WO2021060080A1 - ポリマー、感光性樹脂組成物、樹脂膜、および電子装置 - Google Patents
ポリマー、感光性樹脂組成物、樹脂膜、および電子装置 Download PDFInfo
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- WO2021060080A1 WO2021060080A1 PCT/JP2020/034961 JP2020034961W WO2021060080A1 WO 2021060080 A1 WO2021060080 A1 WO 2021060080A1 JP 2020034961 W JP2020034961 W JP 2020034961W WO 2021060080 A1 WO2021060080 A1 WO 2021060080A1
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- polymer
- carbon atoms
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- photosensitive resin
- resin composition
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- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical class [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- UFULDTPDHIRNGS-UHFFFAOYSA-N hept-6-en-1-ol Chemical compound OCCCCCC=C UFULDTPDHIRNGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- YPQKTLPPOXNDMC-UHFFFAOYSA-N isocyanic acid;methylcyclohexane Chemical compound N=C=O.CC1CCCCC1 YPQKTLPPOXNDMC-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- LLAZQXZGAVBLRX-UHFFFAOYSA-N methyl 2,5-dioxopyrrole-1-carboxylate Chemical compound COC(=O)N1C(=O)C=CC1=O LLAZQXZGAVBLRX-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical compound NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- FYMHIQYSJCOOKI-UHFFFAOYSA-N tert-butyl 2-(2,5-dioxopyrrol-1-yl)acetate Chemical compound CC(C)(C)OC(=O)CN1C(=O)C=CC1=O FYMHIQYSJCOOKI-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/22—Esters containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- 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
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Definitions
- the present invention relates to polymers, photosensitive resin compositions, resin films, and electronic devices. More specifically, the present invention relates to a polymer, a photosensitive resin composition containing the polymer, a resin film made of a cured product of the photosensitive resin composition, and an electronic device including the resin film.
- Patent Document 1 a radiation-sensitive resin composition containing the [A] polymer and the [B] acid generator is described.
- the polymer [A] has a structural unit (I) and a structural unit (II), so that it is excellent in LWR (Line Width Reference) performance and defect suppression property, which indicates a small amount of rattling in the line width. It is described (paragraph 0012 of Patent Document 1).
- the structural unit (I) is N- (t-butyloxycarbonylmethyl) maleimide, N- (1-methyl-1-cyclopentyloxycarbonylmethyl) maleimide, or N- (2-ethyl-2-adamantyloxy). It is described that it is a structural unit derived from (carbonylmethyl) maleimide. Further, it is described that the structural unit (II) is a structural unit derived from 2-norbornene.
- the present inventor examined the durability of the negative photosensitive resin composition. As a result, it was found that the radiation-sensitive resin composition described in Patent Document 1 has room for further improvement in terms of durability and low dielectric constant.
- the present invention provides a photosensitive resin composition having an excellent balance between durability and low dielectric constant, and a polymer for use in such a photosensitive resin composition.
- the present inventor uses a polymer having a structural unit having a specific structure so that the cured product of the photosensitive resin composition containing the polymer has improved heat resistance, improved solvent resistance and low dielectric constant. And completed the present invention.
- R 1 , R 2 , R 3 and R 4 are independently hydrogen or organic groups having 1 to 30 carbon atoms, and n is 0, 1 or 2.
- R 5 is an organic group having 1 to 30 carbon atoms. At least one of R 1 , R 2 , R 3 , R 4 and R 5 is a fluorine-containing organic group having 1 to 30 carbon atoms. ).
- R 1 , R 2 , R 3 and R 4 are independently hydrogen or organic groups having 1 to 30 carbon atoms, and n is 0, 1 or 2.
- R 5 is an organic group having 1 to 30 carbon atoms. At least one of R 1 , R 2 , R 3 , R 4 and R 5 is a fluorine-containing organic group having 1 to 30 carbon atoms. ).
- a resin film made of a cured film of the above-mentioned photosensitive resin composition is provided.
- an electronic device provided with the above resin film is provided.
- a polymer which is excellent in heat resistance and solvent resistance and can be suitably used for producing a low-dielectric resin film.
- polymer P The polymer of the present embodiment (hereinafter referred to as "polymer P") contains structural units represented by the following formulas (1) and (2a).
- R 1 , R 2 , R 3 and R 4 are independently hydrogen or organic groups having 1 to 30 carbon atoms, and n is 0, 1 or 2.
- R 5 is an organic group having 1 to 30 carbon atoms. At least one of R 1 , R 2 , R 3 , R 4 and R 5 is a fluorine-containing organic group having 1 to 30 carbon atoms.
- the polymer P contains the above-mentioned structural units, so that the cured product has excellent heat resistance and solvent resistance, and also has low dielectric properties. Therefore, it can be suitably used as a material for producing a resin film for an electronic device.
- the polymer P has a structural unit derived from a norbornene-type monomer represented by the formula (1) and a structural unit derived from maleic anhydride represented by the formula (2a).
- n is 0, 1 or 2, preferably 0.
- R 1 , R 2 , R 3 and R 4 are independently hydrogen or organic groups having 1 to 30 carbon atoms.
- R 5 is an organic group having 1 to 30 carbon atoms. At least one of R 1 , R 2 , R 3 , R 4 and R 5 is a fluorine-containing organic group having 1 to 30 carbon atoms.
- the ratio of the structural unit represented by the formula (1) in the total structural units of the polymer P is preferably 35 mol% or more and 70 mol% or less, and more preferably 40 mol% or more and 60 mol% or less.
- Examples of the organic group having 1 to 30 carbon atoms that can constitute any of R 1 , R 2 , R 3 and R 4 , and R 5 in the formula (1) and the formula (2a) include an alkyl group, an alkenyl group, and an alkynyl group. Examples include a group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, and a heterocyclic group.
- Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a heptyl group. Examples include octyl group, nonyl group, and decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. Examples of the alkynyl group include an ethynyl group.
- Examples of the alkylidene group include a methylidene group and an ethylidene group.
- Aryl groups include, for example, a phenyl group, a naphthyl group, and an anthrasenyl group.
- Examples of the aralkyl group include a benzyl group and a phenethyl group.
- Examples of the alkaline group include a tolyl group and a xylyl group.
- Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
- the organic group having 1 to 30 carbon atoms may contain at least one atom selected from O, N, S, P and Si in its structure.
- the organic group having 1 to 30 carbon atoms is preferably an organic group having 1 to 15 carbon atoms, and more preferably an organic group having 1 to 10 carbon atoms.
- the organic group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. It is even more preferable to have.
- R 1 , R 2 , R 3 , R 4, and R 5 is a fluorine-containing organic group having 1 to 30 carbon atoms.
- the fluorine-containing organic group having 1 to 30 carbon atoms include a fluoroalkyl group having 1 to 30 carbon atoms and a fluoroalkyl group having 1 to 30 carbon atoms having an ethereal oxygen atom.
- the fluoroalkyl group having 1 to 30 carbon atoms is an organic group in which one or more hydrogen atoms in the alkyl group are substituted with fluorine atoms.
- fluoroalkyl groups include alkyl fluoride groups and perfluoroalkyl groups.
- any one of R 1 , R 2 , R 3 and R 4 is a fluorine-containing organic group having 1 to 30 carbon atoms, and the rest is a hydrogen atom.
- any one of R 1 , R 2 , R 3 and R 4 is a fluoroalkyl group having 1 to 30 carbon atoms, and the rest are hydrogen atoms.
- any one of R 1 , R 2 , R 3 and R 4 is a perfluoroalkyl group having 1 to 30 carbon atoms, and the rest are hydrogen atoms.
- a photosensitive resin composition containing this polymer P because any one of R 1 , R 2 , R 3 and R 4 is a fluorine-containing organic group having 1 to 30 carbon atoms and the rest is a hydrogen atom.
- the film forming property can be improved, and the obtained cured film can be made low in dielectric property.
- R 5 is preferably a fluoroalkyl group having 1 to 30 carbon atoms having a fluoroalkyl group or an etheric oxygen atom having 1 to 30 carbon atoms.
- the organic groups constituting R 1 , R 2 , R 3 and R 4 are preferably organic groups having no acidic functional group. By not having an acidic organic group, it is possible to easily control the acid value of this polymer P.
- the polymer P of the present embodiment may further contain at least one of the structural units represented by the formulas (B2) to (B6).
- R 6 and R 7 are independently organic groups having 1 to 30 carbon atoms.
- R 8 is an organic group having 1 to 30 carbon atoms.
- An organic group having 1 to 30 carbon atoms is synonymous with the above definition. It is preferable that any of R 5 , R 6 and R 7 has a carbon-carbon double bond crosslinked by a photoradical polymerization initiator.
- a vinyl group, a vinylidene group, an allyl group, an acryloyl group, and a methacryloyl group can be mentioned.
- a maleimide-derived structural unit represented by the formula (B5) or the formula (B6) because the heat resistance of the obtained cured film is improved. It is preferable that none of the organic groups constituting R 6 to R 8 has an acidic functional group such as a carboxyl group. This makes it possible to easily control the acid value of the polymer P.
- the polymer P of the present embodiment can be prepared by addition polymerization of a norbornene-type monomer (monomer A) represented by the formula (3) and maleic anhydride (monomer B) represented by the formula (4). it can.
- the polymer P of the present embodiment further contains a structural unit represented by the formula (B5) and / or the formula (B6), it is represented by the norbornene-type monomer (monomer A), maleic anhydride and the formula (5).
- the desired polymer can be prepared by addition polymerization of maleimide and / or the maleimide derivative (monomer B).
- n 0, 1 or 2
- R 1 , R 2 , R 3 and R 4 are independently hydrogen or organic groups having 1 to 30 carbon atoms, respectively.
- R 8 is similar to the above definition.
- Examples of the norbornene-type monomer that can be used include the following norbornene.
- maleimide derivative represented by the above formula (5) examples include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-aminophenyl) maleimide, N-benzylmaleimide, and N-tert-butyl. Included are maleimide, N-ethylmaleimide, N- (2-hydroxyethyl) maleimide, N-methoxycarbonylmaleimide, 3-maleimide propionic acid, 4-maleimide butyric acid and 6-maleimide hexanoic acid. Among these, it is preferable to use N-cyclohexylmaleimide. This makes it possible to improve the heat resistance and chemical resistance of the cured product of the polymer P.
- the polymer P can be synthesized by an addition polymerization reaction between the monomer A and the monomer B. It should be noted that the use of one type or two or more types of monomers as the monomer A and the monomer B is not limited.
- the method of addition polymerization is not limited, but in the present embodiment, a copolymer is synthesized by radical polymerization using a radical polymerization initiator. By addition polymerization using a radical polymerization initiator, a copolymer having a structural unit derived from monomer A and a structural unit derived from monomer B and having a terminal derived from the radical polymerization initiator is synthesized. Can be done.
- the molar ratio of monomer A to monomer B in the copolymer is preferably 1: 0.5 to 1: 2.
- the above 1: 0.5 to 1: 2 includes 1: 0.5 and 1: 2.
- the molar ratio is preferably 1: 1 from the viewpoint of improving the controllability of the molecular structure.
- Monomer A, monomer B, and radical polymerization initiator are dissolved in a solvent and then heated for a predetermined time to allow addition polymerization to proceed.
- the heating temperature is, for example, 50 ° C. or higher and 80 ° C. or lower, and the heating time is 3 hours or longer and 20 hours or lower.
- an additive such as a chain transfer agent may be used in the addition polymerization. It is preferable to control the terminal structure of the copolymer by adding a chain transfer agent and introduce a functional group that reacts with the cross-linking agent into the terminal of the copolymer.
- the radical polymerization initiator is not limited as long as it introduces a functional group that reacts with a cross-linking agent into X, which is one of the ends of the copolymer, and an azo compound or a peroxide can be used. Among these, it is preferable to use an azo compound.
- the azo compound has a carboxyl group such as 4,4'-azobis (4-cyanovaleric acid) and 2,2'-azobis [N- (2-carboxyethyl) -2-methyl].
- Radical polymerization initiator Radical polymerization initiator having an amino group such as 2,2'-azobis (2-methylpropionamidine), 2,2'-azobis [2- (2-imidazolin-2-yl) propane]; Examples thereof include a radical polymerization initiator having a hydroxy group such as 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide].
- a radical polymerization initiator having a carboxyl group it is preferable to use a radical polymerization initiator having a carboxyl group, and among them, it is more preferable to use 4,4'-azobis (4-cyanovaleric acid). Thereby, the heat resistance and chemical resistance of the obtained polymer P can be improved.
- the amount (number of moles) of the radical polymerization initiator added is preferably 1% or more and 10% or less of the total number of moles of the monomer A and the monomer B.
- the weight average molecular weight (Mw) of the obtained copolymer can be adjusted by appropriately setting the amount of the radical polymerization initiator within the above range and appropriately setting the reaction temperature and the reaction time.
- the ring-opening step in the polymer precursor obtained as described above, among the structural units derived from maleic anhydride, some repeating units are ring-closed and the remaining repeating units are ring-opened. Thereby, the amount of carboxyl groups in the copolymer can be adjusted. That is, the acid value of the produced copolymer can be controlled. Then, by controlling the acid value, the alkali solubility of the photosensitive resin composition containing the polymer P can be adjusted.
- the repeating units derived from maleic anhydride of the polymer precursor for example, 50% or more of the repeating units are not ring-opened, and the cyclic structure (anhydrous ring) of the remaining repeating units is opened. .. That is, the ring-opening rate of the copolymer is, for example, less than 50%. Among them, it is preferable to open the ring of 10% or more and 30% or less of the total number of repeating units of the cyclic structure derived from maleic anhydride of the copolymer.
- the ring-opening rate of the repeating unit derived from maleic anhydride can be measured as follows.
- the ring opening rate is calculated from (Abs2) by the following formula.
- Ring-opening rate (%) (((Abs1)-(Abs2)) / (Abs1)) ⁇ 100 Acetonitrile is used as an internal standard substance.
- the polymer precursor shall be treated with either (i) a metal alkoxide as a base, (ii) an alcohol and an alkali metal hydroxide as a base, or (iii) an organic base such as an alcohol and a tertiary amine.
- a metal alkoxide as a base
- an alcohol and an alkali metal hydroxide as a base
- an organic base such as an alcohol and a tertiary amine.
- the maleic anhydride structural unit becomes a ring-opened polymer P.
- the reagent (i) or the reagent (ii) is added to the reaction solution in which the monomers A and B are polymerized, and an organic solvent such as methyl ethyl ketone (MEK) is further added. , 40 ° C. or higher and 50 ° C.
- reaction solution L1 a part of the anhydrous ring of the repeating unit derived from maleic anhydride of the copolymer is opened, and a part of the terminal formed by the ring opening is esterified. The remaining ends are not esterified and have a metal salt structure.
- the number of moles of the metal alkoxide or alkali metal hydroxide is preferably 50% or less of the number of moles of maleic anhydride used in the polymerization step.
- the number of moles of the metal alkoxide or alkali metal hydroxide is preferably 40% or less, 10% or more, and further 30% or less of the number of moles of maleic anhydride used in the polymerization step. Is preferable.
- the amount of the metal alkoxide or the hydroxide of the alkali metal can be reduced, and the concentration of the alkali metal in the finally obtained polymer P can be reduced.
- the alkali metal concentration in the polymer P it is possible to suppress the migration of metal ions in a device using a resin composition using the polymer P.
- metal alkoxide As the metal alkoxide described above, those represented by M (OR 5 ) are preferable (M is a monovalent metal, and R 5 is an organic group having 1 or more and 30 or less carbon atoms). Examples of the metal M include alkali metals, and among them, sodium is preferable from the viewpoint of handleability.
- the R 5, are the same as those for R 5 in example above formula (2a).
- As the metal alkoxide two or more different types may be used. However, from the viewpoint of production stability, it is preferable to use one kind of metal alkoxide.
- the structure derived from maleic anhydride of the polymer precursor may be ring-opened in the presence of (ii) an alcohol and a hydroxide of an alkali metal as a base.
- an alcohol As the alkali metal hydroxide, sodium hydroxide is preferable from the viewpoint of handleability.
- the alcohol monohydric alcohol (R 5 OH) is preferred.
- R 5 is an organic group may be used those described above. It is preferable that R 5 has 1 or more carbon atoms and 30 or less carbon atoms.
- the monovalent alcohol is preferably used in the present embodiment (R 5 OH), allyl alcohol, methallyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, 4-penten - 1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 10-undesen-1- All, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexane.
- the repeating unit derived from maleic anhydride that was ring-opened in this ring-opening step has a structure represented by the following formula (5a) and has a structure having a salt moiety of a carboxyl group.
- R 5 is an organic group having 1 to 30 carbon atoms.
- R 6 and R 7 are independently organic groups having 1 or more and 30 or less carbon atoms.
- a monomer having an epoxy group and a double bond group can be further reacted to obtain a polymer P into which a crosslinkable double bond-containing group has been introduced.
- glycidyl acrylate, glycidyl methacrylate or 3,4-epoxycyclohexylmethyl methacrylate as the monomer having an epoxy group and a double bond group in view of availability.
- fluorine functional group by reacting a monomer having an epoxy group and a fluorine functional group in the same manner.
- 3-perfluorobutyl-1,2-epoxypropane 3-perfluorohexyl-1,2-epoxypropane, 3-perfluorooctyl-1,2-epoxypropane and the like can be used.
- the polymer P includes a group having a double bond, the crosslinkability of the photoradical polymerization initiator can be improved, and as a result, the sensitivity of the polymer P can be improved.
- the copolymer is acid-treated by adding an acidic aqueous solution such as hydrochloric acid or formic acid to the reaction solution L1 to replace the metal ion (Na + ) with a proton (H +).
- an acidic aqueous solution such as hydrochloric acid or formic acid
- the structural unit represented by the above formula (6) becomes the structural unit represented by the following (2a) and (B4) by proton substitution, respectively.
- R 5 is an organic group having 1 to 30 carbon atoms.
- this ring-opening step (S3) it is preferable not to open 50% or more of the repeating units derived from maleic anhydride of the polymer precursor.
- a metal such as Na is bonded to one end formed by opening the anhydrous malein ring, but by not opening the repeating unit of 50% or more.
- the amount of metal contained in the product polymer P can be reduced. Thereby, the amount of the alkali metal in the polymer P finally obtained in the present embodiment can be reduced, and the desired property can be exhibited in the photosensitive resin composition containing the polymer P.
- the obtained solution containing the polymer P may be washed with a mixed solution of water and an organic solvent (for example, methyl ethyl ketone) to remove residual metal components.
- the cleaning step is preferably performed so that the alkali metal concentration in the polymer P is 10 ppm or less, preferably 5 ppm or less.
- the weight average molecular weight (Mw) of the polymer P of the present embodiment is preferably in the range of 1000 or more and 20000 or less, more preferably 1500 or more and 15000 or less, and 2000 or more, from the viewpoint of forming an appropriate crosslinked structure. Even more preferably, it is 10,000 or less.
- the number average molecular weight (Mn) of the polymer P of the present embodiment is preferably 500 or more and 10000 or less, and more preferably 1000 or more and 8000 or less, from the viewpoint of forming an appropriate crosslinked structure.
- the molecular weight distribution (Mw / Mn) of the polymer P is 1.0 or more. It is preferably 5 or less, and more preferably 1.2 or more and 2.0 or less.
- the molecular weight of the polymer P can be controlled by adjusting the type of the above-mentioned monomer used for the preparation of the polymer P, the blending amount thereof, the adjusting conditions, and the like.
- the double bond equivalent of the polymer P of the present embodiment is preferably 500 g / mol or more and 2500 g / mol or less, and more preferably 500 g / mol or more and 2000 g / mol or less.
- the polymer P is suitably used for the photosensitive resin composition to be subjected to the exposure development treatment.
- the fluorine content of the polymer P of the present embodiment is preferably 25 wt% or more and 45 wt% or less, and more preferably 30 wt% or more and 40 wt% or less.
- the fluorine content of the polymer P can be controlled by adjusting the types of the above-mentioned monomers used in the preparation of the polymer P and the blending amounts thereof.
- the polymer P of the present embodiment has excellent alkali solubility, and therefore has excellent processability in an exposure development process using an alkaline aqueous solution as a developing solution.
- the alkali dissolution rate of the polymer P can be, for example, 10 ⁇ / sec or more and 2500 ⁇ / sec or less, and more preferably 50 ⁇ / sec or more and 2000 ⁇ / sec or less.
- the alkali dissolution rate is such that a polymer film obtained by applying a propylene glycol monomethyl ether acetate solution (solid content 35% by mass) of polymer P on a silicon wafer by a spin method and soft-baking at 100 ° C. for 120 seconds is obtained. It is calculated by impregnating a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. and visually measuring the time until the polymer film is erased.
- the polymer P of the present embodiment has, for example, a refractive index of 1.38 or more and 1.48 or less, and more preferably 1.40 or more and 1.46 or less.
- the polymer P having a refractive index within the above range is excellent in processability by exposure development, and the cured product has desired characteristics as a permanent film of an electronic device.
- the polymer P of the present embodiment is used in a photosensitive resin composition for forming a resin film of an electronic device.
- the photosensitive resin composition of the present embodiment is With the above polymer P With a cross-linking agent Includes photosensitizer.
- the photosensitive resin composition of the present embodiment contains the above-mentioned polymer P, so that the cured product has excellent heat resistance and solvent resistance, and also has low dielectric property. Therefore, the photosensitive resin composition of the present embodiment can be suitably used as a material for producing a permanent film of an electronic device.
- the photosensitive resin composition of the present embodiment contains a cross-linking agent.
- the cross-linking agent is not limited as long as it is a compound containing a functional group capable of reacting with the active hydrogen of the polymer P.
- Examples of such a cross-linking agent include compounds having at least one functional group selected from a glycidyl group, an oxetanyl group and a blocked isocyanate group.
- cross-linking agent a compound having a glycidyl group or an oxetanyl group is more preferable, and a compound having a glycidyl group is even more preferable.
- a cross-linking agent an appropriate cross-linked structure can be formed.
- one or more selected from compounds having a blocked isocyanate group, epoxy compounds and oxetane compounds can also be used in combination.
- Examples of the compound having a glycidyl group used as a cross-linking agent include allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and bisphenol A.
- glycidyl ether such as glycidyl ether, glycidyl ester such as adipic acid diglycidyl ester, glycidyl ester such as o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3, 4-Epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2, 3-Epoxycyclopentyl) ether, alicyclic epoxy such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, Epolide GT401, 2,2'-(((((1- (4)) -(2- (4- (Oxylan) -
- bisphenol A type such as LX-01 (manufactured by Daiso), jER1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, jER825 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.).
- Epoxy resin, bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), jER152, 154 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.), etc.
- Phenol novolac type epoxy resin EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.) CY179, 184 (trade name; manufactured by Huntsman Advanced Materials), ERL-4206, 4221, 4234, 4299 (trade name: manufactured by Dow Chemical), Epicron 200, 400 (trade name; manufactured by DIC), jER871, Cyclic aliphatic epoxy resin such as 872 (trade name; manufactured by Mitsubishi Chemical Corporation), poly [(2-oxylanyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propane
- a polyfunctional alicyclic epoxy resin such as diol ether (3: 1), EHPE-3150 (manufactured by Daicel Co., Ltd.) can also be used.
- Examples of the compound having an oxetane group used as a cross-linking agent include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene and bis [1-ethyl (3-oxetanyl)] methyl ether.
- the compound having a blocked isocyanate group used as a cross-linking agent is not limited, and is, for example, a compound in which the isocyanate group of a polyfunctional isocyanate is protected by a blocking agent.
- the polyfunctional isocyanate is an organic compound having a plurality of isocyanate groups in one molecule.
- examples of the polyfunctional isocyanate include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 2,2,4-.
- One or more selected from the derivatives of the diisocyanate compound and the like can be mentioned.
- the blocking agent examples include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, and oximes.
- alcohol compounds phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, and oximes.
- amine compounds, imine compounds, barrous sulfate, pyridine compounds and the like can be mentioned.
- Specific blocking agents include oxime, etanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carpitol, benzyl alcohol, cyclohexanol and the like.
- Alcor compounds such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester; malonic acid Active methylene compounds such as dimethyl, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; Oxime-based compounds such as; oxyimide-based compounds such as succinateimide and maleateimide; imidazole-based compounds such as imidazole and 2-methylimidazole; urea-based compounds such as urea, thiourea and ethyleneurea.
- phenol compounds such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester
- Oxime compounds such as formaldehyde, acetoaldoxime, acetoxime, methylethylketooxime, cyclohexanone oxime; amine compounds such as diphenylamine, aniline, and carbazole; imide compounds such as ethyleneimine and polyethyleneimine; Da- and other heavy sulfites; pyridine-based compounds such as 2-hydroxypyridine and 2-hydroxyquinoline can be mentioned.
- Specific examples of the compound having a blocked isocyanate group used as such a cross-linking agent include Barnock D-500 (tolylene diisocyanate blocked product) and Barnock D-550 manufactured by Dainippon Ink and Chemicals Co., Ltd. 1,6-Hexamethylene diisocyanate blocked product), Vernock D-980K (1,6-hexamethylene diisocyanate blocked product); Takeda Chemical Co., Ltd.
- Takenate B-830 (trilened isocyanate) -Toblocked product), Takenate B-815N (4,4'-methylenebis (cyclohexylisocyanate) blocked product), Takenate B-842N (1,3-bis (isocyanatemethyl) cyclohexaneblocked product), Takenate B-846N (1,3-Bis (isocyanatemethyl) cyclohexane blocked product), Takenate B-874N (isophoron diisocyanate blocked product), Takenate B-882N (1,6-hexamethylene diisocyanate blocked product) , Takenate B-890 (xylylene diisocyanate blocked); Takenate B-820NP (1,3-bis (isocyanatemethyl) cyclohexane blocked), Takenate B-885N (1,6-hexamethylene diisocyanate) -Toblocked product); Examples thereof include Duranate MF-B60X (1,6-hexamethylene diiso
- a photoactive compound can be used as the photosensitizer, and for example, a diazoquinone compound can be used.
- a diazoquinone compound can be used.
- any one or more of the following compounds can be used.
- N2 is an integer of 1 or more and 5 or less.
- Q is any of the structures shown below or a hydrogen atom.
- at least one of the Qs of each compound is any of the following.
- an o-naphthoquinonediazide sulfonic acid derivative having a Q of (a) or (b) is preferable from the viewpoint of transparency and dielectric constant of the photosensitive resin composition.
- the positive photosensitive resin composition may contain an acid generator that generates an acid by light or heat.
- an acid generator that generates an acid by light or heat.
- the cross-linking reaction of the cross-linking agent can be promoted by exposing and developing the photosensitive resin composition and then irradiating or heating with light.
- the amount of the acid generator is preferably 3 parts by mass or less with respect to 100 parts by mass of the cross-linking agent.
- the photoacid generator that generates acid by light those described later can be used.
- the content of the thermoacid generator is preferably 0.1% by mass or more and 5% by mass or less, for example, when the total solid content of the photosensitive resin composition is 100% by mass.
- the total solid content of the photosensitive resin composition means a component excluding the solvent.
- a photoacid generator can be used as the photosensitive agent.
- the photoacid generator may be any agent that absorbs the energy of light to produce blended acid or Lewis acid, for example, triphenylsulfonium trifluoromethanesulfonate, tris (4-t-butylphenyl) sulfonium-trifluo.
- Sulfonium salts such as lomethanesulfonate; diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate; ammonium salts; phosphonium salts; diphenyliodonium trifluoromethanesulfonates, iodonium salts such as (tricmill) iodonium-tetrakis (pentafluorophenyl) borate; quinonediazide , Diazomethanes such as bis (phenylsulfonyl) diazomethane; sulfonic acid esters such as 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, N-hydroxynaphthalimide-trifluoromethanesulfonate; diphenyl Disulfons such as disulfones; tris (2,4,6-trichloromethyl) -s-triazin
- a second cross-linking agent that crosslinks the copolymer by the action of an acid may be included.
- This second cross-linking agent cross-links the copolymer using the acid generated by the photo-acid generator as a catalyst, and is different from the compound used for the cross-linking agent.
- a melamine-based cross-linking agent, a urea-based cross-linking agent, and the like can be mentioned.
- Examples of the melamine-based cross-linking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like, and hexamethoxymethylmelamine is preferable.
- Examples of the urea-based cross-linking agent include methylated urea resin, bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, and the like, and the methylated urea resin is particularly preferable.
- Examples of commercially available products of the methylated urea resin include MX-270, MX-280, and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
- the ratio of the second cross-linking agent in the negative type photosensitive resin composition is preferably 5% by mass or more and 40% by mass or less when the total solid content of the resin composition is 100% by mass, and the resolution is high. From the viewpoint, it is more preferably 5% by mass or more and 30% by mass or less, and further preferably 10 to 25% by mass.
- the ratio of each component is as follows, for example.
- the total solid content of the photosensitive resin composition is 100% by mass, it is preferable that the above-mentioned copolymer is contained in an amount of, for example, 30% by mass or more and 70% by mass or less, and in particular, 40% by mass or more and 60% by mass or less. It is preferably contained below.
- the cross-linking agent is preferably contained, for example, 15% by mass or more and 50% by mass or less, and more than 20% by mass or more and 50% by mass or less. It is preferable to do so.
- the photoactive compound as a photosensitive agent is contained, for example, 5% by mass or more and 40% by mass or less, and 10% by mass or more and 30% by mass. It is more preferably contained in an amount of% by mass or less.
- the ratio of each component is as follows, for example.
- the total solid content of the photosensitive resin composition is 100% by mass, it is preferable that the above-mentioned copolymer is contained in an amount of, for example, 30% by mass or more and 70% by mass, and above all, 40% by mass or more and 60% by mass or less. It is preferable to contain it.
- a cross-linking agent excluding the second cross-linking agent
- the amount of the photoacid generator is, for example, 0.1% by mass or more and 40% by mass or less, forming a high-resolution pattern film. More preferably, it is 1% by mass or more and 30% by mass or less.
- Additives such as a solvent, an antioxidant, a surfactant, an adhesion aid, a dissolution accelerator, a filler, a sensitizer, and polyphenols may be further added to the photosensitive resin composition.
- the resin film according to this embodiment is made of a cured product of the above-mentioned photosensitive resin composition. Since this resin film has excellent heat resistance, it is used as a resist or a permanent film in an electronic device.
- the resist is a coating film obtained by applying the photosensitive resin composition of the present embodiment by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating. Is obtained and the solvent is removed.
- the coating film of the photosensitive resin composition obtained as described above is exposed and developed, patterned into a desired shape, and then cured by heat treatment or the like. Obtained by The permanent film can be used, for example, as a protective film, an interlayer film, or the like of an electronic device.
- the electronic device includes the above resin film.
- the electronic device of this embodiment includes the above resin film.
- the passivation film and the insulating layer constituting the semiconductor chip are formed by the cured product of the photosensitive resin composition of the present embodiment.
- the polymer had a weight average molecular weight Mw of 2,400 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.69.
- the polymer was then collected by filtration, washed with methanol, and vacuum dried at 120 ° C. for 16 hours.
- the yield of the polymer was 14.9 g and the yield was 50%.
- the polymer had a Mw of 4,000 and a Mw / Mn of 1.50.
- V-601 (3.81 g, 15.3 mmol) was added and the reaction was carried out for another 3 hours.
- the reaction mixture was diluted with MEK and then added dropwise to a large amount of methanol to precipitate a polymer. After filtering with Nutche, the solid was further washed with methanol and vacuum dried.
- the weight average molecular weight (Mw) of the obtained polymer was 5,400, and the dispersity (Mw / Mn) was 1.72.
- V-601 (0.74 g, 3.0 mmol) was added and the reaction was carried out for another 3 hours.
- the reaction mixture was diluted with MEK and then added dropwise to a large amount of methanol to precipitate a polymer. After filtering with Nutche, the solid was further washed with methanol and vacuum dried.
- the weight average molecular weight (Mw) of the obtained polymer was 3,700, and the dispersity (Mw / Mn) was 1.64.
- Table 1 shows the blending amounts of the components used in Synthesis Examples 1 to 4, and the weight average molecular weight and dispersity of the obtained precursor polymer.
- the obtained polymer is collected by filtration, washed with pure water, dissolved in propylene glycol monomethyl ether acetate (PGMEA), and residual water is removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%. Obtained.
- the weight average molecular weight (Mw) of the polymer thus obtained was 2,100, and the molecular weight distribution was 1.55.
- the double bond equivalent was 1,700 g / mol.
- the fluorine content in the polymer solids was 30 wt%.
- the reaction mixture was cooled to room temperature and neutralized with formic acid.
- the solution was poured into a large amount of pure water to precipitate the polymer.
- the obtained polymer was collected by filtration, washed with pure water, dissolved in PGMEA, and residual water was removed and concentrated under reduced pressure to obtain a polymer solution having a solid content of about 35%.
- the weight average molecular weight (Mw) of the polymer thus obtained was 4,000, and the molecular weight distribution was 1.50.
- the double bond equivalent was 1,100 g / mol.
- the fluorine content in the polymer solids was 33 wt%.
- Synthesis Example 7 Synthesis of Fluorine-Containing Polymer C-1)
- the precursor polymer C (10.0 g) synthesized in Synthesis Example 3 was weighed and dissolved in MEK (10 g) in an appropriately sized reaction vessel equipped with a stirrer and a cooling tube. Further, 4-hydroxybutyl acrylate (4HBA, manufactured by Mitsubishi Chemical Corporation, 2.48 g, 17.2 mmol) and triethylamine (2.0 g) were added, and the mixture was heated at 70 ° C. for 6 hours. Formic acid was added to the reaction solution for acid treatment, and then the mixture was added dropwise to a large amount of pure water to precipitate a polymer.
- HBA 4-hydroxybutyl acrylate
- triethylamine 2.0 g
- PGMEA was added to the collected solid and concentrated to obtain a polymer PGMEA solution.
- Mw was 4,900
- Mw / Mn was 1.81
- the double bond equivalent was 1,600 g / mol.
- the fluorine content in the polymer was 34 wt%.
- the above-mentioned precursor polymer (50.0 g) was weighed and dissolved in MEK (90 g) in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. Further, 2-hydroxyethyl methacrylate (HEMA, manufactured by Nippon Shokubai Co., Ltd., 21.2 g, 163 mmol) and triethylamine (5.0 g) were added, and the mixture was heated at 70 ° C. for 6 hours. To this reaction solution, glycidyl methacrylate (GMA, 11.1 g, 78 mmol) was added, and the mixture was further stirred at 70 ° C. for 4 hours.
- HEMA 2-hydroxyethyl methacrylate
- GMA glycidyl methacrylate
- Formic acid was added to the reaction solution for acid treatment, and then the mixture was added dropwise to a large amount of pure water to precipitate a polymer.
- the collected solid was dried in a vacuum dryer at 40 ° C. for 16 hours to obtain a polymer.
- the Mw was 7,800 and the Mw / Mn was 1.70.
- the double bond equivalent was 540 g / mol.
- Weight average molecular weight / molecular weight distribution In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) are converted to polystyrene obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement. Use the value.
- the measurement conditions are as follows. Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C Solvent: THF Sample concentration: 2.0 mg / ml
- the double bond equivalents of the fluorine-containing polymers A-1 to D-1 were measured by the following method. First, about 50 mg of the polymer which was dried under reduced pressure to remove the solvent and about 5 mg of dimethyl terephthalate as an internal standard substance were weighed and dissolved in DMSO-d6. This solution was measured by 1H-NMR using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.).
- the fluorine content of the fluorine-containing polymers A-1 to D-1 was measured by the following method. First, about 10 mg of the polymer dried under reduced pressure to remove the solvent was completely burned in a sealed flask replaced with oxygen. The generated gas was collected in a pre-added hydrogen peroxide alkali absorbing solution, and the volume was adjusted to 50 mL, which was used as a test solution. A test solution and a standard solution were introduced into an ion chromatographic analyzer (ICS-3000 type chromatograph manufactured by Dionex Co., Ltd.), the concentration of fluoride ions was determined by a calibration curve method, and the amount of fluorine contained in the sample was calculated.
- ICS-3000 type chromatograph manufactured by Dionex Co., Ltd.
- the refractive index of the fluorine-containing polymers A-1 to D-1 was measured by the following method.
- the polymer was dissolved in PGMEA at a concentration of 35% by weight.
- the obtained polymer solution was applied onto a 3-inch silicon wafer by a spin method and heat-treated under the conditions of 100 ° C. for 120 seconds to obtain a thin film of 1.0 to 1.5 ⁇ m.
- the refractive index at a wavelength of 632.8 nm was measured using a prism coupler (MODEL 2010M manufactured by Metricon).
- Table 2 shows the blending amounts of the components used in Synthesis Examples 5 to 8, the weight average molecular weight distribution of the obtained fluorine-containing polymer, and the double bond equivalent, fluorine content, refractive index, and alkali dissolution rate.
- Photosensitive agent Photosensitizer 1: A photoradical polymerization initiator (Irgaceure OXE02 manufactured by BASF) represented by the following formula (11) was used.
- Adhesion aid 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
- Surfactant 1 Megafuck F-556 (manufactured by DIC Corporation)
- the negative photosensitive resin composition obtained as described above was evaluated for the following items.
- the prepared negative photosensitive resin compositions were each applied on a 3-inch silicon wafer using a spin coater. After coating, it was prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a coating film (thin film A) having a film thickness of about 3.0 ⁇ m.
- This thin film was exposed to g + h + i lines at an exposure amount of 100 mJ / cm 2 with a Canon g + h + i line mask aligner (PLA-501F) via a photomask having a gradation of 1 to 100% transmittance. After the exposure, the unexposed portion was dissolved and removed by developing at 23 ° C. for 60 seconds using 2.38% tetramethylammonium hydroxide as a developing solution, and the mixture was exposed at each exposure amount of 1 to 100 mJ / cm 2.
- a thin film (thin film B) was obtained.
- Residual film ratio after development (%) ⁇ (Thin film thickness of thin film B ( ⁇ m) at each exposure amount) / (Film thickness of thin film A ( ⁇ m)) ⁇ ⁇ 100
- the minimum exposure amount at which the residual film ratio after development obtained by the above formula was 95% or more was defined as the sensitivity of the resist.
- Film thickness change rate (%) [ ⁇ (Film thickness after immersion in chemical solution)-(Film thickness before immersion in chemical solution) ⁇ / (Film thickness before immersion in chemical solution)] ⁇ 100
- the weight loss rate of the cured film was evaluated as follows using the obtained photosensitive resin composition. First, a photosensitive resin composition was applied to a 3-inch wafer, and then heat treatment was performed at 100 ° C. for 120 seconds to remove the solvent. Next, the entire surface of the g + h + i line was exposed with an exposure amount of 100 mJ / cm 2 using a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. The obtained film was heat-treated in an oven at 230 ° C. for 60 minutes to cure the photosensitive resin composition. In this way, a cured film was obtained for each of the Examples and Comparative Examples. Then, the weight loss rate of the sample was measured.
- PVA-501F g + h + i line mask aligner
- the cured product of the photosensitive resin composition of the example had a low dielectric constant and was excellent in heat resistance and chemical resistance.
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Abstract
Description
R1、R2、R3およびR4はそれぞれ独立して水素または炭素数1~30の有機基であり、nは0、1または2であり、
式(2a)中、
R5は、炭素数1~30の有機基であり、
R1、R2、R3、R4およびR5の少なくとも1つは、炭素数1~30の含フッ素有機基である。)。
以下の式(1)および(2a)で示される構造単位を含むポリマーと、
架橋剤と、
感光剤と、を含む感光性樹脂組成物が提供される。
R1、R2、R3およびR4はそれぞれ独立して水素または炭素数1~30の有機基であり、nは0、1または2であり、
式(2a)中、
R5は、炭素数1~30の有機基であり、
R1、R2、R3、R4およびR5の少なくとも1つは、炭素数1~30の含フッ素有機基である。)。
本実施形態のポリマー(以下、「ポリマーP」と称する)は、以下の式(1)および(2a)で示される構造単位を含む。
R1、R2、R3およびR4はそれぞれ独立して水素または炭素数1~30の有機基であり、nは0、1または2であり、
式(2a)中、
R5は、炭素数1~30の有機基であり、
R1、R2、R3、R4およびR5の少なくとも1つは、炭素数1~30の含フッ素有機基である。
R1、R2、R3およびR4はそれぞれ独立して水素または炭素数1~30の有機基である。
式(2a)において、R5は、炭素数1~30の有機基である。
R1、R2、R3、R4およびR5の少なくとも1つは、炭素数1~30の含フッ素有機基である。
アルキル基としては、たとえばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、およびデシル基が挙げられる。
アルケニル基としては、たとえばアリル基、ペンテニル基、およびビニル基が挙げられる。アルキニル基としては、エチニル基が挙げられる。
アルキリデン基としては、たとえばメチリデン基、およびエチリデン基が挙げられる。
アリール基としては、たとえばフェニル基、ナフチル基、およびアントラセニル基が挙げられる。アラルキル基としては、たとえばベンジル基、およびフェネチル基が挙げられる。
アルカリル基としては、たとえばトリル基、キシリル基が挙げられる。シクロアルキル基としては、たとえばアダマンチル基、シクロペンチル基、シクロヘキシル基、およびシクロオクチル基が挙げられる。
ヘテロ環基としては、たとえばエポキシ基、およびオキセタニル基が挙げられる。
式(B6)中、R8は、炭素数1~30の有機基である。
炭素数1~30の有機基は、上述の定義と同義である。
R5、R6、R7のいずれかには光ラジカル重合開始剤により架橋する炭素-炭素二重結合を有していることが好ましい。例えば、ビニル基、ビニリデン基、アリル基、アクリロイル基、メタクリロイル基が挙げられる。
なお、モノマーAおよびモノマーBとして、それぞれ1種または2種以上の種類のモノマーを用いることを制限するものではない。
付加重合の方法としては限定されないが、本実施形態においては、ラジカル重合開始剤を用いたラジカル重合により共重合体を合成する。
ラジカル重合開始剤を用いた付加重合することにより、モノマーAに由来する構造単位と、モノマーBに由来する構造単位とを備え、ラジカル重合開始剤に由来する末端を備える共重合体を合成することができる。
開環前のポリマー(ポリマー前駆体)の酸無水物構造における(C=O)のIR吸収強度(Abs1)を測定し、開環後の酸無水物構造における(C=O)のIR吸収強度(Abs2)より以下式にて開環率を算出する。
開環率(%)=(((Abs1)-(Abs2))/(Abs1))×100
なお、内部標準物質としてアセトニトリルを用いる。
なお、金属アルコキシドとしては、異なるものを2種以上使用してもよい。ただし、製造安定性の観点からは、1種の金属アルコキシドを使用することが好ましい。
アルカリ金属の水酸化物としては、取り扱い性の観点から水酸化ナトリウムが好ましい。
アルコールとしては、1価のアルコール(R5OH)が好ましい。有機基であるR5は、前述したものを使用できる。なお、R5は炭素数1以上30以下であることが好ましい。
上記式(6)で示される構造単位は、それぞれ、プロトン置換によって以下の(2a)、(B4)で示される構造単位になる。
本実施形態のポリマーPは、電子装置の樹脂膜を形成するための感光性樹脂組成物に用いられる。
本実施形態の感光性樹脂組成物は、
上記ポリマーPと、
架橋剤と、
感光剤と、を含む。
(架橋剤)
本実施形態の感光性樹脂組成物は、架橋剤を含む。架橋剤は、ポリマーPの活性水素と反応し得る官能基を含む化合物であれば、限定されない。このような架橋剤としては、例えば、グリシジル基、オキセタニル基およびブロックイソシアネート基から選択される少なくとも1つの官能基を有する化合物が挙げられる。架橋剤としては、グリシジル基またはオキセタニル基を有する化合物がより好ましく、グリシジル基を有する化合物がさらにより好ましい。このような架橋剤を用いることにより、適切な架橋構造を形成することができる。また、架橋剤として、ブロックイソシアネート基を有する化合物、エポキシ化合物およびオキセタン化合物から選択される1種または2種以上を併用することもできる。
感光性樹脂組成物がポジ型である場合には、感光剤として、光活性化合物を使用でき、たとえば、ジアゾキノン化合物を使用することができる。
たとえば、以下のいずれか1種以上の化合物を使用することができる。
なかでも、感光性樹脂組成物の透明性、誘電率の観点から、Qが(a)あるいは(b)であるo-ナフトキノンジアジドスルホン酸誘導体が好ましい。
この場合には、酸発生剤は、架橋剤100質量部に対して、3質量部以下であることが好ましい。
光により酸を発生する光酸発生剤としては、後述するものを使用できる。
熱により酸を発生する熱酸発生剤としては、SI-45L、SI-60L、SI-80L、SI-100L、SI-110L、SI-150L(三新化学工業社製)等の芳香族スルホニウム塩が使用できる。
熱酸発生剤の含有量は、たとえば、感光性樹脂組成物の全固形分を100質量%としたとき、0.1質量%以上5質量%以下であることが好ましい。
なお、本実施形態において、感光性樹脂組成物の全固形分とは、溶媒を除く成分のことを示す。
たとえば、メラミン系架橋剤、尿素系架橋剤などが挙げられる。
メラミン系架橋剤としては、たとえば、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシブチルメラミン等が挙げられ、なかでもヘキサメトキシメチルメラミンが好ましい。
尿素系架橋剤としては、たとえば、メチル化尿素樹脂、ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等が挙げられ、なかでもメチル化尿素樹脂が好ましい。
メチル化尿素樹脂の市販品として、例えば、MX-270、MX-280、MX-290(三和ケミカル社製)などが挙げられる。
感光性樹脂組成物の全固形分を100質量%としたとき、前述した共重合体を、例えば、30質量%以上70質量%以下含有することが好ましく、なかでも、40質量%以上60質量%以下含有することが好ましい。
また、感光性樹脂組成物の全固形分を100質量%としたとき架橋剤を、例えば、15質量%以上50質量%以下含有することが好ましく、なかでも、20質量%以上50質量%以下含有することが好ましい。
さらには、感光性樹脂組成物の全固形分を100質量%としたとき、感光剤である光活性化合物を、例えば、5質量%以上40質量%以下含有することが好ましく、10質量%以上30質量%以下含有することがさらに好ましい。
感光性樹脂組成物の全固形分を100質量%としたとき、前述した共重合体を、例えば、30質量%以上70質量%含有することが好ましく、なかでも、40質量%以上60質量%以下含有することが好ましい。
また、感光性樹脂組成物の全固形分100質量%としたとき架橋剤(第二の架橋剤をのぞく。)を、例えば、15質量%以上50質量%以下含有することが好ましく、なかでも、20質量%以上50質量%以下含有することが好ましい。
さらには、感光性樹脂組成物の全固形分を100質量%としたとき、光酸発生剤の量は、例えば、0.1質量%以上40質量%以下であり、高解像度のパターン膜を形成することができる点から、より好ましくは1質量%以上30質量%以下である。
本実施形態に係る樹脂膜は、上述の感光性樹脂組成物の硬化物からなる。この樹脂膜は、優れた耐熱性を有するため、電子装置におけるレジストや永久膜として用いられる。
例えば、電子装置が、半導体チップである場合、半導体チップを構成するパッシベーション膜や絶縁層が、本実施形態の感光性樹脂組成物の硬化物により形成される。
適切な反応容器内に、5-ノナフルオロブチルビシクロ[2.2.1]ヘプタ-2-エン(NBC4F9、22.9g、72.8mmol)、無水マレイン酸(MAN、7.1g、72.8mmol)、開始剤としての2,2'-アゾビス(2-メチルプロピオン酸)ジメチル(和光純薬工業製、商品名:V-601、3.4g、14.6mmol)およびメチルエチルケトン(MEK)9.5gを加え、撹拌・溶解させた。次いで、窒素バブリングにより系内の溶存酸素を除去したのち、加温し、内温60℃で16時間反応させた。次いで、反応混合物を室温まで冷却し、MEK32.1gを添加し希釈した。希釈後の溶液を大量のメタノールに注ぎ、ポリマーを析出させた。次いでポリマーを濾取し、さらにメタノールで洗浄した後、120℃、16時間真空乾燥させた。ポリマーの収量は25.0g、収率は83%であった。また、ポリマーは、重量平均分子量Mwが2,400であり、分散度(重量平均分子量Mw/数平均分子量Mn)が1.69であった。
適切な反応容器内に、NBC4F9(22.9g、72.8mmol)、MAN(7.1g、72.8mmol)、V-601(1.7g、7.3mmol)およびMEK11.2gを加え、撹拌・溶解させた。次いで、窒素バブリングにより系内の溶存酸素を除去したのち、加温し、内温60℃で5時間反応させた。次いで、内温を80℃まで昇温し、さらに3時間反応させた。反応混合物を室温まで冷却し、大量のメタノールに注ぎ、ポリマーを析出させた。次いでポリマーを濾取し、さらにメタノールで洗浄した後、120℃、16時間真空乾燥させた。ポリマーの収量は14.9g、収率は50%であった。また、ポリマーは、Mwが4,000であり、Mw/Mnが1.50であった。
撹拌機,冷却管を備えた適切なサイズの反応容器に、無水マレイン酸(日本触媒株式会社製、24.3g、247.8mmol)、ビシクロ[2.2.1]ヘプタ-5-エン-2-カルボン酸-3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロオクチル(NBCOOC2H4C6F13、120.0g、247.8mmol)およびジメチル2,2'-アゾビス(2-メチルプロピオネート)(V-601、富士フィルム和光純薬株式会社製、7.61g、30.6mmol)を計量し、メチルエチルケトン(MEK、28.5g)に溶解させた。この溶解液に対して10分間窒素を通気して酸素を除去した後、撹拌しつつ60℃まで昇温して、2時間保持した。引き続き80℃まで昇温して3時間保持したのち、V-601(3.81g、15.3mmol)を追加してさらに3時間反応させた。この反応混合物をMEKで希釈したのち、大量のメタノールに滴下し、ポリマーを析出させた。ヌッチェを用いてろ過した後、さらにメタノールにて固体を洗浄し、真空乾燥した。得られたポリマーの重量平均分子量(Mw)は5,400、分散度(Mw/Mn)は1.72であった。
撹拌機、冷却管を備えた適切なサイズの反応容器に、無水マレイン酸(4.76g、48.5mmol)、5-トリデカフルオロヘキシル-2-ノルボルネン(NBC6F13、20.0g、48.5mmol)およびV-601(1.5g、6.0mmol)を計量し、MEK(4.7g)に溶解させた。この溶解液に対して10分間窒素を通気して酸素を除去した後、撹拌しつつ60℃まで昇温して、2時間保持した。引き続き80℃まで昇温して3時間保持したのち、V-601(0.74g、3.0mmol)を追加してさらに3時間反応させた。この反応混合物をMEKで希釈したのち、大量のメタノールに滴下し、ポリマーを析出させた。ヌッチェを用いてろ過した後、さらにメタノールにて固体を洗浄し、真空乾燥した。得られたポリマーの重量平均分子量(Mw)は3,700、分散度(Mw/Mn)は1.64であった。
合成例1で合成した前駆体ポリマーA15.0gをMEK27.9gに溶解させた。さらに2-ヒドロキシエチルメタクリレート(HEMA)3.0gとトリエチルアミン(TEA)1.5gを添加し、70℃に昇温した後6時間反応させた。次いで、メタクリル酸グリシジル(GMA)1.6gを添加し、さらに4時間反応させた。反応混合液を室温に冷却し、ギ酸にて中和した。溶液を大量の純水に注ぎ、ポリマーを析出させた。得られたポリマーを濾取し、さらに純水で洗浄した後、プロピレングリコールモノメチルエーテルアセテート(PGMEA)に溶解させ、減圧下で残留水分の除去・濃縮を行って固形分約35%のポリマー溶液を得た。
このようにして得られたポリマーの重量平均分子量(Mw)は2,100であり、分子量分布1.55であった。また、二重結合当量は1,700g/molであった。ポリマー固形分中のフッ素含有量は30wt%であった。
合成例2で合成した前駆体ポリマーB5.0gをMEK27.9gに溶解させた。さらに2-ヒドロキシエチルメタクリレート(HEMA)1.0gとトリエチルアミン(TEA)0.75gを添加し、70℃に昇温した後6時間反応させた。次いで、メタクリル酸グリシジル(GMA)0.5gと3-パーフルオロブチル-1,2-エポキシプロパン(PFBEp)1.0gを添加し、さらに70℃で4時間反応させた。反応混合液を室温に冷却し、ギ酸にて中和した。溶液を大量の純水に注ぎ、ポリマーを析出させた。得られたポリマーを濾取し、さらに純水で洗浄した後、PGMEAに溶解させ、減圧下で残留水分の除去・濃縮を行って固形分約35%のポリマー溶液を得た。
このようにして得られたポリマーの重量平均分子量(Mw)は4,000であり、分子量分布1.50であった。また、二重結合当量は1,100g/molであった。ポリマー固形分中のフッ素含有量は33wt%であった。
撹拌機、冷却管を備えた適切なサイズの反応容器に、合成例3で合成した前駆体ポリマーC(10.0g)を計量し、MEK(10g)に溶解させた。さらにアクリル酸4-ヒドロキシブチル(4HBA、三菱ケミカル株式会社製、2.48g、17.2mmol)、トリエチルアミン(2.0g)を添加し、70℃で6時間加熱した。反応液にギ酸を加えて酸処理した後、大量の純水に滴下しポリマーを析出させた。濾取した固体にPGMEAを加えて濃縮し、ポリマーのPGMEA溶液を得た。Mwは4,900、Mw/Mnは1.81、二重結合当量は1,600g/molであった。また、ポリマー中のフッ素含有量は34wt%であった。
撹拌機、冷却管を備えた適切なサイズの反応容器に、合成例4で合成した前駆体ポリマーD(10.0g)を計量し、MEK(10g)に溶解させた。さらに4HBA(2.83g, 17.2mmol)、トリエチルアミン(2.0g)を添加し、70℃で6時間加熱した。反応液にギ酸を加えて酸処理した後、大量の純水に滴下しポリマーを析出させた。濾取した固体にPGMEAを加えて濃縮し、ポリマーのPGMEA溶液を得た。Mwは3,900、Mw/Mnは1.60、二重結合当量は1,400g/molであった。また、ポリマー中のフッ素含有量は39wt%であった。
撹拌機、冷却管を備えた適切なサイズの反応容器に、2-ノルボルネン(75wt%トルエン溶液、丸善石油化学製、125.5g、1.00mol)およびジメチル2,2'-アゾビス(2-メチルプロピオネート)(V-601、和光純薬工業製、9.2g、40mmol)を計量し、メチルエチルケトン(MEK,196.1g)に溶解させた。この溶解液に対して10分間窒素を通気して酸素を除去した後、撹拌しつつ80℃まで加熱した。溶液を80℃に保持しつつ、あらかじめ調製しておいた無水マレイン酸(日本触媒製、98.1g、1.00mol)をMEK119.9gに溶解した溶液を1.5時間で滴下し、その温度でさらに8時間反応させた。この反応混合物を大量のメタノールに滴下し、ポリマーを析出させた。ヌッチェを用いてろ過した後、さらにメタノールにて固体を洗浄し、70℃で真空乾燥した。得られたポリマーの重量平均分子量(Mw)は6,900、分散度(Mw/Mn)は1.76であった。
なお、本明細書において、重量平均分子量(Mw)、数平均分子量(Mn)、および分子量分布(Mw/Mn)は、GPC測定により得られる標準ポリスチレン(PS)の検量線から求めた、ポリスチレン換算値を用いる。測定条件は、以下の通りである。
東ソー社製ゲルパーミエーションクロマトグラフィー装置HLC-8320GPC
カラム:東ソー社製TSK-GEL Supermultipore HZ-M
検出器:液体クロマトグラム用RI検出器
測定温度:40℃
溶媒:THF
試料濃度:2.0mg/ミリリットル
フッ素含有ポリマーA-1~D-1の二重結合当量を以下の方法で測定した。まず、減圧乾燥して溶媒を除去したポリマー約50mgおよび内部標準物質としてテレフタル酸ジメチル約5mgを計量し、DMSO-d6に溶解させた。この溶液について、核磁気共鳴分光装置JNM-AL300(JEOL社製)を用いて1H-NMRの測定を行った。得られたスペクトルチャートの(メタ)アクリル基に由来するシグナル(5-7ppm)と内部標準物質のフェニル基のシグナル(4H、8.1ppm)の積分比から二重結合1モル当たりのポリマー重量(g/mol、二重結合当量)を算出した。
フッ素含有ポリマーA-1~D-1のフッ素含有量を以下の方法で測定した。まず、減圧乾燥して溶媒を除去したポリマー約10mgを酸素と置換した密封系のフラスコ内で完全燃焼させた。生成したガスをあらかじめ添加されている過酸化水素アルカリ吸収液に捕集し50mLに定容したものを検液とした。イオンクロマト分析装置(ダイオネクス社製ICS-3000型クロマトグラフ)に検液および標準液を導入し、検量線法によりフッ化物イオンの濃度を求め、試料中に含まれるフッ素量を算出した。
フッ素含有ポリマーA-1~D-1の屈折率を以下の方法で測定した。ポリマーをPGMEAに35重量%の濃度で溶解させた。得られたポリマー溶液を3インチのシリコンウェハ上にスピン方式で塗布し、100℃、120秒の条件下で熱処理を施すことにより1.0~1.5μmの薄膜を得た。プリズムカプラ(メトリコン社製MODEL2010M)を用いて、波長632.8nmにおける屈折率を測定した。
フッ素含有ポリマーA-1~D-1について、アルカリ溶解速度を以下のように測定した。ポリマーをPGMEAに溶解させ、固形分濃度35%の溶液を調製した。このポリマー溶液を、シリコンウェハ上にスピン方式で塗布し、これを100℃で120秒間ソフトベークして、厚みHが約2.0μmのポリマー膜を形成した。このポリマー膜を形成したシリコンウェハを、2.38%、23℃のテトラメチルアンモニウムハイドロオキサイド水溶液に含浸させ、視覚的にポリマー膜が消去するまでの時間Tを測定した。HおよびTより、以下の式からアルカリ溶解速度を算出した。
(アルカリ溶解速度)[Å/秒]=(膜厚H)/(ポリマー膜が消去するまでの時間T)
各実施例、各比較例について、表3に示される配合量で、合成例5~9で作製したポリマー、感光剤、架橋剤、密着改善剤および界面活性剤をPGMEAおよびシクロヘキサノンに溶解させ撹拌した。撹拌後、0.2μmのフィルターで濾過して、ネガ型感光性樹脂組成物を調製した。
(フッ素含有ポリマー)
・ポリマーA-1:合成例5で調製したフッ素含有ポリマーA-1
・ポリマーB-1:合成例6で調製したフッ素含有ポリマーB-1
・ポリマーC-1:合成例7で調製したフッ素含有ポリマーC-1
・ポリマーD-1:合成例8で調製したフッ素含有ポリマーD-1
(その他のポリマー)
・ポリマー1:合成例9で調製したポリマー1
(架橋剤)
・架橋剤1:以下の式(12)で示されるアクリル系架橋剤(ダイセルサイテック社製 DPHA)。
・感光剤1:以下の式(11)で示される光ラジカル重合開始剤(BASF社製 Irgacure OXE02)を用いた。
・密着助剤1:3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製 KBM-403)
界面活性剤1:メガファックF-556(DIC株式会社製)
溶媒1:プロピレングリコールモノメチルエーテルアセテート(PGMEA)
溶媒2:シクロヘキサノン
調製されたネガ型感光性樹脂組成物を、それぞれ、3インチシリコンウェハ上にスピンコーターを用いて塗布した。塗布後、ホットプレートにて100℃で2分間プリベークし、膜厚約3.0μmの塗膜(薄膜A)を得た。
この薄膜に透過率1~100%の階調を有するフォトマスクを介してキヤノン社製g+h+i線マスクアライナー(PLA-501F)にて100mJ/cm2の露光量でg+h+i線を露光した。
露光後、現像液として2.38%水酸化テトラメチルアンモニウムを用いて23℃、60秒間現像を行うことによって未露光部を溶解除去し、1~100mJ/cm2の各露光量で露光された薄膜(薄膜B)を得た。
現像後残膜率(%)={(各露光量における薄膜Bの膜厚(μm))/(薄膜Aの膜厚(μm))}×100
上記の計算式で得られた現像後残膜率が95%以上となる最低露光量をそのレジストの感度とした。
低抵抗シリコンウェハー(Ω<)に感光性樹脂組成物を塗布した後、100℃、120秒の条件下で熱処理を施すことにより脱溶媒を行った。次いで、キヤノン社製g+h+i線マスクアライナー(PLA-501F)にて100mJ/cm2の露光量でg+h+i線を全面露光した。得られた膜に対し、オーブンで大気中230℃、60分間熱処理を行い、感光性樹脂組成物を硬化させた。このようにして、各実施例および各比較例のそれぞれについて、硬化膜を得た。この薄膜上に金電極を形成し、室温、100kHzにおける条件で、Hewlett Packard社製LCRメータ(4282A)を用いて得られた静電容量から誘電率を算出した。
3インチシリコンウェハに感光性樹脂組成物を塗布した後、100℃、120秒の条件下で熱処理を施すことにより脱溶媒を行った。次いで、キヤノン社製g+h+i線マスクアライナー(PLA-501F)にて100mJ/cm2の露光量でg+h+i線を全面露光した。得られた膜に対し、オーブンで大気中230℃、60分間熱処理を行い、感光性樹脂組成物を硬化させた。このようにして、各実施例および各比較例のそれぞれについて、硬化膜を得た。得られた硬化膜付きシリコンウェハをTOK106(東京応化工業株式会社製)に室温で5分間浸漬した後、純水で30秒間リンスした。この時、以下の演算式で定義される膜厚変化率を求め、耐薬品性の指標とした。膜厚変化率が小さい方が耐薬品性に優れている。
膜厚変化率(%)=[{(薬液浸漬後の膜厚)-(薬液浸漬前の膜厚)}/(薬液浸漬前の膜厚)]×100
縦100mm、横100mmサイズのコーニング社製1737ガラス基板に感光性樹脂組成物を塗布した後、100℃、120秒の条件下で熱処理を施すことにより脱溶媒を行った。次いで、キヤノン社製g+h+i線マスクアライナー(PLA-501F)にて100mJ/cm2の露光量でg+h+i線を全面露光した。得られた膜に対し、オーブンで大気中230℃、60分間熱処理を行い、感光性樹脂組成物を硬化させた。このようにして、各実施例および各比較例のそれぞれについて、硬化膜を得た。この硬化膜について光の波長400nmにおける透過率(%)を、紫外-可視光分光光度計を用いて測定し、膜厚3μmに換算した数値を透過率とした。
各実施例について、得られた感光性樹脂組成物を用いて以下のように硬化膜の重量減少率の評価を行った。
まず、3インチウェハに感光性樹脂組成物を塗布した後、100℃、120秒の条件下で熱処理を施すことにより脱溶媒を行った。次いで、キヤノン社製g+h+i線マスクアライナー(PLA-501F)にて100mJ/cm2の露光量でg+h+i線を全面露光した。得られた膜に対し、オーブンで大気中230℃、60分間熱処理を行い、感光性樹脂組成物を硬化させた。このようにして、各実施例および各比較例のそれぞれについて、硬化膜を得た。
次いで、上記サンプルの重量減少率を測定した。測定は、硬化膜を5mg秤量して得られた試料に対し、熱重量/示差熱測定装置(TG/DTA)を用いて、開始温度30℃、昇温速度10℃/min、N2流量200mL/minの条件下において250℃まで昇温し、250℃で60分間保持した。250℃到達時点の重量から60分経過時点までの重量変化率を重量減少率とした。
上記項目の評価結果を、表3に示す。
Claims (16)
- 前記炭素数1~30の含フッ素有機基が、炭素数1~30のフルオロアルキル基またはエーテル性酸素原子を有する炭素数1~30のフルオロアルキル基である、請求項1に記載のポリマー。
- 前記R1、R2、R3およびR4の少なくとも1つが、炭素数1~30の含フッ素有機基である、請求項1または2に記載のポリマー。
- 前記R1、R2、R3およびR4の少なくとも1つが、炭素数1~30のフルオロアルキル基である、請求項3に記載のポリマー。
- 前記炭素数1~30のフルオロアルキル基が、パーフルオロアルキル基である、請求項4に記載のポリマー。
- 重量平均分子量が1500以上30000以下である、請求項1~6のいずれかに記載のポリマー。
- 前記炭素数1~30の含フッ素有機基が、炭素数1~30のフルオロアルキル基またはエーテル性酸素原子を有する炭素数1~30のフルオロアルキル基である、請求項8に記載の感光性樹脂組成物。
- 前記R1、R2、R3およびR4の少なくとも1つが、炭素数1~30の含フッ素有機基である、請求項8または9に記載の感光性樹脂組成物。
- 前記R1、R2、R3およびR4の少なくとも1つが、炭素数1~30のフルオロアルキル基である、請求項10に記載の感光性樹脂組成物。
- 前記炭素数1~30のフルオロアルキル基が、パーフルオロアルキル基である、請求項11に記載の感光性樹脂組成物。
- 前記ポリマーの重量平均分子量が1500以上30000以下である、請求項8~13のいずれかに記載の感光性樹脂組成物。
- 請求項8~14のいずれかに記載の感光性樹脂組成物の硬化膜からなる樹脂膜。
- 請求項15に記載の樹脂膜を備える電子装置。
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