JPS62215264A - New photosensitive composition - Google Patents
New photosensitive compositionInfo
- Publication number
- JPS62215264A JPS62215264A JP5709586A JP5709586A JPS62215264A JP S62215264 A JPS62215264 A JP S62215264A JP 5709586 A JP5709586 A JP 5709586A JP 5709586 A JP5709586 A JP 5709586A JP S62215264 A JPS62215264 A JP S62215264A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- carbon atoms
- alkyl group
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 125000000732 arylene group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000002837 carbocyclic group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 24
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical group [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 10
- 206010034972 Photosensitivity reaction Diseases 0.000 description 9
- -1 amine compound Chemical class 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 230000036211 photosensitivity Effects 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- SDQJTWBNWQABLE-UHFFFAOYSA-N 1h-quinazoline-2,4-dione Chemical group C1=CC=C2C(=O)NC(=O)NC2=C1 SDQJTWBNWQABLE-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YLHUPYSUKYAIBW-UHFFFAOYSA-N 1-acetylpyrrolidin-2-one Chemical compound CC(=O)N1CCCC1=O YLHUPYSUKYAIBW-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- YFMNMPLJIWVXER-UHFFFAOYSA-N 1,3-bis[4-(dimethylamino)phenyl]prop-2-en-1-one Chemical compound C1=CC(N(C)C)=CC=C1C=CC(=O)C1=CC=C(N(C)C)C=C1 YFMNMPLJIWVXER-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- LVUQCTGSDJLWCE-UHFFFAOYSA-N 1-benzylpyrrolidin-2-one Chemical compound O=C1CCCN1CC1=CC=CC=C1 LVUQCTGSDJLWCE-UHFFFAOYSA-N 0.000 description 1
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KXZSVYHFYHTNBI-UHFFFAOYSA-N 1h-quinoline-2-thione Chemical compound C1=CC=CC2=NC(S)=CC=C21 KXZSVYHFYHTNBI-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- KKLBPVXKMBLCQX-UHFFFAOYSA-N 2,5-bis[[4-(diethylamino)phenyl]methylidene]cyclopentan-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CC1)C(=O)C1=CC1=CC=C(N(CC)CC)C=C1 KKLBPVXKMBLCQX-UHFFFAOYSA-N 0.000 description 1
- LIFWPLOFXPGAJJ-UHFFFAOYSA-N 2,6-bis[[4-(diethylamino)phenyl]methylidene]cyclohexan-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CCC1)C(=O)C1=CC1=CC=C(N(CC)CC)C=C1 LIFWPLOFXPGAJJ-UHFFFAOYSA-N 0.000 description 1
- YXQINXKZKRYRQM-UHFFFAOYSA-N 2,6-bis[[4-(dimethylamino)phenyl]methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1C(=CC=2C=CC(=CC=2)N(C)C)CC(C)CC1=CC1=CC=C(N(C)C)C=C1 YXQINXKZKRYRQM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- YZTUIKZEIMOMGF-UHFFFAOYSA-N 2-[3-[4-(dimethylamino)phenyl]prop-2-enylidene]-3h-inden-1-one Chemical compound C1=CC(N(C)C)=CC=C1C=CC=C1C(=O)C2=CC=CC=C2C1 YZTUIKZEIMOMGF-UHFFFAOYSA-N 0.000 description 1
- YCKZAOPKIOWTEH-UHFFFAOYSA-N 2-[[4-(dimethylamino)phenyl]methylidene]-3h-inden-1-one Chemical compound C1=CC(N(C)C)=CC=C1C=C1C(=O)C2=CC=CC=C2C1 YCKZAOPKIOWTEH-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- SOFPIAMTOZWXKT-UHFFFAOYSA-N 2h-1,2,4-triazine-3-thione Chemical compound SC1=NC=CN=N1 SOFPIAMTOZWXKT-UHFFFAOYSA-N 0.000 description 1
- VLZDYNDUVLBNLD-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C(C)=C VLZDYNDUVLBNLD-UHFFFAOYSA-N 0.000 description 1
- UKERLUWBPOXYSL-UHFFFAOYSA-N 3-(ethylamino)chromen-2-one Chemical compound C1=CC=C2OC(=O)C(NCC)=CC2=C1 UKERLUWBPOXYSL-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- AEMXURHNQSDPCG-UHFFFAOYSA-N 4-[2-[2-(4-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1SC1=CC=CC=C1OC1=CC=C(N)C=C1 AEMXURHNQSDPCG-UHFFFAOYSA-N 0.000 description 1
- AJYDKROUZBIMLE-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C=CC(N)=CC=2)C=1C(C)(C)C1=CC=CC=C1OC1=CC=C(N)C=C1 AJYDKROUZBIMLE-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- CYCKHTAVNBPQDB-UHFFFAOYSA-N 4-phenyl-3H-thiazole-2-thione Chemical compound S1C(S)=NC(C=2C=CC=CC=2)=C1 CYCKHTAVNBPQDB-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 1
- FPVUWZFFEGYCGB-UHFFFAOYSA-N 5-methyl-3h-1,3,4-thiadiazole-2-thione Chemical compound CC1=NN=C(S)S1 FPVUWZFFEGYCGB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000543381 Cliftonia monophylla Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 229960005130 niridazole Drugs 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- PLQCPDHNBLXOEO-UHFFFAOYSA-N oxazine-3,4-dione Chemical group O=C1C=CONC1=O PLQCPDHNBLXOEO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新しい感光性組成物、さらに詳しくいえば、加
熱処理によシ耐熱性高分子化合物に変換しうる感光性組
成物に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new photosensitive composition, and more particularly, to a photosensitive composition that can be converted into a heat-resistant polymer compound by heat treatment. .
従来、ポリイミドに代表される耐熱性高分子化合物は、
その耐熱性や電気特性などを生かして、例えば電気、自
動車、航空機、宇宙、原子力などの分野で、構造部材、
プリント基板材料、耐熱絶縁材料などに広く用いられて
いる。Conventionally, heat-resistant polymer compounds represented by polyimide are
Taking advantage of its heat resistance and electrical properties, it is used as a structural member in fields such as electricity, automobiles, aircraft, space, and nuclear power.
Widely used for printed circuit board materials, heat-resistant insulation materials, etc.
一方、感光性高分子化合物は、塗料や印刷版などの用途
に広く用いられておシ、特に最近ではそのリソグラフィ
ー特性を生かして、プリント回路作成用し・クスト、金
属板エツチング用レジスト、半導体素子作成用レジスト
などの微細加工用材料として、目覚ましい進歩がみられ
ることは周知のところである。On the other hand, photosensitive polymer compounds are widely used in applications such as paints and printing plates, and in recent years, their lithography properties have been particularly utilized to create printed circuits, resists for etching metal plates, and semiconductor devices. It is well known that remarkable progress has been made in materials for microfabrication such as resists.
近年、この耐熱性と感光性という2種の有用な機能を合
わせもつ高分子材料について、特に電子材料や光学材料
用として積極的に開発がなされておす、例えばパッシベ
ーション膜、α線遮へい膜、ジャンクションコート膜な
どの表面保護膜や多層配線用の層間絶縁膜のような半導
体素子用絶縁膜あるいは液晶表示素子用配向膜、薄膜磁
気へツP用絶縁膜などの用途が検討されている〔例えば
、「機能材料」、7月号第9〜19ページ(19■年)
及び、[フォトグラフィック・サイエンス・アンr+エ
ンジニャリン3P (Photographic 5c
ience andEngineering ) J第
303〜309ページ(1979年)参照〕。In recent years, polymer materials that have these two useful functions of heat resistance and photosensitivity have been actively developed, especially for use in electronic and optical materials, such as passivation films, α-ray shielding films, and junction films. Applications are being considered such as surface protection films such as coating films, insulating films for semiconductor devices such as interlayer insulating films for multilayer wiring, alignment films for liquid crystal display devices, and insulating films for thin film magnetic sheets [for example, "Functional Materials", July issue, pages 9-19 (2019)
And, [Photographic Science Anr + Engineer 3P (Photographic 5c
J. 303-309 (1979)].
従来、耐熱性感光性組成物としては、例えばポリイミr
の前駆体であるポリアミr酸のエステル側鎖に二重結合
などの活性官能基を導入したポリマーに、光増感剤や共
重合性モノマーを加えた、光照射によシ架橋構造が形成
されうる組成物が知られている(特公昭55−3020
7号公報、特公昭55−41422号公報)。このもの
はいわゆる感光性ポリイミドに代表されるリソグラフィ
ー用耐熱性高分子材料の基本的な組成物であるが、光感
度が低く、実用に供するには不十分であった。又、この
ような欠点を改良した組成物として、前記の側鎖活性官
能基にメタクリレート基又はアクリレート基を用い、光
開始剤としてp−アセトアミP−フェニルスルホンアジ
rなどの7−)r化合物を加えたものが提案されている
(%開昭55−155347号公報)。Conventionally, heat-resistant photosensitive compositions such as polyimirr
A cross-linked structure is formed by adding a photosensitizer and a copolymerizable monomer to a polymer in which active functional groups such as double bonds are introduced into the ester side chains of polyamic acid, which is a precursor of A moisturizing composition is known (Japanese Patent Publication No. 55-3020
7, Japanese Patent Publication No. 55-41422). This is a basic composition of heat-resistant polymer materials for lithography, typified by so-called photosensitive polyimides, but it had low photosensitivity and was insufficient for practical use. In addition, as a composition that improves these drawbacks, a methacrylate group or an acrylate group is used as the active functional group in the side chain, and a 7-)r compound such as p-acetami-P-phenylsulfonazir is used as a photoinitiator. An additional method has been proposed (Patent Publication No. 55-155347).
しかしながら、この組成物は若干光感度が向上している
ものの、まだ十分であるとはいえ外い。However, although this composition has slightly improved photosensitivity, it is still far from sufficient.
一方、ポリアミr酸と二重結合などの活性官能基を有す
るアミン化合物との混合物を主成分とする感光性組成物
が提案されている(特開昭57−168942号公報、
特開昭54−145794号公報、特開昭59−160
140号公報)。On the other hand, a photosensitive composition containing as a main component a mixture of polyamic acid and an amine compound having an active functional group such as a double bond has been proposed (Japanese Unexamined Patent Publication No. 168942/1989,
JP-A-54-145794, JP-A-59-160
140).
しかしながら、このものはその溶液の粘度が極めて高い
ために、よシ低濃度の溶液で取扱う必要があシ、半導体
素子表面の製膜に汎用されているスピンコーターなどを
用いた場合、厚膜を形成することが困難であった。又、
これらはイオン結合型であるために、塗布乾燥後放置す
ると、吸湿によシフラックを生じやすいという問題点が
あった。However, because the viscosity of this solution is extremely high, it is necessary to handle it with a solution of low concentration, and when using a spin coater, etc., which is commonly used for forming films on the surface of semiconductor elements, it is difficult to form thick films. It was difficult to form. or,
Since these are of the ionic bond type, there is a problem in that if left after application and drying, siflux is likely to occur due to moisture absorption.
これら先行技術に開示されている組成物の使用法につい
ては、いずれも溶液として基体上に塗布し、乾燥後、フ
ォトマスクを通して紫外線などの活性光線を照射したの
ち、適当な現像溶媒で未露光部分を溶解除去して画像を
形成し、次いで高温処理を行なってイミr環などに閉環
し、同時にポリアミ)%酸側鎖や架橋鎖、開始剤などを
気化せしめることによシ耐熱性のフィルムを形成せしめ
るプロセスが代表的な形態として用いられる。The method of using the compositions disclosed in these prior art techniques is to apply the compositions as a solution onto a substrate, dry it, irradiate it with active light such as ultraviolet rays through a photomask, and then remove the unexposed areas with a suitable developing solvent. A heat-resistant film is produced by dissolving and removing polyamide to form an image, followed by high-temperature treatment to close the imir ring, etc., and at the same time vaporize the polyamide acid side chains, crosslinking chains, initiator, etc. A process of forming is used as a typical form.
ところで、従来の先行技術においては、いわゆる感光性
?リイミrの膜厚を厚くしていくと、光感度が極端に低
下して、硬化に必要な露光時間が長くなるという欠点を
有するととが見い出された。By the way, in the conventional prior art, the so-called photosensitivity? It has been found that increasing the film thickness of Reimirr has the drawback that the photosensitivity is extremely reduced and the exposure time required for curing becomes longer.
本発明者らは、このような事情に鑑み、光感度が高く、
特に厚膜で使用する場合においても、高い光感度を有す
る耐熱性感光性組成物を提供すべく鋭意研究を重ねた。In view of these circumstances, the inventors of the present invention have developed a material with high photosensitivity.
We have conducted intensive research to provide a heat-resistant photosensitive composition that has high photosensitivity, especially when used in thick films.
その結果、必須成分として特定の構造を有する重合体、
下記一般式(2)または(3)で示される化合物及び吸
収ピーク波長が250〜500nmにある増感剤を含有
して成る組成物がその目的に適合しうろことを見出し、
この知見に基づいて本発明を完成するに至った。As a result, a polymer with a specific structure as an essential component,
It has been discovered that a composition comprising a compound represented by the following general formula (2) or (3) and a sensitizer having an absorption peak wavelength of 250 to 500 nm is suitable for the purpose,
Based on this knowledge, we have completed the present invention.
すなわち、本発明は、(イ)一般式(1)〔式中のXは
(2+n)価の炭素環式基又は複素環式基、Yは(2+
m)価の炭素環式基又は複素環式0
〇
一〇−0−NH−1..*は炭素−炭素二重結合を有す
る基、Wは熱処理によh、−aooR*のカルゼニル基
と反応して環を形成しうる基、nは1又は2、mは0,
1又は2であシ、かつC0OR*とZは互いにオルト位
又はペリ位の関係にある〕
で示される繰り返し単位を有する重合体(以下(イ)成
分と称す)
(ロ)一般式(2)又は(3)で示される化合物、Rツ
〔式(2) 、 (3)中、R1は水素原子、炭素数1
〜4のアルキル基、炭素数1〜4のアルコキシ基、炭素
数1〜4のアルキルチオ基、P、2.YL3は、炭素数
1〜2のアルキル基、R4,R5は、炭素数1〜4のア
ルキル基、又は−緒になって一〇−もしくは−NR7−
で中断されてもよい炭素数4〜5のアルキレン基、R6
は、炭素数6〜16のアリーレン基、R7は炭素数1〜
4のアルキル基を示す。〕及び、
(ハ)吸収ピーク波長が250〜500nmにある増感
剤を含有して成る感光性組成物を提供するものである。That is, the present invention provides (a) general formula (1) [wherein X is a (2+n)-valent carbocyclic group or heterocyclic group, and Y is a (2+
m) a valent carbocyclic or heterocyclic group
〇10-0-NH-1. .. * is a group having a carbon-carbon double bond, W is a group that can react with the carzenyl group of h and -aooR* to form a ring by heat treatment, n is 1 or 2, m is 0,
1 or 2, and C0OR* and Z are in an ortho- or peri-position relationship with each other] A polymer having a repeating unit (hereinafter referred to as component (a)) (b) General formula (2) or a compound represented by (3), R [formula (2), (3), R1 is a hydrogen atom, carbon number 1
-4 alkyl group, C1-4 alkoxy group, C1-4 alkylthio group, P, 2. YL3 is an alkyl group having 1 to 2 carbon atoms, R4 and R5 are an alkyl group having 1 to 4 carbon atoms, or -together 10- or -NR7-
an alkylene group having 4 to 5 carbon atoms which may be interrupted by R6
is an arylene group having 6 to 16 carbon atoms, and R7 is an arylene group having 1 to 16 carbon atoms.
4 shows the alkyl group. ] and (c) provides a photosensitive composition comprising a sensitizer having an absorption peak wavelength of 250 to 500 nm.
本発明組成物において、(イ)成分として用いる重合体
は、前記一般式(1)で示される繰シ返し単位を有する
ものであシ、式中のXは3又は4価の炭素環式基又は複
素環式基であって、このよりなXとしては、例えばベン
ゼン環や、ナフタレン環、アントラセン環なとの縮合多
環芳香環、ピリジン、チオフェンなどの複素環式基、及
び一般式(If)OH3
1は0又は1、X2はOH3又はOF、である〕で示さ
れる基などが挙げられる。これらの中で炭素数6〜14
の芳香族炭化水素基や、Xlが+0Hr)rOF。In the composition of the present invention, the polymer used as component (a) has a repeating unit represented by the above general formula (1), where X is a trivalent or tetravalent carbocyclic group. or a heterocyclic group, and examples of the more rigid )OH3 1 is 0 or 1, X2 is OH3 or OF], and the like. Among these, carbon number 6-14
aromatic hydrocarbon group, Xl is +0Hr) rOF.
OF3 く、さらに式 %式%) で示されるものが好ましい。OF3 Furthermore, the expression %formula%) Those shown are preferred.
前記一般式(1)におけるYは2,3又は4価の炭素環
式基又は複素環式基であって、このようなものとしては
、例えばナフタレン、アントラセンなどに由来する炭素
数10〜18の2価の芳香族炭化水素環、ピリジン、イ
ミダゾールなどに由来する複素環式基及び式
¥1
3Y4
〔式中のYlはH,OH3、(OH3)20H,00H
3、C!OOH。Y in the general formula (1) is a divalent, trivalent, or tetravalent carbocyclic group or heterocyclic group, and examples of such a group include a group having 10 to 18 carbon atoms derived from naphthalene, anthracene, etc. A heterocyclic group derived from a divalent aromatic hydrocarbon ring, pyridine, imidazole, etc. and the formula ¥1 3Y4 [Yl in the formula is H, OH3, (OH3)20H,00H
3.C! OOH.
ハロゲン原子又は5O3H,Y2は+CH糧(ただし、
?I(。Halogen atom or 5O3H, Y2 is +CH food (however,
? I(.
pは0又は1である) 、−80,−1−0−1OH3
Y3及びY4はH,OH3,02H5,00H3、ハロ
ゲン原子、0OOH,80,H又はNo、、y、及びY
6はH,ON。p is 0 or 1), -80, -1-0-1OH3 Y3 and Y4 are H, OH3, 02H5, 00H3, halogen atom, 0OOH, 80, H or No, , y, and Y
6 is H, ON.
ハロゲン原子、CH3、OCH3,503H又はOHで
ある〕で示される基などが挙げられる。これらの中で炭
素数10〜14の2価の芳香族炭化水素環や、Y2が−
so、−1−〇−又は−S−で、かつY3及びY4がと
もに水素原子である式(I5)で示される基が好ましく
、さらに式
で示される基が好ましい。A halogen atom, a group represented by CH3, OCH3, 503H or OH, and the like. Among these, there are divalent aromatic hydrocarbon rings having 10 to 14 carbon atoms, and Y2 is -
A group represented by the formula (I5) in which so, -1-〇- or -S- and Y3 and Y4 are both hydrogen atoms is preferred, and a group represented by the formula is more preferred.
前記一般式(1)におけるWは、熱処理によシ、−00
0R*のカルゼニル基と反応して環を形成しりる基であ
って、このようなものとしては、特に−O−NH,が好
適である。又、nとしては2が好ましい。W in the general formula (1) is -00 by heat treatment.
It is a group that reacts with the carzenyl group of 0R* to form a ring, and -O-NH is particularly suitable as such a group. Further, n is preferably 2.
さらに、前記一般式(1)におけるR*は炭素−炭素二
重結合を有する基であって、とのようなものとしては、
例えば、
−R”−OH= 0H2(Its)
〔式中R′は、水素原子、又は、メチル基、R“は、炭
素数1ないし3のフルキレン基、nは1又は2〕などが
挙げられる。Furthermore, R* in the general formula (1) is a group having a carbon-carbon double bond, such as,
For example, -R"-OH= 0H2(Its) [In the formula, R' is a hydrogen atom or a methyl group, R" is a fullkylene group having 1 to 3 carbon atoms, and n is 1 or 2]. .
(■1)の例としては、 OH2000H=OH2 (■2)の例としては、 (R3)の例としては、 (R4)の例としては、 (R5)の例としては、 0H20H= 0H2 −OH2−OH2−CH=OHz (R6)の例としては、 OH20H2NHO0H=OHz (R7)の例と−しては、 などが挙げられる。As an example of (■1), OH2000H=OH2 As an example of (■2), As an example of (R3), As an example of (R4), As an example of (R5), 0H20H=0H2 -OH2-OH2-CH=OHz As an example of (R6), OH20H2NHO0H=OHz As an example of (R7), Examples include.
本発明組成物において(ロ)成分として用いる化合物は
、前記一般式(2)又は(3)で示されるものである。The compound used as component (b) in the composition of the present invention is represented by the above general formula (2) or (3).
式中R,は、水素原子、炭素数1〜4のアルキル基、炭
素数1〜4のアルコキシ基、炭素数1〜4のアルキルチ
オ基であシ、好ましくは、水素原子、メチル基、エチル
基、メトキシ基、エトキシ基、メチルチオ基などが挙げ
られる。式中R2+ R3は、炭素数1〜2のアルキル
基であシ、メチル基又はエチル基である。式中R4y
R5は、炭素数1〜4のアルキル基、又は−緒になって
一〇−もしくは−NR,7−で中断されてもよい炭素数
4〜5のアルキレン基であシ、好ましくは、メチル基、
エチル基、けられる。R6は炭素数6〜16のアリーレ
ン基であI
。In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group, or an ethyl group. , methoxy group, ethoxy group, methylthio group, etc. In the formula, R2+R3 is an alkyl group having 1 to 2 carbon atoms, a methyl group, or an ethyl group. In the formula R4y
R5 is an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 4 to 5 carbon atoms which may be interrupted by 10- or -NR,7-, preferably a methyl group. ,
Ethyl group is eclipsed. R6 is an arylene group having 6 to 16 carbon atoms.
R7は、炭素数1〜4のアルキル基である。R7 is an alkyl group having 1 to 4 carbon atoms.
式(2)の例としては、
式(3)の例としては、
02H5
などが挙げられるが、これらに限定されるものではない
。Examples of formula (2) include, and examples of formula (3) include, but are not limited to, 02H5.
本発明組成物において(→成分として用いる増感剤は、
吸収ピーク波長が250〜500nmにあるものであシ
、このような例としては、
〔式中R1* ’fL2は、メチル基又はエチル基、R
3は、水素原子又はメチル基、R4は、炭素数6〜10
の芳香族炭化水素、’R,は、メチル基、エチル基又は
炭素数6〜10の芳香族炭化水素、R6* R7は、水
素原子、脂肪族基、置換脂肪族基、炭素数6〜10の芳
香族炭化水素からなる基であり、R11t R7の少な
くとも一方は水素原子ではガい基でるり、R,は、水素
原子、メチル基、エチル基、水酸基、m 、 nは、0
.1又は2〕などが挙げられる。In the composition of the present invention (→ the sensitizer used as a component is
The absorption peak wavelength is in the range of 250 to 500 nm, such as [where R1*'fL2 is a methyl group or an ethyl group, R
3 is a hydrogen atom or a methyl group, R4 is a carbon number of 6 to 10
'R is a methyl group, an ethyl group, or an aromatic hydrocarbon having 6 to 10 carbon atoms, R6* R7 is a hydrogen atom, an aliphatic group, a substituted aliphatic group, and 6 to 10 carbon atoms is a group consisting of an aromatic hydrocarbon, at least one of R11t and R7 is a hydrogen atom, R is a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, m and n are 0
.. 1 or 2].
増感剤の例としては、ミヒラーズケトン、4.4’−ヒ
ス−(ジエチルアミノ)−ベンゾフェノン、2.5−ビ
ス−(4′−ジエチルアミノベンザル)−シクロペンタ
ノン、2.6−ビス−(4′−ジエチルアミノベンザル
)−シクロヘキサノン、2.6−ビス−(4′−ジメチ
ルアミノベンザル)−4−メチル−シクロヘキサノン、
2.6−ビス−(4/ 、)エチルアミノベンザル)
−4−メチル−シクロヘキサノン、4.4’−ビス−(
ジメチルアミノ)−カルコン、4.4’−ヒス−(ジエ
チルアミノ)−カルコン、4−ジメチルアミノシンナミ
リデンインダノン、4−ジメチルアミノベンジリデンイ
ンダノン、2−(4’−ジメチルアミノフェニルビニレ
ン)−ベンゾチアゾール、2−(4’−ジメチルアミノ
フェニルビニレン)−イソナフトチアゾール、1.3−
ビス−(4/ 、)メチルアミノシンザル)−アセト
ン、1 、3− ヒス−(4/ 、)エチルアミノベ
ンザル)−アセトン、3.3’−カルシニル−ビス−(
7−−、、ffエチルアミノクマリン)、7−−jエチ
ルアミノ−3−ペンゾイルクマリン、7−ダニチルアミ
ノ−4−メチルクマリン、N−フェニル−ジェタノール
アミン、N−p−)リルージエチルアミンなどが挙げら
れるか、これらに限定されるものではない。Examples of sensitizers include Michler's ketone, 4,4'-his-(diethylamino)-benzophenone, 2,5-bis-(4'-diethylaminobenzal)-cyclopentanone, 2,6-bis-(4 '-diethylaminobenzal)-cyclohexanone, 2,6-bis-(4'-dimethylaminobenzal)-4-methyl-cyclohexanone,
2.6-bis-(4/,)ethylaminobenzal)
-4-methyl-cyclohexanone, 4,4'-bis-(
dimethylamino)-chalcone, 4,4'-his-(diethylamino)-chalcone, 4-dimethylaminocinnamylideneindanone, 4-dimethylaminobenzylideneindanone, 2-(4'-dimethylaminophenylvinylene)-benzo Thiazole, 2-(4'-dimethylaminophenylvinylene)-isonaphthothiazole, 1.3-
Bis-(4/,)methylaminobenzal)-acetone, 1,3-his-(4/,)ethylaminobenzal)-acetone, 3,3'-carcinyl-bis-(
7--,,ff ethylaminocoumarin), 7-j ethylamino-3-penzoylcoumarin, 7-danitylamino-4-methylcoumarin, N-phenyl-getanolamine, N-p-)lyludiethylamine, etc. However, it is not limited to these.
なおこれらは単独でも複数を混合して使用してもよい。Note that these may be used alone or in combination.
好ましくは、(■りないしく■8)の構造を有する増感
剤と(■9)の構造を有する増感剤を混合して使用する
。Preferably, a sensitizer having the structure (1) to (4) and a sensitizer having the structure (2) are used in combination.
本発明の組成物には、必要に応じて炭素−炭素二重結合
を有する化合物を添加することができる。A compound having a carbon-carbon double bond can be added to the composition of the present invention, if necessary.
この炭素−炭素二重結合を有する化合物は添加すること
により光重合反応を容易にするような化合物であって、
このようなものとしては、2−エチルへキシルアクリレ
ート、2−ヒPロキシエチルアクリレート、N−ビニル
−2−ピロリドン、カルピトールアクリレート、テトラ
ヒrロフルフリルアクリレート、イソデルニルアクリレ
ート、1.6−ヘキサンジオールジアクリレート、ネオ
ペンチルグリコールジアクリレート、エチレングリコー
ルジアクリレート、ポリエチレングリコールジアクリレ
ート、ペンタエリスリトールジアクリレート、トリメチ
ロールプロパントリアクリレート、ペンタエリスリトー
ルトリアクリレート、ジペンタエリスリトールへキサア
クリレート、テトラメチロ・−ルメタンテトラアクリレ
ート、テトジエチレングリコールジアクリレート、ノナ
エチレングリコールシアクリV−ト、メチレンビスアク
リルアミド、N−メチロールアクリルアミr及び、上記
のアクリレート又はアクリルアミrをメタクリレート又
はメタクリルアミPに変えたもの等が挙げられ、これら
の中で好ましいものは、2つ以上の炭素−炭素二重結合
を有する化合物である。This compound having a carbon-carbon double bond is a compound that facilitates the photopolymerization reaction when added,
These include 2-ethylhexyl acrylate, 2-hydroxyproxyethyl acrylate, N-vinyl-2-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, isodernyl acrylate, 1.6- Hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethanetetra Examples include acrylate, tethodiethylene glycol diacrylate, nonaethylene glycol cyacrylate, methylene bisacrylamide, N-methylolacrylamide r, and those in which the above acrylate or acrylamide r is replaced with methacrylate or methacrylamide P. Preferred among these are compounds having two or more carbon-carbon double bonds.
さらに本発明組成物にメルカプタン化合物を添加するこ
とによシ、光感度をさらに向上させることができる。メ
ルカプタン化合物の例としては、例えば、2−メルカプ
トベンズイミダゾール、2−メルカプトベンゾチアゾー
ル、1−フェニル−5−メルカプト−IH−テトラゾー
ル、2−メルカプトチアゾリン、2−メルカプト−4−
7エニルチアゾール、2−アミノ−5−メルカプト−1
,3゜4−チアジアゾール、2−メルカプトイミダゾー
ル、2−メルカプト−5−メチル−1,3,4−チアジ
アゾール、5−メルカプト−1−メチル−IH−テトラ
ゾール、2,4.6−ドリメルカプトーs −)リアジ
ン、2−ジブチルアミノ−4,6−ジメルカプト−s
−)リア、ジン、2.5−uメルカプト−1゜3.4−
チアジアゾール、5−メルカプト−1,3゜4−チアジ
アゾール、1−エチル−5−メルカプ)−1,2,3,
4−テトラゾール、 2−メルカプト−6−ニトロチア
ゾール、2−メルカプトベンゾオキサゾール、4−フェ
ニル−2−メルカプトチアゾール、メルカプトピリジン
、2−メルカプトキノリン、1−メチル−2−メルカプ
トイミダゾール、2−メルカプト−β−ナフトチアゾー
ルなどが挙げられる。Furthermore, by adding a mercaptan compound to the composition of the present invention, the photosensitivity can be further improved. Examples of mercaptan compounds include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-IH-tetrazole, 2-mercaptothiazoline, 2-mercapto-4-
7-enylthiazole, 2-amino-5-mercapto-1
, 3゜4-thiadiazole, 2-mercaptoimidazole, 2-mercapto-5-methyl-1,3,4-thiadiazole, 5-mercapto-1-methyl-IH-tetrazole, 2,4.6-drimercaptos -) Riazine, 2-dibutylamino-4,6-dimercapto-s
-) Leah, Jin, 2.5-u Mercapto-1゜3.4-
Thiadiazole, 5-mercapto-1,3゜4-thiadiazole, 1-ethyl-5-mercap)-1,2,3,
4-tetrazole, 2-mercapto-6-nitrothiazole, 2-mercaptobenzoxazole, 4-phenyl-2-mercaptothiazole, mercaptopyridine, 2-mercaptoquinoline, 1-methyl-2-mercaptoimidazole, 2-mercapto-β -Naphthothiazole and the like.
又、さらに本発明組成物には、必要に応じて官能性ジア
ルコキシシラン化合物を添加又は、基材にプレコートし
て用いることができる。このジアルコキシシラン化合物
は、本発明組成物の耐熱性高分子膜と基材であるSl及
び無機絶縁膜との界面の接着性を向上するような化合物
であって、これらの例としては、例えば、γ−アミノプ
ロピルメチルジメトキシシラン、N−β(アミノエチル
)γ−アミノプロピルジメトキシシラン、γ−グリシド
キシプロビルメチルジメトキシシラン、γ−メルカプト
プロピルメチルジメトキシシラン、ジメトキシ−3−メ
ルカプトプロピルメチルシラン、3−メタクリロキシプ
ロピルジメトキシメチルシラン、3−メタクリロキシプ
ロピルトリメトキシシラン、ジメトキシメチル−3−ピ
ペリジノプロビルシラン、ジェトキシ−3−グリシドキ
シプロビルメチルシラン、N−(a−ジェトキシメチル
シリルプロビル)スクシンイミド等が挙げられる。Furthermore, a functional dialkoxysilane compound can be added to the composition of the present invention, or a base material can be precoated therewith, if necessary. This dialkoxysilane compound is a compound that improves the adhesion of the interface between the heat-resistant polymer film of the composition of the present invention and the base material Sl and inorganic insulating film, and examples thereof include, for example. , γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane , 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinoprobylsilane, jetoxy-3-glycidoxypropylmethylsilane, N-(a-jetoxy Methylsilylprobyl) succinimide and the like.
これらジアルコキシシラン化合物の使用方法及び効果に
ついては、例えば、特願昭60−38242号に詳しく
記載されている。又、本発明組成物の溶液の保存安定性
を向上させるために、重合禁止剤を添加することもでき
る。この重合禁止剤としては、例えば、ハイド四キノン
、N−ニトロソジフェニルアミン、p−tert−ブチ
ルカテコール、フェノチアジン、N−フェニルナフチル
アミン、2,6−シーtert−ブチル−p−メチルフ
ェノール等が挙げられるが、これらに限定されるもので
はない。The usage and effects of these dialkoxysilane compounds are described in detail in, for example, Japanese Patent Application No. 38242/1983. Furthermore, a polymerization inhibitor may be added to improve the storage stability of the solution of the composition of the present invention. Examples of the polymerization inhibitor include hydridetetraquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, and 2,6-tert-butyl-p-methylphenol. , but not limited to these.
本発明における(→成分の一般式(2)又は(3)で示
される化合物の含有割合については、特に制限はないが
、好ましくは(イ)成分の重合体に対し0.1〜20重
量%、さらに好ましくは、1〜15重量%の範囲で含有
させることが望ましい。又、本発明におけるe今成分の
増感剤の含有割合については、(イ)成分の重合体に対
し、0.01〜20重量%さらに好ましくは、0.05
〜15重景%の範囲で含有させることが望ましい。炭素
−炭素二重結合を有する化合物の添加量は、0)成分の
重合体に対して20重景%以下が望ましい。メルカプタ
ン化合物の添加量は、好ましくはC)成分の重合体に対
して、10重量%以下が望ましく、さらに好ましくは、
5重量%以下である。又、前記官能性・クアルコキシシ
ラン化合物を添加して用いる場合、その添加量は、(イ
)成分の重合体に対して0.05〜10重量%1好まし
くは0.1〜4重量%である。In the present invention, the content ratio of the compound represented by the general formula (2) or (3) of the (→ component) is not particularly limited, but is preferably 0.1 to 20% by weight based on the polymer of the component (A). , more preferably in the range of 1 to 15% by weight.Also, the content ratio of the sensitizer as the component e in the present invention is 0.01% to the polymer of component (a). ~20% by weight, more preferably 0.05%
It is desirable to contain it in a range of 15% to 15%. The amount of the compound having a carbon-carbon double bond added is preferably 20% or less based on the polymer of component 0). The amount of the mercaptan compound added is preferably 10% by weight or less based on the polymer of component C), and more preferably,
It is 5% by weight or less. Further, when the functional qualkoxysilane compound is added and used, the amount added is 0.05 to 10% by weight, preferably 0.1 to 4% by weight, based on the polymer of component (A). be.
又、前記重合禁止剤は、0)成分の重合体に対して5重
量%以下、好ましくは、0.5重量%以下添加して用い
られる。The polymerization inhibitor is used in an amount of 5% by weight or less, preferably 0.5% by weight or less, based on the polymer of component 0).
本発明組成物において0)成分として用いる重合体は、
例えば、一般式
で示される化合物と、一般式
で示される化合物とを重縮合又は重付加することによシ
得られる。前記一般式(至)におけるzlの例としては
、−000H(III)、−0001(L)、−Neo
(IIIg)、−NHz(L)、−0H(firs)が
あシ、それぞれに対応する一般式(至)の略号を0内に
示す。又、一般式(財)におけるZ2の例としては、−
oocl(fl/l)、−000H(IVz)、−No
o(■x)、−NHt(■4)があシ、それぞれに対応
する一般弐ωの略号を0内に示す。なお、X、R,Y及
びWは前記と同じ意味をもつ。The polymer used as component 0 in the composition of the present invention is:
For example, it can be obtained by polycondensation or polyaddition of a compound represented by the general formula and a compound represented by the general formula. Examples of zl in the general formula (to) are -000H (III), -0001 (L), -Neo
(IIIg), -NHz(L), -0H(first), and the abbreviations of the corresponding general formulas (to) are shown within 0. Also, as an example of Z2 in the general formula (goods), −
oocl (fl/l), -000H (IVz), -No
o(■x), -NHt(■4), and the corresponding abbreviations of general 2ω are shown within 0. Note that X, R, Y and W have the same meanings as above.
前記の一般式(至)で示される化合物と一般式(転)で
示される化合物との重縮合又F1重付加反応によシーZ
tとZ、−とが反応して結合鎖2が形成される。Sea Z
t and Z, - react to form a bond chain 2.
この際の21とz2との好ましい組み合わせ、生成する
2の種類及び得られた重合体を加熱処理した時に生成す
る環構造基をまとめて第1表に示す。Table 1 summarizes the preferred combinations of 21 and z2, the types of 2 produced, and the ring structural groups produced when the obtained polymer is heat-treated.
以下余白
第 1 表
〔注〕*1 環構造
IM:イミド環
QD:キナゾリンジオン環
ODニオキサジンジオン環
(イ)成分の重合体は、次に示す方法によっても製造す
ることができる。すなわち、一般式%式%)
〔式中のXは前記と同じ意味をもつ〕
で示される化合物を前記一般式(tVj)又は(■4)
で示される化合物と反応させて得られた生成物のカルゼ
キシル基を、一般式
〔式中のR*は前記と同じ意味をもつ〕で示されるエポ
キシ化合物、又は、たとえば一般式
で示されるアミン化合物、又は、一般式で示される四級
アンモニウム塩と反応させることによシ、該重合体が得
られる。Table 1 Notes *1 Ring structure IM: Imide ring QD: Quinazolinedione ring OD Nioxazinedione ring The polymer of component (a) can also be produced by the method shown below. That is, the compound represented by the general formula (% formula %) [X in the formula has the same meaning as above] is converted into the compound represented by the general formula (tVj) or (■4)
The carzexyl group of the product obtained by reacting with the compound represented by the formula is an epoxy compound represented by the general formula [R* in the formula has the same meaning as above], or an amine compound represented by the general formula, for example. Alternatively, the polymer can be obtained by reacting with a quaternary ammonium salt represented by the general formula.
なお、これらの反応は、例えば特開昭56−32524
号公報、特開昭60−19444今号公報に記載されて
いる。Note that these reactions are described, for example, in JP-A-56-32524.
No. 60-19444, this issue.
前記の一般式(TITI)で示される化合物は、例えば
、一般式(■6)
で示される酸無水物なR*OH(R*は前記と同じ意味
をもつ)で開環させて得られる。核酸無水物(■6)と
しては、例えば、無水ピロメリット酸、3.3’。The compound represented by the general formula (TITI) can be obtained, for example, by ring-opening with an acid anhydride R*OH (R* has the same meaning as above) represented by the general formula (6). Examples of the nucleic acid anhydride (■6) include pyromellitic anhydride, 3.3'.
4.4′−ペンゾフエノンテトラカルゼン酸二無水物、
3.3’、4.4’−−jフェニルエーテルテトラカル
ジン酸二無水物、3.3’、4.4’−ジフェニルテト
ラカルジン酸二無水物、313’、4,4/−ジフェニ
ルスルホンテトラカルぽン酸二無水物、2,3,6.7
−ナツタレンチトラカルジン酸無水物、チオフェン−2
゜3.4.5−テトラカルジン酸無水物、2,2−ビス
−(3,4−ヒスカルブキシフェニル)フロパン無水物
等が挙げられ、アルコールR*OHとしては、2−ヒド
ロキシエチルメタクリレート、2−ヒrロキシエチルア
クリレート、2−ヒrロキシプロぎルメタクリレート、
2−ヒドロキシゾロビルアクリレート、アリルアルコー
ル及びエチレングリコールモノアリルエーテル等が挙げ
られる。4.4'-penzophenonetetracarzenic dianhydride,
3.3', 4.4'--j phenyl ethertetracardic dianhydride, 3.3', 4.4'-diphenyltetracardic dianhydride, 313', 4,4/-diphenyl Sulfone tetracarponic dianhydride, 2,3,6.7
-Natsuta lentithracaldic acid anhydride, thiophene-2
゜3.4.5-Tetracardic acid anhydride, 2,2-bis-(3,4-hiscarboxyphenyl)furopane anhydride, etc., and alcohol R*OH includes 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, -hyroxyethyl acrylate, 2-hyroxyprogyl methacrylate,
Examples include 2-hydroxyzorobyl acrylate, allyl alcohol, and ethylene glycol monoallyl ether.
これらの酸無水物(■6)をアルコールR*OHと反応
させるに際して、ピリジン、ジメチルアミノピリジン等
を添加することによシ反応が加速される。When these acid anhydrides (6) are reacted with alcohol R*OH, the reaction is accelerated by adding pyridine, dimethylaminopyridine, etc.
前記の第1表における番号1及び1′の組み合わせは好
ましい実施態様の1例であシ、この組み合わせで用いら
れる一般式(■4)で示されるジアミンとしては、例え
ば、4.4’−ジアミノジフェニルエーテル、4.4’
−ジアミノビフェニル、2,4′−ジアミノトルエン、
4.4’−ジアミノベンゾフェノン、4゜4’−ジアミ
ノジフェニルスルホン、フェニルインダンジアミン、4
.4’−ジアミノジフェニルメタン、p−フェニレンジ
アミン、m−フェニレンジアミン、1,5−ジアミノナ
フタレン、3.3’−ジメトキシ414’ ) yミ
ノビフェニル、3.3’−−9メチ/l/−4,4’−
ジアミノビフェニル、〇−トルイジンスルホン、2,2
−ビス(4−アミノフェノキシフェニル)プロパン、ビ
ス(4−アミノフェノキシフェニル)スルホン、ビス(
4−アミノフェノキシフェニル)スルフィr、1.a−
ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス
(4−7ミノフエノキシ)ベンゼン、3.4’ −−7
アミノジフエニルエーテル、9.9−ビス(4−アミノ
フェニル)アントラセン−(10)、9,9−ビス(4
−7ミノフエニル)フルオレン、3.3’−ジアミノジ
フェニルスルホン、4.4’−ジー(3−アミノフェノ
キシ)ジフェニルスルホン、4.4’−−、ffアミノ
4ンズアニ+7 )’、3.4’−Jアミノジフェニル
エーテル、4.4’−[1,3−フェニレンビス(1−
メチルエチリデン)〕、4.4’−〔1,4−7二二レ
ンビス(1−メチルエチリデン) ]、4 、4’ −
(m−フェニレンジイソプロピリデン)ビス(m−1−
ルイジン)、4゜4’−(p−−yエニレンジイソプロ
ヒリテン)ビス(m−トルイジン)等が挙げられる。The combination of numbers 1 and 1' in Table 1 above is one example of a preferred embodiment, and the diamine represented by the general formula (4) used in this combination is, for example, 4,4'-diamino diphenyl ether, 4.4'
-diaminobiphenyl, 2,4'-diaminotoluene,
4.4'-diaminobenzophenone, 4゜4'-diaminodiphenylsulfone, phenylindane diamine, 4
.. 4'-diaminodiphenylmethane, p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 3.3'-dimethoxy414') yminobiphenyl, 3.3'--9methy/l/-4, 4'-
Diaminobiphenyl, 〇-Toluidine sulfone, 2,2
-Bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(
4-aminophenoxyphenyl)sulfur, 1. a-
Bis(4-aminophenoxy)benzene, 1,3-bis(4-7minophenoxy)benzene, 3.4' --7
Aminodiphenyl ether, 9,9-bis(4-aminophenyl)anthracene-(10), 9,9-bis(4
-7minophenyl)fluorene, 3.3'-diaminodiphenylsulfone, 4.4'-di(3-aminophenoxy)diphenylsulfone, 4.4'--, ffamino4densani+7)', 3.4'- J aminodiphenyl ether, 4,4'-[1,3-phenylene bis(1-
methylethylidene)], 4.4'-[1,4-7 22lenebis(1-methylethylidene)], 4,4'-
(m-phenylene diisopropylidene) bis(m-1-
luidine), 4°4'-(p--yenylenediisoprohyritene)bis(m-toluidine), and the like.
この組み合わせのうち、一般式(■1)で示される化合
物と一般式(■4)で示される化合物との反応は、カル
ゼジイミP型脱水縮合剤、例えば、ジシクロへキシルカ
ルぎジイミPを用いて行なうことができる。Of this combination, the reaction between the compound represented by the general formula (■1) and the compound represented by the general formula (■4) is carried out using a calzediimi P type dehydration condensation agent, for example, dicyclohexyl calzediimi P. be able to.
又、前記一般式(■2)で示される化合物は、一般式(
■1)で示される半エステルに塩化チオニルや五塩化リ
ンなどを反応させることによシ得ることができる。In addition, the compound represented by the general formula (■2) is represented by the general formula (
(2) It can be obtained by reacting the half ester shown in 1) with thionyl chloride, phosphorus pentachloride, etc.
これらの反応の方法については、例えば、特願昭59−
193737号、特願昭60−9918号、特願昭59
−238545号等に詳しく記載されている。For the methods of these reactions, see, for example, Japanese Patent Application No. 1983-
No. 193737, patent application No. 1983-9918, patent application No. 1983
-238545 etc. in detail.
本発明組成物は、該組成物中のすべての成分を溶解しう
る溶媒に溶解して所定の基体上に塗布して用いる。この
際、基体との密着性を高めるために、前記ジアルコキシ
シラン化合物を基体にプレコートして用いることもでき
る。The composition of the present invention is used by dissolving it in a solvent that can dissolve all the components in the composition and coating it on a predetermined substrate. At this time, in order to improve the adhesion to the substrate, the dialkoxysilane compound may be pre-coated on the substrate.
前記溶媒としては極性溶媒が好ましく、例えばジメチル
ホルムアミr1N−メチルピロリドン、ジメチルアセト
アミr1 ジグライム、酢酸イソブチル、シクロペンタ
ノンなど沸点が高すぎないものが望ましい。さらに、ア
ルコール、芳香族炭化水素、エーテル、ケトン、エステ
ルなどの溶媒を成分を析出させない範囲で加えることも
できる。The solvent is preferably a polar solvent, such as dimethylformamyl N-methylpyrrolidone, dimethylacetamyl diglyme, isobutyl acetate, or cyclopentanone, which does not have an excessively high boiling point. Furthermore, solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, and esters can be added to the extent that the components are not precipitated.
基体上に塗布する方法としては、前記のようにして得ら
れた溶液を、フィルターでろ過した後、例えばスピンコ
ーター、ノ々−コーター、ブレードコーター、スクリー
ン印刷法などで基体に塗布する方法、基体を該溶液に浸
漬する方法、該溶液を基体に噴霧する方法などを用いる
ことができる。The method for coating the substrate on the substrate includes a method in which the solution obtained as described above is filtered and then coated on the substrate using, for example, a spin coater, a no-no-coater, a blade coater, a screen printing method, etc.; A method of immersing the substrate in the solution, a method of spraying the solution onto the substrate, etc. can be used.
基体としては、例えば金属ガラス、シリコン半導体、金
属酸化物絶縁体、窒化ケイ素などの耐熱材料が好ましく
、又、加熱処理しない場合は、銅張ガラスエポキシ積層
板などの材料を用いることができる。As the substrate, heat-resistant materials such as metallic glass, silicon semiconductors, metal oxide insulators, and silicon nitride are preferable, and when heat treatment is not performed, materials such as copper-clad glass epoxy laminates can be used.
次に、このようにして得られた塗膜を風乾、加熱乾燥、
真空乾燥などを組み合わせて乾燥したのち、通常フォト
マスクを通して露光を行なう。この際、用いる活性光線
としては、例えば紫外線、X線、電子線などが挙げられ
、これらの中で紫外線が好ましく、その光源としては、
例えば低圧水銀灯、高圧水銀灯、超高圧水銀灯、ハロゲ
ンランプなどが挙げられる。これらの光源の中で超高圧
水銀灯が好適である。又、露光は窒素雰囲気下で行なう
ことが好ましい。Next, the coating film obtained in this way is air-dried, heat-dried,
After drying using a combination of vacuum drying and the like, exposure is usually performed through a photomask. At this time, the active light used includes, for example, ultraviolet rays, X-rays, electron beams, etc. Among these, ultraviolet rays are preferable, and the light source thereof is as follows:
Examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. Among these light sources, ultra-high pressure mercury lamps are preferred. Further, it is preferable that the exposure is performed under a nitrogen atmosphere.
このようにして露光したのち、未照射部を除去すべく、
浸漬法やスプレー法などを用いて現像を行なう。この除
用いる現像液としては、未露光膜を適当な時間内に完全
に溶解除去しうるようなものが好ましく、例えばN−メ
チルピロリドン、N−アセチル−2−ピロリドン、N、
N−ジメチルホルムアミFIXN、N−ジメチルアセト
アミr、ジメチルスルホキシP1ヘキサメチルホスホリ
ックトリアミド、N−ベンジル−2−ピロリドン、γ−
ブチ四ラクトンなどの非プロトン性極性溶媒を単独で用
いてもよいし、るるいはこれらに第2成分として、例え
ばエタノール、イソプロパツールなどのアルコール、ト
ルエン、キシレンカドの芳香族炭化水素化合物、メチル
エチルケトン、メチルイソブチルケトンなどのケトン、
酢酸エチル、プロピオン酸メチルなどエステル、テトラ
ヒドロ7ラン、ジオキサンのようなエーテルなどの溶媒
を混合して用いてもよい。さらに、現像直後に前記第2
成分として示したような溶媒でリンスすることが好まし
い。After exposing in this way, in order to remove the unexposed area,
Development is performed using a dipping method, a spray method, etc. The developer used for this removal is preferably one that can completely dissolve and remove the unexposed film within an appropriate time, such as N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N-acetylpyrrolidone,
N-dimethylformamide FIXN, N-dimethylacetamide, dimethylsulfoxy P1 hexamethylphosphoric triamide, N-benzyl-2-pyrrolidone, γ-
Aprotic polar solvents such as butytetralactone may be used alone, or they may be combined with alcohols such as ethanol and isopropanol, aromatic hydrocarbon compounds such as toluene and xylene, and methyl ethyl ketone. , ketones such as methyl isobutyl ketone,
A mixture of solvents such as esters such as ethyl acetate and methyl propionate, and ethers such as tetrahydro7rane and dioxane may be used. Furthermore, immediately after development, the second
It is preferred to rinse with a solvent such as those indicated as components.
このようにして得られた画像は乾燥後、150〜450
℃の温度範囲で加熱することによシ、イミP環、イソイ
ン)%oキナゾリンジオン環、オキサジンジオン環、キ
ナゾリンジオン環などを有する耐熱性高分子化合物に変
換される。After drying, the image obtained in this way has an image density of 150 to 450
By heating in the temperature range of °C, it is converted into a heat-resistant polymer compound having a quinazolinedione ring, an oxazinedione ring, a quinazolinedione ring, etc.
本発明組成物は、従来の先行技術で開示されている組成
物に比べて多くの利点を有している。この利点としては
、まず、高い光感度が達成されたことが挙げられ、又、
フォトレジストの特性として重要視されているリソグラ
フィー特性も著しく改良されたことが挙げられる。これ
らの結果として本発明組成物は、低露光量で高解像度を
示すというフォトレジストとして理想的な特性を有して
いることが分る。さらに該組成物は、長期の放置安定性
を有し、塗膜乾燥時における好ましからざるゲル化及び
クラックの発生もないという利点がある。The compositions of the present invention have many advantages over compositions disclosed in the prior art. The advantages of this include, first, that high photosensitivity was achieved;
The lithography properties, which are considered important as photoresist properties, have also been significantly improved. These results show that the composition of the present invention has ideal properties as a photoresist, such as exhibiting high resolution at low exposure doses. Furthermore, the composition has the advantage of long-term storage stability and no undesirable gelation or cracking during coating drying.
本発明組成物は、半導体素子用の層間絶縁膜や表面保護
膜などに用いれば、前記の特性を反映してプロセスがよ
シ短縮され、かつ微細加工が容易となシ、その上、よシ
平坦な層を形成しうるなどの特徴を発揮する。When the composition of the present invention is used as an interlayer insulating film or a surface protective film for semiconductor devices, the above-mentioned characteristics can greatly shorten the process and facilitate microfabrication. It exhibits characteristics such as being able to form a flat layer.
次に、実施例によシ本発明をさらに詳細に説明するが、
本発明はこれらの例によって何ら限定されるものではな
い。なお、実施例に用いた?リマ−、一般式(2)又は
(3)の化合物、増感剤、炭素−炭素二重結合を有する
化合物(モノマー)、メルカプタン化合物、官能性ジア
ルコキシシラン化合物、重合禁止剤の名称等を表1に示
す。Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples in any way. In addition, ? used in the example? Displays the names of reamers, compounds of general formula (2) or (3), sensitizers, compounds with carbon-carbon double bonds (monomers), mercaptan compounds, functional dialkoxysilane compounds, and polymerization inhibitors. Shown in 1.
表 1
(1) ポリマー
(2)一般式(2)又は(3)で示される化合物(3)
増感剤
吸収ピーク波長は、/々リアン社製キヤIJギヤ19分
光光度計(Varian 0ARY2195pectr
o Photometer)によシ、溶媒にエタノール
を用いて測定した。Table 1 (1) Polymer (2) Compound (3) represented by general formula (2) or (3)
The sensitizer absorption peak wavelength was measured using a Varian 0ARY2195pectr spectrophotometer (Varian 0ARY2195pectr).
o Photometer) using ethanol as a solvent.
(4)モノマー
(5) メルカプタン化合物
(6)官能性ジアルコキシシラン化合物(7)重合禁止
剤
実施例1〜15
表2に示したポリマー100重量部に対し、添加剤を同
表に示した重量部加え、130重量部のNメチルピロリ
ドンに溶解した。この溶液をシリコンウェハー上にスピ
ンコード(1300rpm X 30 sec ) L
、70℃空気中で1時間乾燥して均一な塗膜を得た。(4) Monomer (5) Mercaptan compound (6) Functional dialkoxysilane compound (7) Polymerization inhibitor Examples 1 to 15 For 100 parts by weight of the polymer shown in Table 2, add the additive by weight shown in the same table. part by weight and dissolved in 130 parts by weight of N-methylpyrrolidone. This solution was applied to a silicon wafer using a spin code (1300 rpm x 30 sec) L
, and dried in air at 70° C. for 1 hour to obtain a uniform coating film.
次に窒素雰囲気下でグレースケール(KodakPho
tograpic 5tep Tablet A2 )
を通して、超高圧水銀灯(8mW/cm2)で5分間露
光した。このウェハー23℃で30分間放置した後、揺
動浸漬式現像機を用い、23℃でN−メチルピロリドン
とキシレンの2:3(体積比)混合液で現像し、キシレ
ンでリンスして乾燥した。グレースケールの各ステップ
の硬化状態よシ感度を段数として求めた。(段数が高い
ほど感度が高いことを示し、段数が1段上がると、その
露光量がVl−だけ低いことを意味する。)
得られた結果を同表に示す。Next, under a nitrogen atmosphere, gray scale (KodakPho)
tographic 5tep Tablet A2)
The film was exposed to light for 5 minutes using an ultra-high pressure mercury lamp (8 mW/cm2). After this wafer was left at 23°C for 30 minutes, it was developed with a 2:3 (volume ratio) mixture of N-methylpyrrolidone and xylene at 23°C using a rocking immersion developer, rinsed with xylene, and dried. . The curing state and sensitivity of each gray scale step were calculated as the number of steps. (The higher the number of steps, the higher the sensitivity; increasing the number of steps by one means that the exposure amount is lower by Vl-.) The obtained results are shown in the same table.
比較例1〜5
実施例1〜15と同様にして表3の組成物について実験
を行ない、同表に示した結果を得た。Comparative Examples 1 to 5 Experiments were conducted on the compositions in Table 3 in the same manner as in Examples 1 to 15, and the results shown in the table were obtained.
比較例6〜1〇
一般式(2)又は(3)で示される化合物の変わシに、
他の光重合開始剤を用いて、実施例1〜15と同様にし
て、表4の組成物について実験を行ない、同表に示した
結果を得た。Comparative Examples 6 to 10 In place of the compound represented by general formula (2) or (3),
Experiments were conducted on the compositions in Table 4 in the same manner as in Examples 1 to 15 using other photopolymerization initiators, and the results shown in the table were obtained.
以下余白Margin below
Claims (1)
・・・(1) 〔式中のXは(2+n)価の炭素環式基又は複素環式基
、Yは(2+m)価の炭素環式基又は複素環式基、Zは
▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼又は ▲数式、化学式、表等があります▼、R^*は炭素−炭
素二重結合を有する基、Wは熱処理により、−COOR
^*のカルボニル基と反応して環を形成しうる基、nは
1又は2、mは0、1又は2であり、かつCOOR^*
とZは互いにオルト位又はペリ位の関係にある〕で示さ
れる繰返し単位を有する重合体、及び、 (ロ)一般式(2)又は(3)で示される化合物▲数式
、化学式、表等があります▼・・・・・・・・・・・・
(2) ▲数式、化学式、表等があります▼・・・・・・・・・
(3) 〔式中、R_1は水素原子、炭素数1〜4のアルキル基
、炭素数1〜4のアルコキシ基、炭素数1〜4のアルキ
ルチオ基、R_2、R_3は、炭素数1〜2のアルキル
基、R_4、R_5は、炭素数1〜4のアルキル基、又
は一緒になつて−O−もしくは−NR_7−で中断され
てもよい炭素数4〜5のアルキレン基、R_6は、炭素
数6〜16のアリーレン基、R_7は、炭素数1〜4の
アルキル基を示す〕及び (ハ)吸収ピーク波長が、250〜500nmにある増
感剤を有して成る新しい感光性組成物[Claims] 1 (a) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(1) [In the formula, X is a (2+n)-valent carbocyclic group or heterocyclic group, Y is a (2+m)-valent carbocyclic group or heterocyclic group, and Z is , tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R^* is a group with a carbon-carbon double bond, W is -COOR by heat treatment
A group that can react with the carbonyl group of ^* to form a ring, n is 1 or 2, m is 0, 1 or 2, and COOR^*
and Z are in an ortho- or peri-position relationship with each other], and (b) a compound represented by the general formula (2) or (3). Yes▼・・・・・・・・・・・・
(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(3) [In the formula, R_1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and R_2 and R_3 are hydrogen atoms having 1 to 2 carbon atoms. The alkyl group, R_4, R_5 is an alkyl group having 1 to 4 carbon atoms, or together is an alkylene group having 4 to 5 carbon atoms which may be interrupted by -O- or -NR_7-, and R_6 is an alkyl group having 6 carbon atoms. ~16 arylene group, R_7 represents an alkyl group having 1 to 4 carbon atoms] and (iii) a sensitizer having an absorption peak wavelength of 250 to 500 nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5709586A JPS62215264A (en) | 1986-03-17 | 1986-03-17 | New photosensitive composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5709586A JPS62215264A (en) | 1986-03-17 | 1986-03-17 | New photosensitive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS62215264A true JPS62215264A (en) | 1987-09-21 |
Family
ID=13045946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5709586A Pending JPS62215264A (en) | 1986-03-17 | 1986-03-17 | New photosensitive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62215264A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0651512A (en) * | 1992-07-30 | 1994-02-25 | Sumitomo Bakelite Co Ltd | Photosensitive resin composition |
WO2005101125A1 (en) * | 2004-03-31 | 2005-10-27 | Hitachi Chemical Dupont Microsystems Ltd. | Heat-resistant photosensitive resin composition, process for producing pattern from the composition, and electronic part |
US7335517B2 (en) * | 1996-12-02 | 2008-02-26 | Kabushiki Kaisha Toshiba | Multichip semiconductor device, chip therefor and method of formation thereof |
CN102250115A (en) * | 2011-05-13 | 2011-11-23 | 深圳市有为化学技术有限公司 | Carbazole cyclic derived type aromatic ketone compound as well as preparation method and photo initiator thereof |
CN111620845A (en) * | 2020-05-18 | 2020-09-04 | 北京化工大学常州先进材料研究院 | Long-wavelength morpholinyl acetophenone photoinitiator and preparation method thereof |
-
1986
- 1986-03-17 JP JP5709586A patent/JPS62215264A/en active Pending
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0651512A (en) * | 1992-07-30 | 1994-02-25 | Sumitomo Bakelite Co Ltd | Photosensitive resin composition |
US7335517B2 (en) * | 1996-12-02 | 2008-02-26 | Kabushiki Kaisha Toshiba | Multichip semiconductor device, chip therefor and method of formation thereof |
US7829975B2 (en) | 1996-12-02 | 2010-11-09 | Kabushiki Kaisha Toshiba | Multichip semiconductor device, chip therefor and method of formation thereof |
US8174093B2 (en) | 1996-12-02 | 2012-05-08 | Kabushiki Kaisha Toshiba | Multichip semiconductor device, chip therefor and method of formation thereof |
US8283755B2 (en) | 1996-12-02 | 2012-10-09 | Kabushiki Kaisha Toshiba | Multichip semiconductor device, chip therefor and method of formation thereof |
WO2005101125A1 (en) * | 2004-03-31 | 2005-10-27 | Hitachi Chemical Dupont Microsystems Ltd. | Heat-resistant photosensitive resin composition, process for producing pattern from the composition, and electronic part |
JPWO2005101125A1 (en) * | 2004-03-31 | 2008-03-06 | 日立化成デュポンマイクロシステムズ株式会社 | Heat-resistant photosensitive resin composition, pattern manufacturing method using the composition, and electronic component |
US7932012B2 (en) | 2004-03-31 | 2011-04-26 | Hitachi Chemical Dupont Microsystems Ltd. | Heat-resistant photosensitive resin composition, method for forming pattern using the composition, and electronic part |
CN102250115A (en) * | 2011-05-13 | 2011-11-23 | 深圳市有为化学技术有限公司 | Carbazole cyclic derived type aromatic ketone compound as well as preparation method and photo initiator thereof |
CN111620845A (en) * | 2020-05-18 | 2020-09-04 | 北京化工大学常州先进材料研究院 | Long-wavelength morpholinyl acetophenone photoinitiator and preparation method thereof |
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