JP2010197887A - Cresol resin for photoresist, method for producing the same, and photoresist composition containing the resin - Google Patents
Cresol resin for photoresist, method for producing the same, and photoresist composition containing the resin Download PDFInfo
- Publication number
- JP2010197887A JP2010197887A JP2009044965A JP2009044965A JP2010197887A JP 2010197887 A JP2010197887 A JP 2010197887A JP 2009044965 A JP2009044965 A JP 2009044965A JP 2009044965 A JP2009044965 A JP 2009044965A JP 2010197887 A JP2010197887 A JP 2010197887A
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- JP
- Japan
- Prior art keywords
- resin
- cresol
- photoresist
- parts
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 239000011347 resin Substances 0.000 title claims abstract description 83
- 229930003836 cresol Natural products 0.000 title claims abstract description 72
- 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 title claims abstract description 71
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 125000006839 xylylene group Chemical group 0.000 claims abstract description 5
- 125000000732 arylene group Chemical group 0.000 claims abstract description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 94
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 34
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 15
- 239000005011 phenolic resin Substances 0.000 claims description 13
- 150000001896 cresols Chemical class 0.000 claims description 12
- 239000003504 photosensitizing agent Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229940100630 metacresol Drugs 0.000 claims description 10
- 238000006482 condensation reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 24
- 238000004132 cross linking Methods 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- -1 naphthoquinonediazide compound Chemical class 0.000 description 17
- 239000003377 acid catalyst Substances 0.000 description 15
- 229920003986 novolac Polymers 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000004849 alkoxymethyl group Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 4
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 4
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000003739 xylenols Chemical class 0.000 description 3
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 2
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 2
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 2
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-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
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- LEEBETSNAGEFCY-UHFFFAOYSA-N [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC(=O)C=C1 Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC(=O)C=C1 LEEBETSNAGEFCY-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- ZDROXNKXVHPNBJ-UHFFFAOYSA-N (2,6-dihydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=C(O)C=CC=C1O ZDROXNKXVHPNBJ-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- FYFNKGINBOBCKR-UHFFFAOYSA-N 1,4-bis(ethoxymethyl)benzene Chemical compound CCOCC1=CC=C(COCC)C=C1 FYFNKGINBOBCKR-UHFFFAOYSA-N 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- UQWJRHXJJRTQCX-UHFFFAOYSA-N 1-(ethoxymethyl)-4-[4-(ethoxymethyl)phenyl]benzene Chemical group C1=CC(COCC)=CC=C1C1=CC=C(COCC)C=C1 UQWJRHXJJRTQCX-UHFFFAOYSA-N 0.000 description 1
- XXYVCSHZYMXBOT-UHFFFAOYSA-N 1-benzhydryl-2,3,4,5-tetramethylbenzene Chemical compound CC=1C(=C(C(=C(C1)C(C1=CC=CC=C1)C1=CC=CC=C1)C)C)C XXYVCSHZYMXBOT-UHFFFAOYSA-N 0.000 description 1
- UIMJANTUJQGSEX-UHFFFAOYSA-N 2,2'-biphenyldimethanol Chemical group OCC1=CC=CC=C1C1=CC=CC=C1CO UIMJANTUJQGSEX-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NBLFJUWXERDUEN-UHFFFAOYSA-N 4-[(2,3,4-trihydroxyphenyl)methyl]benzene-1,2,3-triol Chemical compound OC1=C(O)C(O)=CC=C1CC1=CC=C(O)C(O)=C1O NBLFJUWXERDUEN-UHFFFAOYSA-N 0.000 description 1
- FNFYXIMJKWENNK-UHFFFAOYSA-N 4-[(2,4-dihydroxyphenyl)methyl]benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1CC1=CC=C(O)C=C1O FNFYXIMJKWENNK-UHFFFAOYSA-N 0.000 description 1
- YMSALPCDWZMQQG-UHFFFAOYSA-N 4-[2-(2,4-dihydroxyphenyl)propan-2-yl]benzene-1,3-diol Chemical compound C=1C=C(O)C=C(O)C=1C(C)(C)C1=CC=C(O)C=C1O YMSALPCDWZMQQG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- QEYKYHBKQHGNPQ-UHFFFAOYSA-N [4-[2-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=CC=C1CO QEYKYHBKQHGNPQ-UHFFFAOYSA-N 0.000 description 1
- SFHGONLFTNHXDX-UHFFFAOYSA-N [4-[4-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=C(CO)C=C1 SFHGONLFTNHXDX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229940118056 cresol / formaldehyde Drugs 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical class C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Abstract
Description
本発明は、半導体やＬＣＤを製造する際のリソグラフィ−に使用されるフォトレジスト用として、高耐熱、高感度、高残膜率、高解像度なフォトレジストの製造を可能にするクレゾール樹脂に関するものである。 The present invention relates to a cresol resin that enables the production of a photoresist with high heat resistance, high sensitivity, high residual film rate, and high resolution for use in a photoresist used in lithography in manufacturing semiconductors and LCDs. is there.
一般にポジ型フォトレジストはナフトキノンジアジド化合物等のキノンジアジド基を有する感光剤とアルカリ可溶性樹脂（例えば、ノボラック型フェノール樹脂）が用いられる。このような組成からなるポジ型フォトレジストはアルカリ溶液による現像によって高い解像力を示し、ＩＣ、ＬＳＩ等の半導体製造、ＬＣＤなどの回路基材の製造に利用されている。またノボラック型フェノール樹脂は露光後のドライエッチングに対し、芳香環を多く持つ構造に起因する高い耐熱性も有しており、これまでノボラック型フェノール樹脂とナフトキノンジアジド系感光剤とを含有する数多くのポジ型フォトレジストが開発、実用化されている。
上記のフォトレジスト用フェノール樹脂は、ｍ−またはｐ−またはｏ−クレゾ−ルとホルムアルデヒドを酸触媒の存在下で反応させて得られる樹脂であり、フォトレジストの特性を調整または向上させるために、ｍ−またはｐ−またはｏ−クレゾ−ルの比率や分子量などの検討がなされている。特に、半導体用フォトレジストでは、高耐熱、高感度、高残膜率、高解像度をバランスよく保つフェノール樹脂が重要視されている。
耐熱性を向上させる方法としては、キシレノール、トリメチルフェノールなどのアルキルフェノール類を用いて検討された例があるが、この方法では若干の向上程度であり、目的にかなうフォトレジスト用フェノール樹脂としては不十分である。
また、他に耐熱性向上の方法として、フェノール樹脂として、フェノール類（フェノール、ｍ−／ｐ−クレゾール）、ホルムアルデヒド及びモノヒドロキシ芳香族アルデヒド類を併用する方法が開示されている。（特許文献１、特許文献２）
しかし、ＬＣＤ等の分野においても、ＴＦＴ、ＳＴＮなどの技術の進展に伴い画像の線幅が細くなり、ますます微細化の傾向が強まっている。最近では、高精細なＴＦＴ表示素子では、設計寸法が数μｍレベルまで向上している。かかる用途においては、特に高い解像力、高耐熱性、高感度、高残膜率を有するフォトレジストが要求され、従来の上記のポジ型フォトレジストでは対応できないのが現状である。
In general, a positive photoresist uses a photosensitizer having a quinonediazide group such as a naphthoquinonediazide compound and an alkali-soluble resin (for example, a novolac-type phenolic resin). A positive photoresist having such a composition exhibits high resolving power when developed with an alkaline solution, and is used for the production of semiconductors such as IC and LSI, and circuit substrates such as LCDs. In addition, novolak-type phenolic resins have high heat resistance due to the structure with many aromatic rings against dry etching after exposure, and so far many novolak-type phenolic resins and naphthoquinone diazide photosensitizers have been included. A positive photoresist has been developed and put into practical use.
The above-mentioned phenol resin for photoresist is a resin obtained by reacting m-, p- or o-cresol and formaldehyde in the presence of an acid catalyst. In order to adjust or improve the characteristics of the photoresist, Studies have been made on the ratio and molecular weight of m- or p- or o-cresol. In particular, in semiconductor photoresists, a phenol resin that maintains a high balance between high heat resistance, high sensitivity, high residual film ratio, and high resolution is regarded as important.
As a method for improving heat resistance, there are examples examined using alkylphenols such as xylenol and trimethylphenol, but this method is only slightly improved and is insufficient as a phenolic resin for photoresists for the purpose. It is.
In addition, as a method for improving heat resistance, a method in which phenols (phenol, m- / p-cresol), formaldehyde, and monohydroxy aromatic aldehydes are used in combination as a phenol resin is disclosed. (Patent Document 1, Patent Document 2)
However, in the field of LCDs or the like, the line width of an image becomes narrower with the progress of technologies such as TFT and STN, and the tendency of miniaturization becomes stronger. Recently, the design dimension of high-definition TFT display elements has been improved to several μm level. In such applications, a photoresist having a particularly high resolving power, high heat resistance, high sensitivity, and a high residual film ratio is required, and the conventional positive photoresist cannot cope with the present situation.
本発明は、高耐熱性・高解像度・高感度・高残膜率を両立したフォトレジスト用クレゾール樹脂および、それから得られるレジスト組成物を提供することを目的とする。 An object of the present invention is to provide a cresol resin for a photoresist that has both high heat resistance, high resolution, high sensitivity, and a high residual film ratio, and a resist composition obtained therefrom.
本研究者らは、アリール基含有架橋基を持つフェノール型ノボラック樹脂の高耐熱性物性を生かし、かつ高解像度、高感度、高残膜率を両立したフォトレジスト用フェノール樹脂を得るために鋭意検討した結果、分子内の架橋基にアルキレン型重合体単位と、クレゾール・ホルムアルデヒド重合体単位を共に有し、両者の重合度の比を特定の範囲にすることにより、高耐熱性、高解像度、高感度、高残膜率を有するフォトレジスト用クレゾール樹脂が得られることを見出し、本発明を完成した。 The researchers have made extensive studies to obtain a phenolic resin for photoresists that takes advantage of the high heat resistance of phenolic novolak resins with aryl group-containing crosslinking groups, and that has both high resolution, high sensitivity, and high residual film ratio. As a result, it has both an alkylene type polymer unit and a cresol / formaldehyde polymer unit in the cross-linking group in the molecule, and by setting the ratio of the degree of polymerization of both to a specific range, high heat resistance, high resolution, high The inventors found that a cresol resin for photoresist having high sensitivity and a high residual film ratio can be obtained, and completed the present invention.
すなわち本発明は、下記一般式（１）で表される構成成分を含有するフォトレジスト用クレゾール樹脂である。 That is, this invention is the cresol resin for photoresists containing the structural component represented by following General formula (1).
下記一般式（１）： The following general formula (1):
（式中、Ｒは下記一般式（２）：
(Wherein R is the following general formula (2):
で示されるビフェニレン基及びキシリレン基から選ばれる少なくとも１の２価のアリーレン基を表し、Ｒ１、Ｒ２およびＲ３は、同一でも異なっていてもよく、それぞれ、水素又は、ヒドロキシ基又は炭素数１から６個のアルキル基であり、ｐ、ｑ及びｒは、それぞれ０〜２の整数である。ただし、メタクレゾールを必ず含有する。）の構成成分を含有し、そのモル比（ｍ／ｎ）が９７／３−７０／３０であることを特徴とするフォトレジスト用クレゾール樹脂。
ｍ／ｎが９７／３を超えると感度が高すぎて耐熱性に劣り、７０／３０未満であると感度が低すぎて実使用に向かない。
Represents at least one divalent arylene group selected from a biphenylene group and a xylylene group, and R 1, R 2, and R 3 may be the same or different, and each represents hydrogen, a hydroxy group, or a carbon number of 1 to 6 It is an alkyl group, and p, q, and r are integers of 0-2, respectively. However, it must contain metacresol. ), And its molar ratio (m / n) is 97 / 3-70 / 30.
If m / n exceeds 97/3, the sensitivity is too high and the heat resistance is poor, and if it is less than 70/30, the sensitivity is too low to be suitable for actual use.
また、本発明は、クレゾール類、一般式（２）のＲを構成する架橋体（ｎモル）及びホルムアルデヒド（ｍモル）その使用モル比（ｍ／ｎ）を９７／３−７０／３０とし、酸触媒存在下で縮合させることを特徴とする上記式（１）の構成成分を含有するフォトレジスト用クレゾール樹脂の製造方法である。 Further, the present invention provides a cresol, a cross-linked product (n mole) constituting R of the general formula (2) and formaldehyde (m mole), a use molar ratio (m / n) of 97 / 3-70 / 30, A method for producing a cresol resin for a photoresist containing a constituent of the above formula (1), wherein the condensation is carried out in the presence of an acid catalyst.
さらに、本発明のレジスト組成物は、上記フォトレジスト用クレゾール樹脂を含有するレジスト組成物であり、好ましくは感光剤成分を含有し、より好ましくは感光剤として１，２−キノンジアジド化合物を含有するレジスト組成物である。 Further, the resist composition of the present invention is a resist composition containing the above-mentioned cresol resin for photoresist, preferably containing a photosensitizer component, more preferably a resist containing a 1,2-quinonediazide compound as a photosensitizer. It is a composition.
本発明により、従来の方法では得られなかった高耐熱性・高解像度・高感度・高残膜率を両立したフォトレジスト用クレゾール樹脂を提供できる。
本発明により製造されたフォトレジスト用クレゾール樹脂を使用したフォトレジストは、高集積半導体を製造する際のリソグラフィ−や液晶用の薄膜フィルムトランジスター（ＴＦＴ）材料に使用され、半導体や液晶製品の歩留まりの向上および高集積化に極めて貢献できる。
According to the present invention, it is possible to provide a cresol resin for a photoresist that achieves both high heat resistance, high resolution, high sensitivity, and a high residual film ratio that cannot be obtained by a conventional method.
The photoresist using the cresol resin for photoresist manufactured according to the present invention is used as a thin film transistor (TFT) material for lithography and liquid crystal when manufacturing highly integrated semiconductors. It can greatly contribute to improvement and high integration.
以下に本発明について詳細に説明する。
本発明のフォトレジスト用クレゾール樹脂は、メタクレゾ−ルを含有するクレゾール類と、ホルムアルデヒド（ｍモル数）及び、上記一般式（１）で示されるＲを構成する架橋体（ｎモル数）との縮合生成物であり、そのモル比（ｍ／ｎ）が９７／３−７０／３０を特徴とするフォトレジスト用クレゾール樹脂である。好ましくは９７／３−８０／２０であり、さらに好ましくは、９６／４−８５／１５であるフォトレジスト用クレゾール樹脂である。
ｍ／ｎが９７／３を超えると感度が高すぎて耐熱性に劣り、７０／３０未満であると感度が低すぎて実使用に向かない。
The present invention is described in detail below.
The cresol resin for photoresists of the present invention comprises cresols containing metacresol, formaldehyde (mole number), and a cross-linked product (n mole number) constituting R represented by the general formula (1). A cresol resin for photoresists, which is a condensation product and has a molar ratio (m / n) of 97 / 3-70 / 30. Preferably it is 97 / 3-80 / 20, More preferably, it is cresol resin for photoresists which is 96 / 4-85 / 15.
If m / n exceeds 97/3, the sensitivity is too high and the heat resistance is poor, and if it is less than 70/30, the sensitivity is too low to be suitable for actual use.
本発明では、メタクレゾール（ｍ−クレゾール）が必須であるが、その他使用できるクレゾール類としては、具体的には、フェノール、ｐ−クレゾ−ル、ｏ−クレゾ−ル、キシレノ−ル、トリメチルフェノ−ルが挙げられる。キシレノ−ルは、２、３−キシレノ−ル、２、４−キシレノ−ル、２、５−キシレノ−ル、２、６−キシレノ−ル、３、４−キシレノ−ル、３、５−キシレノ−ルの各構造異性体が使用でき、トリメチルフェノ−ルにおいても、２、３、５−トリメチルフェノ−ル、２、３、６−トリメチルフェノ−ル等の各異性体が使用できる。また、カテコール、レゾルシノール、ヒドロキノン等の２価フェノール類も使用できる。
好ましくは、Ｐ−クレゾールおよびトリメチルフェノールである。
In the present invention, metacresol (m-cresol) is essential, but other cresols that can be used include, specifically, phenol, p-cresol, o-cresol, xylenol, and trimethylphenol. -May be mentioned. Xylenol is 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol. Each structural isomer can be used, and also in trimethylphenol, each isomer such as 2,3,5-trimethylphenol, 2,3,6-trimethylphenol and the like can be used. Divalent phenols such as catechol, resorcinol and hydroquinone can also be used.
P-cresol and trimethylphenol are preferable.
本発明でメチレン架橋基を形成する化合物としては、ホルムアルデヒドが好適に挙げられる。さらにホルムアルデヒドの形態としては、特に制限はないが、ホルムアルデヒド水溶液、及びパラホルムアルデヒド、トリオキサンなど酸存在下で分解してホルムアルデヒドとなる重合物を用いることも出来る。
好ましくは、取り扱いの容易なホルムアルデヒド水溶液であり、市販品の４２％ホルムアルデヒド水溶液をそのまま使用することも出来る。
As the compound that forms a methylene crosslinking group in the present invention, formaldehyde is preferably exemplified. Furthermore, the form of formaldehyde is not particularly limited, but a formaldehyde aqueous solution and a polymer that decomposes in the presence of an acid such as paraformaldehyde and trioxane to formaldehyde can also be used.
A formaldehyde aqueous solution that is easy to handle is preferable, and a commercially available 42% formaldehyde aqueous solution can be used as it is.
本発明で使用する架橋基Ｒは、次式（２）で表されるビフェニリレン基またはキシリレン基であり、具体的には４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等があげられる。これらの異性体においては、単独でも混合しても使用することができる。
好ましくは、４，４’−ビフェニリレン基および１，４−キシリレン基が挙げられる。
The bridging group R used in the present invention is a biphenylylene group or a xylylene group represented by the following formula (2), specifically, a 4,4′-biphenylylene group, a 2,4′-biphenylylene group, or 2 , 2'-biphenylylene group and / or 1,4-xylylene group, 1,2-xylylene group, 1,3-xylylene group, and the like. These isomers can be used alone or in combination.
Preferably, 4,4'-biphenylylene group and 1,4-xylylene group are mentioned.
これらの架橋基は、次式（３）で表される化合物により誘導される。
These crosslinking groups are derived from a compound represented by the following formula (3).
（ここで、式中、Ｙはハロゲン原子、ヒドロキシル基又は炭素原子数１〜６のアルコキシル基を表す。）で示される。
具体的には、４，４’−ジ（ハロゲノメチル）ビフェニル、２，４’−ジ（ハロゲノメチル）ビフェニル、２，２’−ジ（ハロゲノメチル）ビフェニル、４，４’−ジ（アルコキシメチル）ビフェニル、２，４’−ジ（アルコキシメチル）ビフェニル、２，２’−ジ（アルコキシメチル）ビフェニル、１，４−ジ（ハロゲノメチル）ベンゼン、１，４−ジ（アルコキシメチル）ベンゼン、１，２−ジ（ハロゲノメチル）ベンゼン、１，２−ジ（アルコキシメチル）ベンゼン、１，３−ジ（ハロゲノメチル）ベンゼンおよび１，３−ジ（アルコキシメチル）ベンゼンを用いることにより導かれる。
あるいは、４，４’−ジ（ヒドロキシメチル）ビフェニル、２，４’−ジ（ヒドロキシメチル）ビフェニル、２，２’−ジ（ヒドロキシメチル）ビフェニル、１，４−ジ（ヒドロキシメチル）ベンゼン、１，３−ジ（ヒドロキシメチル）ベンゼンおよび１，２−ジ（ヒドロキシメチル）ベンゼンを用いることもできる。
ここで、ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素が挙げられるが、塩素が好ましい。アルコキシル基としては、特に制限はないが、炭素数１〜６個の脂肪族アルコキシが好ましい。具体的には、メトキシおよびエトキシが挙げられる。
好ましい具体的な化合物としては、４，４’−ジ（クロロメチル）ビフェニル、４，４’−ジ（メトキシメチル）ビフェニル、４，４’−ジ（エトキシメチル）ビフェニル、１，４−ジ（クロロメチル）ベンゼン、１，４−ジ（メトキシメチル）ベンゼン及び１，４−ジ（エトキシメチル）ベンゼンが挙げられる。
これら、（１）式中のＲを構成する架橋体としては、ビフェニリレン基および／又はキシリレン基を単一でも混合して使用することも何ら問題ではない。
Here, Y represents a halogen atom, a hydroxyl group, or an alkoxyl group having 1 to 6 carbon atoms.
Specifically, 4,4′-di (halogenomethyl) biphenyl, 2,4′-di (halogenomethyl) biphenyl, 2,2′-di (halogenomethyl) biphenyl, 4,4′-di (alkoxymethyl) ) Biphenyl, 2,4′-di (alkoxymethyl) biphenyl, 2,2′-di (alkoxymethyl) biphenyl, 1,4-di (halogenomethyl) benzene, 1,4-di (alkoxymethyl) benzene, 1 , 2-di (halogenomethyl) benzene, 1,2-di (alkoxymethyl) benzene, 1,3-di (halogenomethyl) benzene and 1,3-di (alkoxymethyl) benzene.
Alternatively, 4,4′-di (hydroxymethyl) biphenyl, 2,4′-di (hydroxymethyl) biphenyl, 2,2′-di (hydroxymethyl) biphenyl, 1,4-di (hydroxymethyl) benzene, 1 , 3-Di (hydroxymethyl) benzene and 1,2-di (hydroxymethyl) benzene can also be used.
Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine, with chlorine being preferred. Although there is no restriction | limiting in particular as an alkoxyl group, A C1-C6 aliphatic alkoxy is preferable. Specific examples include methoxy and ethoxy.
Preferred specific compounds include 4,4′-di (chloromethyl) biphenyl, 4,4′-di (methoxymethyl) biphenyl, 4,4′-di (ethoxymethyl) biphenyl, 1,4-di ( Chloromethyl) benzene, 1,4-di (methoxymethyl) benzene and 1,4-di (ethoxymethyl) benzene.
As the cross-linked product constituting R in the formula (1), it is not a problem to use a single biphenylylene group and / or xylylene group in combination.
［フォトレジスト用クレゾール樹脂の製造］
一般式（１）で示される構成成分を含むフォトレジスト用クレゾール樹脂の製造方法は、酸触媒存在下、一定量のクレゾール類に対して、ｎ倍モルのＲ、即ち４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等とｍ倍モルのホルムアルデヒドを同時に添加して１段の縮合反応で行なうことができる。
この場合はクレゾール類１モルに対して、（１）式中のＲを構成する架橋体及びホルムアルデヒドの合計モル数Ｆの値は、特に限定はされないが、０．６〜１．２倍モルにするのが好ましく、より好ましくは０．７〜１．１５倍モルの範囲である。
（１）式中のＲを構成する架橋体及びホルムアルデヒドの合計が０．６倍モル未満であると感度が高すぎて耐熱性に劣り、１．２倍モルを超えると感度が低すぎて実使用に向かない場合がある。
１段での縮合反応では、反応温度を低温（一例として１００℃前後）にてクレゾール類とホルムアルデヒドの反応を優先的に行ない、主として低分子量のメチレン架橋基のクレゾール樹脂を形成させ、次いで昇温または触媒を増量してメチレン架橋基フェノール樹脂、（１）式中のＲを構成する架橋体及びクレゾール類を反応させる方式を採用するのが好ましい。
[Manufacture of cresol resin for photoresist]
A method for producing a cresol resin for a photoresist containing a constituent represented by the general formula (1) is as follows: n-fold mole of R, that is, 4,4′-biphenylylene group with respect to a certain amount of cresol in the presence of an acid catalyst. Or 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4-xylylene group, 1,2-xylylene group, 1,3-xylylene group, etc. Can be added simultaneously and carried out in a one-stage condensation reaction.
In this case, the value of the total number of moles F of the cross-linked product constituting R in the formula (1) and formaldehyde with respect to 1 mole of cresols is not particularly limited, but is 0.6 to 1.2 times mole. Preferably, it is in a range of 0.7 to 1.15 times mole.
(1) If the total of the cross-linked body and formaldehyde constituting R in the formula is less than 0.6 times mole, the sensitivity is too high and the heat resistance is poor, and if it exceeds 1.2 times mole, the sensitivity is too low. May not be suitable for use.
In the one-stage condensation reaction, the reaction between cresols and formaldehyde is preferentially performed at a low reaction temperature (for example, around 100 ° C. as an example) to form a cresol resin mainly having a low molecular weight methylene crosslinking group, and then the temperature is raised. Or it is preferable to employ | adopt the system which increases a catalyst and reacts the methylene crosslinking group phenol resin, the crosslinked body which comprises R in Formula (1), and cresol.
別法としては、架橋基ホルムアルデヒドと（１）式中のＲを構成する４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋体の添加順序をずらす方法も挙げられる。
一例として、酸触媒の存在下で、予めクレゾール類とホルムアルデヒドを縮合させ、次いで（１）式中のＲを構成する架橋体を添加して縮合させる２段の縮合反応で製造する方法である。このような２段の縮合反応では、２段目の反応において新たにクレゾール類を添加することができる。２段目の反応において追加する（１）式中のＲを構成する架橋体及びクレゾール類は、仕込むクレゾール類１モルに対して、仕込む（１）式中のＲを構成する架橋体と縮合反応済みのホルムアルデヒドの合計モル数Ｆが０．６〜１．２倍モルにするのが好ましく、０．７〜１．１５倍モルの範囲で使用することがさらに好ましい。（１）式中のＲを構成する架橋体及びホルムアルデヒドの合計モル数Ｆが０．６倍モル未満であると感度が高すぎて耐熱性に劣り、１．２倍モルを超えると感度が低すぎて実使用に向かない場合がある。
Alternatively, the bridging group formaldehyde and the 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4 constituting R in the formula (1) A method of shifting the addition order of a crosslinked product such as a -xylylene group, a 1,2-xylylene group, or a 1,3-xylylene group is also included.
As an example, there is a method of producing by a two-stage condensation reaction in which cresols and formaldehyde are condensed in advance in the presence of an acid catalyst, and then a crosslinked product constituting R in the formula (1) is added and condensed. In such a two-stage condensation reaction, cresols can be newly added in the second-stage reaction. The cross-linked product and cresol constituting R in the formula (1) added in the second stage reaction are condensed with the cross-linked product constituting R in the formula (1) to be charged with respect to 1 mol of the cresol charged. The total number of moles F of the used formaldehyde is preferably 0.6 to 1.2 times mole, and more preferably 0.7 to 1.15 times mole. (1) If the total number of moles F of the crosslinked body and formaldehyde constituting R in the formula is less than 0.6 times mole, the sensitivity is too high and the heat resistance is poor, and if it exceeds 1.2 times mole, the sensitivity is low. It may not be suitable for actual use.
さらなる別法としては、酸触媒の存在下で、予めクレゾール類と（１）式中のＲを構成する４，４’−ビフェニリレン基または、２，４’−ビフェニリレン基または、２，２’−ビフェニリレン基および／又は１，４−キシリレン基または、１，２−キシリレン基または、１，３−キシリレン基等の架橋体を縮合させ、次いでホルムアルデヒドを添加して縮合させる２段の縮合反応で製造することもできる。このような２段の縮合反応では、２段目の反応において新たにクレゾール類を添加することができる。２段目の反応において追加するホルムアルデヒドおよびクレゾール類は、クレゾール１モルに対して、縮合反応済みの（１）式中のＲを構成する架橋体とホルムアルデヒドの合計モル数Ｆが０．６〜１．２倍モルが好ましく、０．７〜１．１５倍モルの範囲になるように調整するのがさらに好ましい。（１）式中のＲを構成する架橋体及びホルムアルデヒドの合計モル数Ｆが０．６倍モル未満であると感度が高すぎて耐熱性に劣り、１．２倍モルを超えると感度が低すぎて実使用に向かない場合がある。このような２段反応で行なうと、アルキレン基含有架橋基型フェノール樹脂及びメチレン架橋基含有フェノール樹脂の各重合単位の重合度、すなわちｎ及びｍの分布が狭くなり、分子量のコントロールが容易となり、所望の重合体が得やすいので、本発明の目的のためには好ましい。 As a further alternative, in the presence of an acid catalyst, a cresol and a 4,4′-biphenylylene group, a 2,4′-biphenylylene group, or a 2,2′- Produced by a two-stage condensation reaction in which a biphenylylene group and / or a 1,4-xylylene group, a 1,2-xylylene group, or a 1,3-xylylene group or the like is condensed and then formaldehyde is added to condense. You can also In such a two-stage condensation reaction, cresols can be newly added in the second-stage reaction. Formaldehyde and cresols added in the second-stage reaction are such that the total number of moles F of the cross-linked product constituting R in the formula (1) and formaldehyde after condensation reaction is 0.6 to 1 with respect to 1 mole of cresol. .2 moles are preferred, and it is more preferred to adjust so as to be in the range of 0.7 to 1.15 moles. (1) If the total number of moles F of the crosslinked body and formaldehyde constituting R in the formula is less than 0.6 times mole, the sensitivity is too high and the heat resistance is poor, and if it exceeds 1.2 times mole, the sensitivity is low. It may not be suitable for actual use. When carried out in such a two-stage reaction, the degree of polymerization of each polymer unit of the alkylene group-containing crosslinkable phenol resin and the methylene crosslinkable group-containing phenol resin, that is, the distribution of n and m becomes narrow, and the control of the molecular weight becomes easy. It is preferred for the purposes of the present invention because the desired polymer is easily obtained.
本発明のフォトレジスト用クレゾール樹脂の合成に使用される酸触媒としては、特に限定はなく、ベンゼンスルホン酸、パラトルエンスルホン酸、メタンスルホン酸などの有機スルホン酸、塩酸、硫酸などの無機酸、蓚酸、ギ酸などの有機カルボン酸など公知のものを単独であるいは２種以上併用して使用することができるが、硫酸、蓚酸またはパラトルエンスルホン酸が特に好ましい。使用量は、クレゾール類に対して０．０１重量％から１重量％であるが、フォトレジスト用レジンの特性のために極力少ない方が好ましい。樹脂中に酸触媒が残存するとフォトレジストの特性に弊害を及ぼすため、アミン類または無機アルカリを使用して酸触媒を中和することが好ましい。 The acid catalyst used for the synthesis of the cresol resin for photoresist of the present invention is not particularly limited, and organic sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid and methanesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, Known organic carboxylic acids such as oxalic acid and formic acid can be used alone or in combination of two or more, and sulfuric acid, oxalic acid or paratoluenesulfonic acid is particularly preferred. The amount used is 0.01% to 1% by weight with respect to the cresols, but is preferably as small as possible due to the characteristics of the resin for photoresist. If the acid catalyst remains in the resin, it adversely affects the characteristics of the photoresist. Therefore, it is preferable to neutralize the acid catalyst using an amine or an inorganic alkali.
反応温度は、使用するクレゾール類、一般式（１）のＲを構成する架橋体およびホルムアルデヒドの配合割合にもよるが、通常５０〜２００℃、好ましくは７０〜１８０℃、より好ましくは８０〜１７０℃である。５０℃より低いと重合が遅く、２００℃より高いと反応の制御が難しくなり、目的のノボラック型フェノール樹脂を安定的に得ることが困難となる。
反応溶媒は、クレゾール類自体、（１）式中のＲを構成する架橋体ならびにホルムアルデヒドを溶解する水がその役割を担うが、場合によっては反応に影響を及ぼさない有機溶媒を使用することもできる。
これらの有機溶媒としては、ジエチレングリコールジメチルエーテル、１，２−ジメトキシエタン、１，２−ジエトキシエタン等のエーテル類；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エステル類；テトラヒドロフラン、ジオキサン等の環状エーテル類等が挙げられる。これらの有機溶媒の使用量は、通常、クレゾール類１００重量部当り、２０〜１０００重量部である。
The reaction temperature is usually 50 to 200 ° C., preferably 70 to 180 ° C., more preferably 80 to 170, although it depends on the mixing ratio of the cresol to be used, the cross-linked product constituting R of the general formula (1) and formaldehyde. ° C. When it is lower than 50 ° C., the polymerization is slow, and when it is higher than 200 ° C., it becomes difficult to control the reaction, and it becomes difficult to stably obtain the desired novolak type phenol resin.
As the reaction solvent, the cresol itself, the cross-linked product constituting R in the formula (1), and water for dissolving formaldehyde play a role, but in some cases, an organic solvent that does not affect the reaction can also be used. .
Examples of these organic solvents include ethers such as diethylene glycol dimethyl ether, 1,2-dimethoxyethane, and 1,2-diethoxyethane; esters such as propylene glycol monomethyl ether acetate; and cyclic ethers such as tetrahydrofuran and dioxane. It is done. The amount of these organic solvents used is usually 20 to 1000 parts by weight per 100 parts by weight of cresols.
反応時間は、反応温度にもよるが、通常は２０時間以内である。 Although the reaction time depends on the reaction temperature, it is usually within 20 hours.
反応圧力は、通常は常圧下で行われるが、若干の加圧ないし減圧下でも行うことができる。 The reaction pressure is usually carried out under normal pressure, but it can also be carried out under slight pressure or reduced pressure.
反応終了後、反応を停止するために塩基を添加して酸触媒を中和し、続いて酸触媒を除去するために水を加えて水洗を実施する。
酸触媒の中和のための塩基としては、特に限定されることはなく、酸触媒を中和し、水に可溶となる塩を形成するものであれば使用可能である。金属水酸化物や金属炭酸塩などの無機塩基ならびにアミンや有機アミンなどの有機塩基が挙げられる。無機塩基としては、具体的には水酸化ナトリウム、水酸化カリウム、水酸化カルシウムや炭酸ナトリウム、炭酸水素ナトリウム、炭酸カルシウムが挙げられる。有機塩基のアミンあるいは有機アミンの具体例としては、アンモニア、トリメチルアミン、トリエチルアミン、ジエチルアミン、トリブチルアミンなどが挙げられる。好ましくは有機アミンが使用される。
使用量は酸触媒の量にもよるが、酸触媒を中和し、反応系内のｐＨが４〜８の範囲に入るような量で使用することが好ましい。
水洗水の量と回数は特に限定されないが、酸触媒を実使用に影響ない程度の量まで除去する水洗回数としては、１〜５回程度が好ましい。また、水洗温度は、特に限定されないが、触媒種除去の効率と作業性の観点から４０〜９５℃で行うのが好ましい。水洗中、樹脂と水洗水の分離が悪い場合は、レジンの粘度を低下させる溶媒の添加や水洗温度を上昇させることが効果的である。溶媒種は特に限定されないが、クレゾール樹脂を溶解し、粘度を低下させるものであれば使用することができる。
After completion of the reaction, a base is added to neutralize the acid catalyst in order to stop the reaction, and then water is added and water washing is performed to remove the acid catalyst.
The base for neutralizing the acid catalyst is not particularly limited, and any base that neutralizes the acid catalyst and forms a salt that is soluble in water can be used. Examples include inorganic bases such as metal hydroxides and metal carbonates, and organic bases such as amines and organic amines. Specific examples of the inorganic base include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, and calcium carbonate. Specific examples of organic base amines or organic amines include ammonia, trimethylamine, triethylamine, diethylamine, and tributylamine. Preferably organic amines are used.
The amount used depends on the amount of the acid catalyst, but it is preferable to neutralize the acid catalyst so that the pH in the reaction system falls within the range of 4-8.
The amount and number of times of washing water are not particularly limited, but the number of times of washing to remove the acid catalyst to such an amount that does not affect actual use is preferably about 1 to 5 times. The washing temperature is not particularly limited, but is preferably 40 to 95 ° C. from the viewpoint of the efficiency of removing the catalyst species and the workability. If the resin and the washing water are poorly separated during washing, it is effective to add a solvent that lowers the viscosity of the resin and raise the washing temperature. The solvent species is not particularly limited, and any solvent can be used as long as it dissolves the cresol resin and lowers the viscosity.
酸性触媒を除去した後、一般的には、反応系の温度を１３０℃〜２３０℃に上げて、減圧下、例えば２０〜５０ｔｏｒｒの圧力下で、反応系内に存在する未反応原料、有機溶媒等の揮発分を留去して、クレゾール樹脂を回収する。 After removing the acidic catalyst, generally, the temperature of the reaction system is increased to 130 ° C. to 230 ° C., and the unreacted raw materials and organic solvents present in the reaction system under reduced pressure, for example, 20 to 50 torr. The cresol resin is recovered by distilling off the volatile components such as.
本発明のフォトレジスト用クレゾール樹脂の重量平均分子量は、特に限定されないが、フォトレジストの性能や製造上のハンドリング性から４０００〜２００００が好ましい。より好ましくは５０００〜１５０００である。重量平均分子量が４０００より小さい場合は、感度が高すぎて耐熱性に劣り、２００００より大きい場合は感度が低すぎて実使用に向かない場合がある。 Although the weight average molecular weight of the cresol resin for photoresists of the present invention is not particularly limited, it is preferably from 4,000 to 20,000 from the viewpoint of the performance of the photoresist and the handling properties in production. More preferably, it is 5000-15000. When the weight average molecular weight is less than 4000, the sensitivity is too high and the heat resistance is poor, and when it is more than 20000, the sensitivity is too low to be suitable for actual use.
本発明のフォトレジスト用クレゾール樹脂の軟化点は、耐熱性から１４０℃以上が好ましく、さらに好ましくは１５０℃以上、もっとも好ましくは１６０℃以上である。軟化点が１４０℃より低いと、フォトレジスト用として使用する場合に、耐熱性に劣る。 The softening point of the cresol resin for photoresists of the present invention is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and most preferably 160 ° C. or higher in view of heat resistance. When the softening point is lower than 140 ° C., the heat resistance is poor when used as a photoresist.
［レジスト組成物］
得られたフォトレレジスト用クレゾール樹脂は、該樹脂を含むレジスト組成物として使用することができる。
この組成物には、さらに、感光剤成分を含有することが好ましい。
感光剤成分としては、キノンジアジド基を含む化合物であり、好ましくは１、２−キノンジアジド化合物を含有する感光剤である。
[Resist composition]
The obtained cresol resin for photoresist can be used as a resist composition containing the resin.
This composition preferably further contains a photosensitizer component.
The photosensitizer component is a compound containing a quinonediazide group, preferably a photosensitizer containing a 1,2-quinonediazide compound.
このキノンジアジド基を含む化合物の感光剤としては、従来キノンジアジド−ノボラック系レジストで用いられている公知の感光剤のいずれのものをも用いることができる。このような感光剤としては、ナフトキノンジアジドスルホン酸クロライドやベンゾキノンジアジドスルホン酸クロライド等と、これら酸クロライドと縮合反応可能な官能基を有する低分子化合物または高分子化合物とを反応させることによって得られた化合物が好ましいものである。ここで酸クロライドと縮合可能な官能基としては水酸基、アミノ基等があげられるが、特に水酸基が好適である。水酸基を含む酸クロライドと縮合可能な化合物としては、例えばハイドロキノン、レゾルシン、２、４−ジヒドロキシベンゾフェノン、２、３、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、４、４’−トリヒドロキシベンゾフェノン、２、３、４、４’−テトラヒドロキシベンゾフェノン、２、２’、４、４’−テトラヒドロキシベンゾフェノン、２、２’、３、４、６’−ペンタヒドロキシベンゾフェノン等のヒドロキシベンゾフェノン類、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、ビス（２、４−ジヒドロキシフェニル）プロパン等のヒドロキシフェニルアルカン類、４、４’、３”、４”−テトラヒドロキシ−３、５、３’、５’−テトラメチルトリフェニルメタン、４、４’、２”、３”、４”−ペンタヒドロキシ−３、５、３’、５’−テトラメチルトリフェニルメタン等のヒドロキシトリフェニルメタン類などを挙げることができる。これらは単独で用いてもよいし、また２種以上を組合せて用いてもよい。 As the photosensitizer of the compound containing a quinonediazide group, any of the known photosensitizers conventionally used in quinonediazide-novolak resists can be used. As such a photosensitizer, it was obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride, etc. with a low molecular compound or a high molecular compound having a functional group capable of condensation reaction with these acid chlorides. Compounds are preferred. Here, examples of the functional group capable of condensing with an acid chloride include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferred. Examples of the compound that can be condensed with an acid chloride containing a hydroxyl group include hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2, 4, 4 and the like. '-Trihydroxybenzophenone, 2, 3, 4, 4'-tetrahydroxybenzophenone, 2, 2', 4, 4'-tetrahydroxybenzophenone, 2, 2 ', 3, 4, 6'-pentahydroxybenzophenone, etc. Hydroxyphenyl alkanes such as hydroxybenzophenones, bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane, 4, 4 ′ 3 ", 4" -tetrahydroxy-3, 5, 3 ', 5 -Mentioning hydroxytriphenylmethanes such as tetramethyltriphenylmethane, 4, 4 ', 2 ", 3", 4 "-pentahydroxy-3, 5, 3', 5'-tetramethyltriphenylmethane These may be used alone or in combination of two or more.
また、ナフトキノンジアジドスルホン酸クロライドやベンゾキノンジアジドスルホン酸クロライドなどの酸クロライドとしては、例えば、１、２−ナフトキノンジアジド−５−スルフォニルクロライド、１、２−ナフトキノンジアジド−４−スルフォニルクロライドなどが好ましいものとして挙げられる。 Further, as acid chlorides such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride, for example, 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride and the like are preferable. Can be mentioned.
キノンジアジド基を含む感光剤の配合量は、フォトレジスト用クレゾール樹脂１００重量部当たり、通常５〜５０重量部、好ましくは、１０〜４０重量部である。これよりも少なくと、感光性樹組成物として十分な感度が得られないことがあり、またこれよりも多いと成分の析出の問題が起こることがあるので注意が必要である。 The amount of the photosensitizer containing a quinonediazide group is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the cresol resin for photoresist. If it is less than this, sufficient sensitivity as a photosensitive tree composition may not be obtained, and if it is more than this, a problem of precipitation of components may occur.
本発明により、従来の方法では得られなかった高耐熱性・高解像度・高感度・高残膜率を両立したフォトレジスト用クレゾール樹脂を提供できる。 According to the present invention, it is possible to provide a cresol resin for a photoresist that achieves both high heat resistance, high resolution, high sensitivity, and a high residual film ratio that cannot be obtained by a conventional method.
以下に実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、部は重量部を示す。
また、成分の含有量および樹脂の物性値等の分析方法は以下の通りである。
（１）（ＧＰＣ測定方法）
型式 ：ＨＬＣ−８２２０ 東ソー（株）製
カラム ：ＴＳＫ−ＧＥＬ Ｈタイプ Ｇ２０００Ｈ×Ｌ ４本
Ｇ３０００Ｈ×Ｌ １本
Ｇ４０００Ｈ×Ｌ １本
測定条件：カラム圧力 １３．５ＭＰａ
溶離液 ：テトラヒドロフラン（ＴＨＦ）フローレート １ｍｌ／ｍｉｎ
温度 ：４０℃
検出器 スペクトロフォトメーター（ＵＶ−８０２０）ＲＡＮＧＥ ２．５６
ＷＡＶＥ ＬＥＮＧＴＨ ２５４ｎｍ とＲＩ
（２）（軟化点）
ＪＩＳ Ｋ−７２３４に準じた方法で測定
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, a part shows a weight part.
Moreover, analysis methods, such as a content of a component and a physical-property value of resin, are as follows.
(1) (GPC measurement method)
Model: HLC-8220 Tosoh Co., Ltd. column: TSK-GEL H type G2000H × L 4 G3000H × L 1 G4000H × L 1 Measurement condition: Column pressure 13.5 MPa
Eluent: Tetrahydrofuran (THF) flow rate 1 ml / min
Temperature: 40 ° C
Detector Spectrophotometer (UV-8020) RANGE 2.56
WAVE LENGTH 254nm and RI
(2) (Softening point)
Measured according to JIS K-7234
［参考例１］（ベースレジン）
温度計、仕込・留出口および攪拌機を備えた容量１０００容量部のガラス製フラスコにｍ−クレゾール１００部（０．９３モル）、ｐ−キシレングリコールジメチルエーテル（以下、１，４−ＰＸＤＭと略記する。）２８部（０．１７モル）及びパラトルエンスルホン酸０．２部を三つ口フラスコに入れ、１４０℃で３時間反応させた。その後、反応温度を１６０℃に昇温し、３時間反応を行った。その間、生成するメタノールを留去した。反応終了後、９０℃まで冷却してトリエチルアミン０．３部添加し、イオン交換水１００部を添加して攪拌、静置した。静置することにより分離した分離水のｐＨを５．５〜７．０となるように調整し、分離水を除去した。この操作を２回行った。その後、１８５℃まで昇温して脱水した後、３０ｔｏｒｒで２時間減圧蒸留にて未反応ｍ−クレゾールを留去し、ノボラック型クレゾール樹脂５０部を得た。
このときの得られたノボラック型クレゾール樹脂中のクレゾール分は、０．２０モルに相当し、該樹脂の重量平均分子量は、７７６であり、軟化点は９５℃であった。
[Reference Example 1] (Base resin)
It is abbreviated as 100 parts (0.93 mol) of m-cresol and p-xylene glycol dimethyl ether (hereinafter abbreviated as 1,4-PXDM) in a glass flask having a capacity of 1000 parts by volume equipped with a thermometer, a charging / distilling outlet and a stirrer. ) 28 parts (0.17 mol) and 0.2 parts of paratoluenesulfonic acid were placed in a three-necked flask and reacted at 140 ° C. for 3 hours. Thereafter, the reaction temperature was raised to 160 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the mixture was cooled to 90 ° C., 0.3 parts of triethylamine was added, 100 parts of ion exchange water was added, and the mixture was stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Then, after heating up to 185 degreeC and dehydrating, unreacted m-cresol was distilled off under reduced pressure distillation at 30 torr for 2 hours, and 50 parts of novolak-type cresol resin was obtained.
The cresol content in the novolak cresol resin obtained at this time was 0.20 mol, the weight average molecular weight of the resin was 776, and the softening point was 95 ° C.
［参考例２］（ベースレジン）
参考例１において、１，４−ＰＸＤＭを４，４−ビス（メトキシメチル）ビフェニル（以下、４，４’−ＢＭＭＢと略記する。）４０部（０．１７モル）に代えた以外は、同様にしてノボラック型クレゾール樹脂６０部を得た。
このときの得られたノボラック型クレゾール樹脂中のクレゾール分は、０．１８モルに相当し、該樹脂の重量平均分子量は、１００２であり、軟化点は７３℃であった。
[Reference Example 2] (Base resin)
The same as in Reference Example 1, except that 1,4-PXDM was replaced with 40 parts (0.17 mol) of 4,4-bis (methoxymethyl) biphenyl (hereinafter abbreviated as 4,4′-BMMB). Thus, 60 parts of a novolac cresol resin was obtained.
The cresol content in the novolak cresol resin obtained at this time was equivalent to 0.18 mol, the weight average molecular weight of the resin was 1002, and the softening point was 73 ° C.
［実施例１］（ベースレジン＋ｍ／ｐ−６／４）
温度計、仕込・留出口および攪拌機を備えた容量５００容量部のガラス製フラスコにｍ−クレゾール１００部（０．９３モル）、ｐ−クレゾール６６．７部（０．６２モル）、上記［参考例１］で合成したクレゾール樹脂（以下、樹脂Ａと略記する。）６３部、４２％ホルマリン７６部（１．０８モル）及びシュウ酸０．５８部を三つ口フラスコに入れ、１００℃で１８ｈ反応を行った。その後、１８５℃まで昇温して脱水した後、３０ｔｏｒｒで２時間減圧蒸留を行い、ノボラック型クレゾール樹脂８０部を得た。
このときの１，４−ＰＸＤＭの使用量は、６３．０／５０×０．１７＝０．２１モルに相当し、樹脂Ａ中に含まれるクレゾール分は、６３．０／５０×０．２０＝０．２５モルに相当する。よって、ｍ／ｎの値は８４／１６となり、Ｆの値は（１．０８＋０．２１）／（０．９３＋０．６２＋０．２５）＝０．７２であった。
得られたノボラック型クレゾール樹脂の重量平均分子量は、５４９７であり、軟化点は１４３℃、下記評価例１の溶解速度は１１５Å／ｓであった。
[Example 1] (Base resin + m / p-6 / 4)
In a glass flask having a capacity of 500 parts by volume equipped with a thermometer, a charging / distilling outlet and a stirrer, 100 parts (0.93 mol) of m-cresol, 66.7 parts (0.62 mol) of p-cresol, [Reference 63 parts of cresol resin synthesized in Example 1 (hereinafter abbreviated as “resin A”), 76 parts of 42% formalin (1.08 mol) and 0.58 part of oxalic acid were placed in a three-necked flask at 100 ° C. The reaction was performed for 18 hours. Thereafter, the temperature was raised to 185 ° C. for dehydration, and then vacuum distillation was performed at 30 torr for 2 hours to obtain 80 parts of a novolac cresol resin.
The amount of 1,4-PXDM used at this time corresponds to 63.0 / 50 × 0.17 = 0.21 mol, and the cresol content in Resin A is 63.0 / 50 × 0.20. = Corresponds to 0.25 mol. Therefore, the value of m / n was 84/16, and the value of F was (1.08 + 0.21) / (0.93 + 0.62 + 0.25) = 0.72.
The obtained novolac cresol resin had a weight average molecular weight of 5,497, a softening point of 143 ° C., and a dissolution rate of the following Evaluation Example 1 of 115 kg / s.
［実施例２］（ベースレジン＋ｍ−１００）
温度計、仕込・留出口および攪拌機を備えた容量５００容量部のガラス製フラスコにｍ−クレゾール１００部（０．９３モル）、樹脂Ａ４０部、４２％ホルマリン６１．５部（０．８７モル）及びシュウ酸０．５部を三つ口フラスコに入れ、１００℃で１８ｈ反応を行った。その後、１８５℃まで昇温して脱水した後、３０ｔｏｒｒで２時間減圧蒸留を行い、ノボラック型クレゾール樹脂１００部得た。
このときの１，４−ＰＸＤＭの使用量は、４０／５０×０．１７＝０．１４モルに相当し、樹脂Ａ中に含まれるクレゾール分は、４０／５０×０．２０＝０．１６モルに相当する。よって、ｍ／ｎの値は８６／１４となり、Ｆの値は（０．８７＋０．１４）／（０．９３＋０．１６）＝０．９３であった。
得られたノボラック型クレゾール樹脂の重量平均分子量は、９８４５であり、軟化点は１５３℃、下記評価例１の溶解速度は１４３Å／ｓであった。
[Example 2] (Base resin + m-100)
In a glass flask having a capacity of 500 parts by volume equipped with a thermometer, a charging / discharging outlet and a stirrer, 100 parts (0.93 mol) of m-cresol, 40 parts of resin A, 61.5 parts (0.87 mol) of 42% formalin And 0.5 part of oxalic acid was put into a three-necked flask and reacted at 100 ° C. for 18 hours. Then, after heating up to 185 degreeC and dehydrating, it distilled under reduced pressure at 30 torr for 2 hours, and obtained 100 parts of novolak-type cresol resins.
The amount of 1,4-PXDM used at this time corresponds to 40/50 × 0.17 = 0.14 mol, and the cresol content in Resin A is 40/50 × 0.20 = 0.16. Corresponds to moles. Therefore, the value of m / n was 86/14, and the value of F was (0.87 + 0.14) / (0.93 + 0.16) = 0.93.
The obtained novolac cresol resin had a weight average molecular weight of 9845, a softening point of 153 ° C., and a dissolution rate of the following Evaluation Example 1 of 143 kg / s.
［実施例３］（ホルマリン１ｓｔ）
温度計、仕込・留出口および攪拌機を備えた容量５００容量部のガラス製フラスコにｍ−クレゾール１００部（０．９３モル）、４２％ホルマリン４７．０部（０．６７モル）及びパラトルエンスルホン酸０．１部を三つ口フラスコに入れ、１００℃で４時間反応させた。その後、１，４−ＰＸＤＭ２４．６部（０．１５モル）を入れ、１４０℃で４時間反応させた。反応終了後、９０℃まで冷却してトリエチルアミン０．３部添加し、イオン交換水１００部を添加して攪拌、静置した。静置することにより分離した分離水のｐＨを５．５〜７．０となるように調整し、分離水を除去した。この操作を２回行った。その後、１８５℃まで昇温して脱水した後、３０ｔｏｒｒで２時間減圧蒸留を行い、ノボラック型クレゾール樹脂１３０部得た。
このときのｍ／ｎは８２／１８であり、Ｆの値は（０．６７＋０．１５）／０．９３＝０．８８であった。
得られたノボラック型クレゾール樹脂の重量平均分子量は、４７６４であり、軟化点は１４４℃、下記評価例１の溶解速度は８００Å／ｓであった。
[Example 3] (Formalin 1st)
In a 500-volume glass flask equipped with a thermometer, charging / distilling outlet and stirrer, 100 parts (0.93 mole) of m-cresol, 47.0 parts (0.67 mole) of 42% formalin and para-toluenesulfone The acid 0.1 part was put into the three necked flask, and it was made to react at 100 degreeC for 4 hours. Thereafter, 24.6 parts (0.15 mol) of 1,4-PXDM was added and reacted at 140 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.3 parts of triethylamine was added, 100 parts of ion exchange water was added, and the mixture was stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Thereafter, the temperature was raised to 185 ° C. and dehydration was performed, followed by distillation under reduced pressure at 30 torr for 2 hours to obtain 130 parts of a novolac-type cresol resin.
The m / n at this time was 82/18, and the value of F was (0.67 + 0.15) /0.93=0.88.
The obtained novolac cresol resin had a weight average molecular weight of 4,764, a softening point of 144 ° C., and the dissolution rate of the following Evaluation Example 1 was 800 Å / s.
［実施例４］（ホルマリン１ｓｔ）
温度計、仕込・留出口および攪拌機を備えた容量５００容量部のガラス製フラスコにｍ−クレゾール１００部（０．９３モル）、４２％ホルマリン５０．６部（０．７２モル）及びパラトルエンスルホン酸０．１部を三つ口フラスコに入れ、１００℃で４時間反応させた。その後、１，４−ＰＸＤＭ１３．２部（０．０８モル）を入れ、１４０℃で４時間反応させた。反応終了後、９０℃まで冷却してトリエチルアミン０．３部添加し、イオン交換水１００部を添加して攪拌、静置した。静置することにより分離した分離水のｐＨを５．５〜７．０となるように調整し、分離水を除去した。この操作を２回行った。その後、１８５℃まで昇温して脱水した後、３０ｔｏｒｒで２時間減圧蒸留を行い、ノボラック型クレゾール樹脂１１０部得た。
このときのｍ／ｎは９０／１０であり、Ｆの値は（０．７２＋０．０８）／０．９３＝０．８６であった。
得られたノボラック型クレゾール樹脂の重量平均分子量は、１３５６４であり、軟化点は１６５℃、下記評価例１の溶解速度は１２１Å／ｓであった。
[Example 4] (Formalin 1st)
In a glass flask having a capacity of 500 parts by volume equipped with a thermometer, a charging / distilling outlet and a stirrer, 100 parts (0.93 mol) of m-cresol, 50.6 parts (0.72 mol) of 42% formalin and paratoluenesulfone The acid 0.1 part was put into the three necked flask, and it was made to react at 100 degreeC for 4 hours. Thereafter, 13.2 parts (0.08 mol) of 1,4-PXDM was added and reacted at 140 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.3 parts of triethylamine was added, 100 parts of ion exchange water was added, and the mixture was stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Then, after heating up to 185 degreeC and dehydrating, it distilled under reduced pressure at 30 torr for 2 hours, and obtained 110 parts of novolak-type cresol resins.
The m / n at this time was 90/10, and the value of F was (0.72 + 0.08) /0.93=0.86.
The obtained novolac cresol resin had a weight average molecular weight of 13,564, a softening point of 165 ° C., and a dissolution rate of the following Evaluation Example 1 of 121 kg / s.
［実施例５］（ベースレジン＋ｍ−１００）
温度計、仕込・留出口および攪拌機を備えた容量５００容量部のガラス製フラスコにｍ−クレゾール１００部（０．９３モル）、上記［参考例２］で合成したフェノール樹脂（以下、樹脂Ｂと略記する。）１７．７部、４２％ホルマリン５８．７部（１．０６モル）及びシュウ酸０．４部を三つ口フラスコに入れ、１００℃で１８ｈ反応を行った。その後、１８５℃まで昇温して脱水した後、３０ｔｏｒｒで２時間減圧蒸留を行い、ノボラック型クレゾール樹脂１００部得た。
このときの４，４’−ＢＭＭＢの使用量は、１７．７／６０×０．１７＝０．０５モルに相当し、樹脂Ｂ中に含まれるクレゾール分は、１７．７／６０×０．１８＝０．０５モルに相当する。よって、ｍ／ｎは９５／５となり、Ｆの値は（１．０６＋０．０５）／（０．９３＋０．０５）＝１．１３であった。
得られたノボラック型クレゾール樹脂の重量平均分子量は、９７１３であり、軟化点は１６２℃、下記評価例１の溶解速度は２１２Å／ｓであった。
[Example 5] (Base resin + m-100)
A phenolic resin (hereinafter referred to as resin B) synthesized in 100 parts (0.93 mol) of m-cresol and the above [Reference Example 2] in a glass flask having a capacity of 500 parts by volume equipped with a thermometer, a charging / distilling outlet and a stirrer. (Abbreviated) 17.7 parts, 58.7 parts (1.06 mol) of 42% formalin and 0.4 parts of oxalic acid were placed in a three-necked flask and reacted at 100 ° C. for 18 hours. Then, after heating up to 185 degreeC and dehydrating, it distilled under reduced pressure at 30 torr for 2 hours, and obtained 100 parts of novolak-type cresol resins.
The amount of 4,4′-BMMB used at this time corresponds to 17.7 / 60 × 0.17 = 0.05 mol, and the cresol content in Resin B is 17.7 / 60 × 0. 18 corresponds to 0.05 mol. Therefore, m / n was 95/5, and the value of F was (1.06 + 0.05) / (0.93 + 0.05) = 1.13.
The obtained novolac cresol resin had a weight average molecular weight of 9713, a softening point of 162 ° C., and a dissolution rate of Evaluation Example 1 below was 212 kg / s.
［実施例６］（ホルマリン１ｓｔ）
温度計、仕込・留出口および攪拌機を備えた容量５００容量部のガラス製フラスコにｍ−クレゾール１００部（０．９３モル）、４２％ホルマリン４７．０部（０．６７モル）及びパラトルエンスルホン酸０．１部を三つ口フラスコに入れ、１００℃で４時間反応させた。その後、４，４−ＢＭＭＢ１８．０部（０．０７モル）を入れ、１４０℃で４時間反応させた。反応終了後、９０℃まで冷却してトリエチルアミン０．３部添加し、イオン交換水１００部を添加して攪拌、静置した。静置することにより分離した分離水のｐＨを５．５〜７．０となるように調整し、分離水を除去した。この操作を２回行った。その後、１８５℃まで昇温して脱水した後、３０ｔｏｒｒで２時間減圧蒸留を行い、ノボラック型クレゾール樹脂１１０部得た。
このときのｍ／ｎは９１／９となり、Ｆの値は（０．６７＋０．０７）／０．９３＝０．８０であった。
得られたノボラック型クレゾール樹脂の重量平均分子量は、６４１９であり、軟化点は１４６℃、下記評価例１の溶解速度は１０９Å／ｓであった。
[Example 6] (Formalin 1st)
In a 500-volume glass flask equipped with a thermometer, charging / distilling outlet and stirrer, 100 parts (0.93 mole) of m-cresol, 47.0 parts (0.67 mole) of 42% formalin and para-toluenesulfone The acid 0.1 part was put into the three necked flask, and it was made to react at 100 degreeC for 4 hours. Thereafter, 18.0 parts (0.07 mol) of 4,4-BMMB was added and reacted at 140 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 0.3 parts of triethylamine was added, 100 parts of ion exchange water was added, and the mixture was stirred and allowed to stand. The pH of the separated water separated by allowing to stand was adjusted to 5.5 to 7.0, and the separated water was removed. This operation was performed twice. Then, after heating up to 185 degreeC and dehydrating, it distilled under reduced pressure at 30 torr for 2 hours, and obtained 110 parts of novolak-type cresol resins.
The m / n at this time was 91/9, and the value of F was (0.67 + 0.07) /0.93=0.80.
The obtained novolac cresol resin had a weight average molecular weight of 6419, a softening point of 146 ° C., and a dissolution rate of Evaluation Example 1 below was 109 kg / s.
［比較例１］（汎用）
温度計、仕込・留出口および攪拌機を備えた容量１０００容量部のガラス製フラスコに１段目の重合として、ｍ−クレゾール２１６部（２．００モル）、ｐ−クレゾール３１４部（３．００モル）、４２％ホルマリン２１３．８部（２．９９モル）及び蓚酸１．９部を三つ口フラスコに入れ、１００℃で５ｈ反応させた後１８０℃まで昇温して脱水し、さらに２１０℃まで昇温し，減圧４０ｔｏｒｒで、スチーム条件下で９時間と減圧蒸留することにより、ノボラック型クレゾール樹脂を得た。
このときのｎは０であるが、今回ｍ／ｎは１００／０と記載した。Ｆの値は２．９９／（２．００＋３．００）＝０．６０であった。
得られたノボラック型クレゾール樹脂の重量平均分子量は、９５００であり、軟化点は１５８℃、下記評価例１の溶解速度は２５０Å／ｓであった。
[Comparative Example 1] (General purpose)
As a first-stage polymerization in a glass flask having a capacity of 1000 parts by volume equipped with a thermometer, a charging / distilling outlet and a stirrer, 216 parts (2.00 moles) of m-cresol and 314 parts (3.00 moles) of p-cresol ), 213.8 parts (2.99 mol) of 42% formalin and 1.9 parts of oxalic acid were placed in a three-necked flask, reacted at 100 ° C. for 5 hours, then heated to 180 ° C. for dehydration, and further 210 ° C. And novolak cresol resin was obtained by distillation under reduced pressure for 40 hours under reduced pressure at 40 torr.
Although n at this time is 0, m / n was described as 100/0 this time. The value of F was 2.99 / (2.00 + 3.00) = 0.60.
The obtained novolac cresol resin had a weight average molecular weight of 9,500, a softening point of 158 ° C., and a dissolution rate of Evaluation Example 1 below was 250 kg / s.
［比較例２］（サリチルアルデヒドレジン）
温度計、仕込・留出口および攪拌機を備えた容量５００容量部のガラス製フラスコにメタクレゾ−ル１００部、パラクレゾ−ル６０部、２，３，５−トリメチルフェノ−ル４０部、サリチルアルデヒド１８部、パラトルエンスルホン酸２部を仕込み、８８〜９２℃で５時間反応を行った後、エチルセロソルブ８０部を添加して内温６０℃まで冷却させ、次いで３７％ホルマリン９７部を５８−６２℃で１．５時間で逐添し、さらに３０分反応させた。その後、段階的に昇温させ、最終的に還流温度（９７−１０３℃）で３時間反応させた。反応終了後、９０℃まで冷却してトリエチルアミン１．３部を添加し、さらにアセトン２０部、イオン交換水８０部を添加して約７０℃で攪拌・静置した。静置することにより分離した分離水のｐＨを５．５−７．０となるように調整し、分離水を除去した。アセトン２０部、イオン交換水８０部を使用して、この水洗操作をもう一度繰り返した後、常圧下で内温１４０℃まで脱水し、さらに８０ｔｏｒｒで１９５℃まで減圧下で脱水・脱モノマ−を行い、フォトレジスト用クレゾール樹脂を得た。
１，４−ＰＸＤＭおよび４，４’−ＢＭＭＢのかわりにサリチルアルデヒドを使用した。
この樹脂は、通常よく使用されているフォトレジスト用クレゾール樹脂であり、重量平均分子量は５６００、軟化点は１６２℃、下記評価例１の溶解速度は６８０Å／ｓであった。
[Comparative Example 2] (Salicylaldehyde resin)
A glass flask having a capacity of 500 parts by volume equipped with a thermometer, charging / distilling outlet and stirrer, 100 parts of metacresol, 60 parts of paracresol, 40 parts of 2,3,5-trimethylphenol, 18 parts of salicylaldehyde Then, 2 parts of paratoluenesulfonic acid was added and reacted at 88-92 ° C. for 5 hours. Then, 80 parts of ethyl cellosolve was added and allowed to cool to 60 ° C. Next, 97 parts of 37% formalin was 58-62 ° C. At 1.5 hours and further reacted for 30 minutes. Then, it heated up in steps, and was finally made to react at reflux temperature (97-103 degreeC) for 3 hours. After completion of the reaction, the mixture was cooled to 90 ° C., 1.3 parts of triethylamine was added, 20 parts of acetone and 80 parts of ion-exchanged water were further added, and the mixture was stirred and allowed to stand at about 70 ° C. The pH of the separated water separated by standing was adjusted to 5.5 to 7.0, and the separated water was removed. This water washing operation was repeated once again using 20 parts of acetone and 80 parts of ion-exchanged water, and then dehydrated to an internal temperature of 140 ° C. under normal pressure, and further dehydrated and de-monomerized under reduced pressure to 195 ° C. at 80 torr. A cresol resin for photoresist was obtained.
Salicylaldehyde was used in place of 1,4-PXDM and 4,4′-BMMB.
This resin is a commonly used cresol resin for photoresist, having a weight average molecular weight of 5600, a softening point of 162 ° C., and a dissolution rate of Evaluation Example 1 below was 680 kg / s.
実施例１〜６および比較例１〜２で得られたフォトレジスト用クレゾール樹脂を下記の各評価方法に従って物性測定を行った。その結果を表１にまとめて示した。
この結果、本願発明のフェトレジスト用クレゾール樹脂は、残幕率、耐熱性および解像度をバランス良く備えた樹脂であり、従来品よりも優れている。また、該樹脂を含むレジスト組成物を提供できる。
The physical properties of the cresol resins for photoresist obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were measured according to the following evaluation methods. The results are summarized in Table 1.
As a result, the cresol resin for photoresist of the present invention is a resin having a good balance of the remaining curtain ratio, heat resistance and resolution, and is superior to the conventional products. Moreover, the resist composition containing this resin can be provided.
《評価例１》
溶解速度の評価方法
フォトレジスト用クレゾール樹脂をＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）に溶解し、樹脂溶液を調合した。これらを０．２ミクロンメンブレンフィルタ−で濾過した。これを４インチシリコンウェハー上に約１５０００Åの厚みになるようにスピンコーターで塗布し、１１０℃で６０秒間ホットプレ−ト上で乾燥させた。次いで現像液（２．３８％テトラメチルアンモニウムヒドロオキサイド水溶液）を用い、完全に膜が消失するまでの時間を計測した。初期膜厚を溶解するまでの時間で割った値を溶解速度とした。
<< Evaluation Example 1 >>
Method for evaluating dissolution rate A cresol resin for photoresist was dissolved in PGMEA (propylene glycol monomethyl ether acetate) to prepare a resin solution. These were filtered through a 0.2 micron membrane filter. This was coated on a 4 inch silicon wafer with a spin coater so as to have a thickness of about 15000 mm, and dried on a hot plate at 110 ° C. for 60 seconds. Next, using a developing solution (2.38% tetramethylammonium hydroxide aqueous solution), the time until the film completely disappeared was measured. The value obtained by dividing the initial film thickness by the time until dissolution was taken as the dissolution rate.
《評価例２》
感度、解像度及び残膜率の評価方法
フォトレジスト用クレゾール樹脂２０部とナフトキノン１、２−ジアジド−５−スルホン酸の２，３，４，４’−テトラヒドロキシベンゾフェノンエステル５部とをＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）に溶解し、レジスト溶液を調合した。これらを０．２ミクロンメンブレンフィルタ−で濾過し、レジスト液とした。これを４インチシリコンウェハー上に約１５０００Åの厚みになるようにスピンコーターで塗布し、１１０℃、６０秒間ホットプレ−ト上で乾燥させた。その後、縮小投影露光装置を用い、露光時間を段階的に変えて露光した。次いで現像液（２．３８％テトラメチルアンモニウムヒドロオキサイド水溶液）を用い、６０秒間現像した。リンス、乾燥後、各ショットの膜減り量と露光時間をプロットして、感度を求めた。また未露光部の残膜厚から残膜率を求めた。また、解像度は、テストチャートマスクを用い、下記基準で評価した。
○：１．０μライン＆スペースが解像できる。
×：１．０μライン＆スペースが解像できない。
<< Evaluation Example 2 >>
Evaluation Method of Sensitivity, Resolution and Residual Film Ratio 20 parts of cresol resin for photoresist and 5 parts of 2,3,4,4′-tetrahydroxybenzophenone ester of naphthoquinone 1,2-diazide-5-sulfonic acid were combined with PGMEA (propylene Glycol monomethyl ether acetate) was dissolved to prepare a resist solution. These were filtered through a 0.2 micron membrane filter to obtain a resist solution. This was coated on a 4 inch silicon wafer with a spin coater so as to have a thickness of about 15000 mm, and dried on a hot plate at 110 ° C. for 60 seconds. Thereafter, exposure was performed using a reduced projection exposure apparatus while changing the exposure time stepwise. Subsequently, it developed for 60 second using the developing solution (2.38% tetramethylammonium hydroxide aqueous solution). After rinsing and drying, the amount of film loss and the exposure time for each shot were plotted to determine the sensitivity. Moreover, the remaining film rate was calculated | required from the remaining film thickness of the unexposed part. The resolution was evaluated according to the following criteria using a test chart mask.
○: 1.0 μ line & space can be resolved.
X: 1.0 μ line & space cannot be resolved.
《評価例３》
耐熱性の評価方法
フォトレジスト用クレゾール樹脂２０部とナフトキノン１、２−ジアジド−５−スルホン酸の２，３，４，４’−テトラヒドロキシベンゾフェノンエステル５部とをＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）に溶解し、レジスト溶液を調合した。これらを０．２ミクロンメンブレンフィルタ−で濾過し、レジスト液とした。これを４インチシリコンウェハー上に約１５０００Åの厚みになるようにスピンコーターで塗布し、１１０℃、６０秒間ホットプレ−ト上で乾燥させた。その後、縮小投影露光装置を用い、露光時間を段階的に変えて露光した。次いで現像液（２．３８％テトラメチルアンモニウムヒドロオキサイド水溶液）を用い、６０秒間現像した。得られたシリコンウエハ−を温度を変えたホットプレ−ト上で２分間放置し、シリコウエハ−上のレジストパタ−ンの形状を走査型電子顕微鏡で観察し、耐熱性を下記基準により評価した。
○：１４０℃でパターン形状を維持できる。
×：１４０℃でパターン形状を維持できない。
<< Evaluation Example 3 >>
Evaluation Method of Heat Resistance 20 parts of cresol resin for photoresist and 5 parts of 2,3,4,4′-tetrahydroxybenzophenone ester of naphthoquinone 1,2-diazide-5-sulfonic acid are combined with PGMEA (propylene glycol monomethyl ether acetate) And a resist solution was prepared. These were filtered through a 0.2 micron membrane filter to obtain a resist solution. This was coated on a 4 inch silicon wafer with a spin coater so as to have a thickness of about 15000 mm, and dried on a hot plate at 110 ° C. for 60 seconds. Thereafter, exposure was performed using a reduced projection exposure apparatus while changing the exposure time stepwise. Subsequently, it developed for 60 second using the developing solution (2.38% tetramethylammonium hydroxide aqueous solution). The obtained silicon wafer was allowed to stand for 2 minutes on a hot plate with different temperatures, the shape of the resist pattern on the silicon wafer was observed with a scanning electron microscope, and the heat resistance was evaluated according to the following criteria.
○: The pattern shape can be maintained at 140 ° C.
X: The pattern shape cannot be maintained at 140 ° C.
Claims (9)
（式中、Ｒは下記一般式（２）：
で示されるビフェニレン基及びキシリレン基から選ばれる少なくとも１つの２価のアリーレン基を表し、Ｒ１、Ｒ２およびＲ３は、同一でも異なっていてもよく、それぞれ、水素又は、ヒドロキシ基又は炭素数１から６個のアルキル基であり、ｐ、ｑ及びｒは、それぞれ０〜２の整数である。ただし、メタクレゾールを必ず含有する。）の構成成分を含有し、そのモル比（ｍ／ｎ）が９７／３−７０／３０であることを特徴とするフォトレジスト用クレゾール樹脂。 The following general formula (1):
(Wherein R is the following general formula (2):
Represents at least one divalent arylene group selected from a biphenylene group and a xylylene group, and R 1, R 2, and R 3 may be the same or different and each represents hydrogen, a hydroxy group, or a carbon number of 1 to 6 It is an alkyl group, and p, q, and r are integers of 0-2, respectively. However, it must contain metacresol. ), And its molar ratio (m / n) is 97 / 3-70 / 30.
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| JP2013015642A (en) * | 2011-07-01 | 2013-01-24 | Asahi Kasei E-Materials Corp | Phenolic resin composition, method for producing cured relief pattern, and semiconductor device |
| WO2013085004A1 (en) * | 2011-12-09 | 2013-06-13 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition, method for producing hardened relief pattern, semiconductor device and display device |
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| JP2005290319A (en) * | 2004-04-05 | 2005-10-20 | Ube Ind Ltd | Phenolic resin for rubber composition additive |
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