obtained novolac resin (1 ′) had a number average molecular weight (Mn) of 1,032, a weight average molecular weight (Mw) of 2,234, and a polydispersity (Mw / Mn) of 2.16.
保存安定性の評価
実施例1、2及び比較製造例1で得たノボラック型樹脂をプロピレングリコールモノメチルエーテルアセテートに溶解させ、樹脂濃度が15質量%のサンプルと、30質量%のサンプルとを用意した。該サンプルを25℃、55℃、80℃の各温度条件に設定した恒温槽に入れ、二週間の保存試験を行った。保存試験前後での重量平均分子量(Mw)の変化率を測定し、変化率の絶対値が10%以下の場合をA、変化率の絶対値が±10%を超える場合をBとして評価した。結果を表1に示す。Evaluation of Storage Stability The novolak resin obtained in Examples 1 and 2 and Comparative Production Example 1 was dissolved in propylene glycol monomethyl ether acetate to prepare a sample having a resin concentration of 15% by mass and a sample having 30% by mass. . The sample was put in a thermostat set to 25 ° C., 55 ° C., and 80 ° C. and subjected to a storage test for two weeks. The rate of change of the weight average molecular weight (Mw) before and after the storage test was measured, and the case where the absolute value of the rate of change was 10% or less was evaluated as A, and the case where the absolute value of the rate of change exceeded ± 10% was evaluated as B. The results are shown in Table 1.
実施例3、4及び比較例1
実施例1、2及び比較製造例1で得たノボラック型樹脂について、下記の要領で評価した。結果を表2に示す。Examples 3 and 4 and Comparative Example 1
The novolac resins obtained in Examples 1 and 2 and Comparative Production Example 1 were evaluated in the following manner. The results are shown in Table 2.
硬化性組成物の製造
ノボラック型樹脂溶液53質量部(樹脂分16質量部)、硬化剤(東京化成工業株式会社製「1,3,4,6−テトラキス(メトキシメチル)グリコールウリル」)4質量部をプロピレングリコールモノメチルエーテルアセテート143質量部に溶解させ、これを0.2μmのメンブレンフィルターで濾過し、硬化性組成物を得た。Production of curable composition 53 parts by mass of novolak resin solution (16 parts by mass of resin), 4 parts by mass of curing agent (“1,3,4,6-tetrakis (methoxymethyl) glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.) Part was dissolved in 143 parts by mass of propylene glycol monomethyl ether acetate, and this was filtered through a 0.2 μm membrane filter to obtain a curable composition.
耐熱性の評価
先で得た硬化性組成物を5インチシリコンウェハー上に約1μmの厚さになるようにスピンコーターで塗布し、110℃のホットプレート上で60秒乾燥させた後、230℃で300秒間加熱処理し、硬化塗膜を得た。得られた硬化塗膜をウェハーから削り取り、示差熱熱重量同時測定装置(TG/DTA)を用い、下記条件で昇温させた時の質量減少を測定し、1質量%減少温度(Td1)を求めた。
測定機器:セイコーインスツールメント社製「TG/DTA 6200」
測定範囲:室温〜400℃
昇温速度:10℃/分Evaluation of heat resistance The curable composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, dried on a 110 ° C. hot plate for 60 seconds, and then 230 ° C. Was heated for 300 seconds to obtain a cured coating film. The obtained cured coating film is scraped off from the wafer, and the mass decrease when the temperature is raised under the following conditions is measured using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA). Asked.
Measuring instrument: “TG / DTA 6200” manufactured by Seiko Instruments Inc.
Measurement range: room temperature to 400 ° C
Temperature increase rate: 10 ° C / min
実施例5、6、比較例2
実施例1、2及び比較製造例1で得たノボラック型樹脂について、下記の要領で評価した。結果を表3に示す。Examples 5 and 6, Comparative Example 2
The novolac resins obtained in Examples 1 and 2 and Comparative Production Example 1 were evaluated in the following manner. The results are shown in Table 3.
感光性組成物の製造
前記ノボラック型樹脂24質量部をプロピレングリコールモノメチルエーテルアセテート60質量部に溶解させ、この溶液に感光剤16質量部を加えて溶解させた。これを0.2μmのメンブレンフィルターで濾過し、感光性組成物を得た。
感光剤は東洋合成工業株式会社製「P−200」(4,4’−[1−[4−[1−(4−ヒドロキシフェニル)−1メチルエチル]フェニル]エチリデン]ビスフェノール1モルと1,2−ナフトキノン−2−ジアジド−5−スルホニルクロリド2モルとの縮合物)を用いた。Production of Photosensitive Composition 24 parts by mass of the novolak resin was dissolved in 60 parts by mass of propylene glycol monomethyl ether acetate, and 16 parts by mass of a photosensitizer was added to the solution to dissolve. This was filtered through a 0.2 μm membrane filter to obtain a photosensitive composition.
The photosensitizer was “P-200” (4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol 1 mol and 1, manufactured by Toyo Gosei Co., Ltd. 2-naphthoquinone-2-diazide-5-sulfonyl chloride condensate).
アルカリ現像性[ADR(nm/s)]の評価
先で得た感光性組成物を5インチシリコンウェハー上に約1μmの厚さになるようにスピンコーターで塗布し、110℃のホットプレート上で60秒乾燥させた。このウェハーを2枚用意し、一方を「露光なしサンプル」とした。他方を「露光有サンプル」としてghi線ランプ(ウシオ電機株式会社製「マルチライト」)を用いて100mJ/cm2のghi線を照射したのち、140℃、60秒間の条件で加熱処理を行った。
「露光なしサンプル」と「露光有サンプル」の両方をアルカリ現像液(2.38%水酸化テトラメチルアンモニウム水溶液)に60秒間浸漬した後、110℃のホットプレート上で60秒乾燥させた。各サンプルの現像液浸漬前後の膜厚を測定し、その差分を60で除した値をアルカリ現像性[ADR(nm/s)]とした。Evaluation of Alkali Developability [ADR (nm / s)] The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and then on a hot plate at 110 ° C. Dried for 60 seconds. Two wafers were prepared, and one of the wafers was designated as “no exposure sample”. The other was used as an “exposed sample” and irradiated with 100 mJ / cm 2 of ghi line using a ghi line lamp (“Multi Light” manufactured by USHIO INC.), And then heat-treated at 140 ° C. for 60 seconds. .
Both the “non-exposed sample” and the “exposed sample” were immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness of each sample before and after immersion in the developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability [ADR (nm / s)].
光感度の評価
先で得た感光性組成物を5インチシリコンウェハー上に約1μmの厚さになるようにスピンコーターで塗布し、110℃のホットプレート上で60秒乾燥させた。このウェハー上にラインアンドスペースが1:1であり、ライン幅が1〜10μmまで1μmごとに設定されたレジストパターン対応のマスクを密着させた後、ghi線ランプ(ウシオ電機株式会社製「マルチライト」)を用いてghi線を照射し、140℃、60秒間の条件で加熱処理を行った。次いで、アルカリ現像液(2.38%水酸化テトラメチルアンモニウム水溶液)に60秒間浸漬した後、110℃のホットプレート上で60秒乾燥させた。
ghi線露光量を30mJ/cm2から5mJ/cm2毎に増加させた場合の、ライン幅3μmを忠実に再現することのできる露光量(Eop露光量)を評価した。Evaluation of Photosensitivity The photosensitive composition obtained above was applied on a 5 inch silicon wafer with a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. A mask corresponding to a resist pattern having a line-and-space ratio of 1: 1 and a line width of 1 to 10 μm set every 1 μm is brought into close contact with the wafer, and then a ghi line lamp (“Multi Light” manufactured by USHIO INC. )) Was used for irradiation with ghi rays, and heat treatment was performed at 140 ° C. for 60 seconds. Next, the film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds.
The exposure amount (Eop exposure amount) capable of faithfully reproducing the line width of 3 μm when the ghi line exposure amount was increased from 30 mJ / cm 2 to 5 mJ / cm 2 was evaluated.
解像度の評価
先で得た感光性組成物を5インチシリコンウェハー上に約1μmの厚さになるようにスピンコーターで塗布し、110℃のホットプレート上で60秒乾燥させた。得られたウェハー上にフォトマスクを乗せ、先のアルカリ現像性評価の場合と同様の方法でghi線200mJ/cm2を照射し、アルカリ現像操作を行った。レーザーマイクロスコープ(株式会社キーエンス製「VK−X200」)を用いてパターン状態を確認し、L/S=1/1の線幅が5μmで解像できているものをA、L/S=1/1の線幅が5μmで解像できていないものをBとして評価した。Evaluation of Resolution The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. A photomask was placed on the obtained wafer, and an alkali development operation was performed by irradiating with 200 mJ / cm 2 of ghi line in the same manner as in the previous alkali developability evaluation. The pattern state is confirmed using a laser microscope ("VK-X200" manufactured by Keyence Corporation), and A / L / S = 1 is obtained when the line width of L / S = 1/1 is resolved at 5 μm. A line width of 1 was evaluated as B when the line width was 5 μm and could not be resolved.
Claims (11)
で表される構造部位(I)を有する請求項1記載のノボラック型樹脂。 At the molecular end, the following structural formula (1)
The novolak-type resin according to claim 1, which has a structural site (I) represented by:
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IL96551A0 (en) * | 1989-12-18 | 1991-09-16 | Rohm & Haas | Preparation of high glass transition temperature novolak resins useful in high resolution photoresist compositions |
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