CN109814336A - Alkali soluble negative photosensitive polyimide resin combination - Google Patents
Alkali soluble negative photosensitive polyimide resin combination Download PDFInfo
- Publication number
- CN109814336A CN109814336A CN201910053285.8A CN201910053285A CN109814336A CN 109814336 A CN109814336 A CN 109814336A CN 201910053285 A CN201910053285 A CN 201910053285A CN 109814336 A CN109814336 A CN 109814336A
- Authority
- CN
- China
- Prior art keywords
- negative photosensitive
- alkali soluble
- photosensitive polyimide
- polyimide resin
- soluble negative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 96
- 239000003513 alkali Substances 0.000 title claims abstract description 68
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 55
- 239000004642 Polyimide Substances 0.000 claims abstract description 41
- -1 ethylmercapto group Chemical group 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000012965 benzophenone Substances 0.000 claims abstract description 13
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 claims abstract description 13
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000005513 chalcones Nutrition 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 125000004427 diamine group Chemical group 0.000 claims abstract description 3
- 125000006159 dianhydride group Chemical group 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 24
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- 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 claims description 18
- 238000000016 photochemical curing Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 150000004985 diamines Chemical class 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- PXHIYFMTRHEUHZ-UHFFFAOYSA-N 5-hydroxy-2-benzofuran-1,3-dione Chemical compound OC1=CC=C2C(=O)OC(=O)C2=C1 PXHIYFMTRHEUHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000005375 organosiloxane group Chemical group 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- RDLGTRBJUAWSAF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-2-one Chemical compound CC(=O)CC1C=CC=CC1(C)O RDLGTRBJUAWSAF-UHFFFAOYSA-N 0.000 claims description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004258 Ethoxyquin Substances 0.000 claims description 3
- 235000017858 Laurus nobilis Nutrition 0.000 claims description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 3
- FPUXVOPOMLHSJA-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCON1C(=O)NC(=O)NC1=O Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCON1C(=O)NC(=O)NC1=O FPUXVOPOMLHSJA-UHFFFAOYSA-N 0.000 claims description 3
- 235000005212 Terminalia tomentosa Nutrition 0.000 claims description 3
- 244000125380 Terminalia tomentosa Species 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- WCHFOOKTKZYYAE-UHFFFAOYSA-N ethoxyperoxyethane Chemical compound CCOOOCC WCHFOOKTKZYYAE-UHFFFAOYSA-N 0.000 claims description 3
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940093500 ethoxyquin Drugs 0.000 claims description 3
- 235000019285 ethoxyquin Nutrition 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 125000005462 imide group Chemical group 0.000 claims 4
- YAPQBXQYLJRXSA-UHFFFAOYSA-N theobromine Chemical compound CN1C(=O)NC(=O)C2=C1N=CN2C YAPQBXQYLJRXSA-UHFFFAOYSA-N 0.000 claims 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 229960004559 theobromine Drugs 0.000 claims 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 4
- 230000036211 photosensitivity Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 125000006157 aromatic diamine group Chemical class 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000011161 development Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 150000003949 imides Chemical class 0.000 description 7
- 206010034960 Photophobia Diseases 0.000 description 6
- 208000013469 light sensitivity Diseases 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- IKRMLSLDSFGOQR-UHFFFAOYSA-N C1=CC=CC2=CC3=CC=CC=C3C=C12.C(C)(C)C1=CC=CC=2SC3=CC=CC=C3C(C12)=O Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C12.C(C)(C)C1=CC=CC=2SC3=CC=CC=C3C(C12)=O IKRMLSLDSFGOQR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- FJWVDERMKUPZDG-UHFFFAOYSA-N methyl prop-2-enoate pentane Chemical compound CCCCC.COC(=O)C=C FJWVDERMKUPZDG-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- SIMFZBAGLIDEPJ-UHFFFAOYSA-N C1(=CC=CC=C1)CC(C)=O.C(C)OOOCC Chemical compound C1(=CC=CC=C1)CC(C)=O.C(C)OOOCC SIMFZBAGLIDEPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention is suitable for field of material technology, provide a kind of alkali soluble negative photosensitive polyimide resin combination, the composition includes following component according to the mass fraction: 30 parts~60 parts alkali soluble negative photosensitive polyimide copolymers, 1.5 parts~15 parts acrylate monomers, 1 part~4 parts photoinitiators, 90 parts~220 parts organic solvents and 0.05 part~0.3 part surfactant；The structural formula of the alkali soluble negative photosensitive polyimide copolymer is as shown in Equation 1, in which: x=5~80, R are the segment with carboxyl and unsaturated double-bond, wherein A1For the fluorinated aromatic diamine unit with ethylmercapto group, A2For benzophenone dianhydride units, A3For the dianhydride units of main chain group containing chalcone, A4For the diamine unit containing loop coil.The present invention has better photosensitivity and resolution ratio, while after overexposure, non-exposed area can be developed with inorganic alkali solution, can be widely applied to the fields such as aerospace.
Description
Technical field
The invention belongs to field of material technology more particularly to a kind of alkali soluble negative photosensitive polyimide resin combinations.
Background technique
Polyimides has the comprehensive performances such as high-fire resistance, high intensity, high dielectric property, due to its material forms multiplicity
Change, be used widely in fields such as aerospace, electric appliance, machinery, microelectronics, is mainly used for integrated line in microelectronic field
Road multilayer wiring, the insulating layer of multichip module, chip protection film and circuit package etc..It is sub- compared to traditional non-photosensitivity polyamides
Amine, light-sensitive polyimide had not only played photoresist but also had played dielectric material, and technical process is simplified, and improves life
Produce efficiency.At present using it is wide be ester type photosensitive polyimide, ionic light-sensitive polyimide and from perception is increased it is photosensitive poly-
Gather before acid imide, ester type photosensitive polyimide and ionic the light-sensitive polyimide actually polyimides with photosensitive group
Body, but through overexposure, first movie queen, the high temperature as needed for hot imidization can cause film layer loss serious, and process
It is more many and diverse, therefore the application of this kind of material is extremely limited.And it is although overcome from perceptual light-sensitive polyimide is increased
The shortcomings that stating two kinds of light-sensitive polyimides, but have the shortcomings that resolution ratio is low.Therefore, light can both be carried out by researching and developing and developing
Crosslinking, simultaneously membrane left rate and resolution ratio and high full imidization light-sensitive polyimide become the master of research light-sensitive polyimide
Want direction.
CN 1448421A discloses a kind of Intrinsical photo-sensistive polyimide resin, and the resin in main chain by introducing
Ketone carbonyl and make polyimide resin have light sensitivity, improve photonasty, and highly polar, high boiling solvent can be dissolved in,
It can be dissolved in general polarity, low boiling point solvent again, but organic solvent can only be used as developer solution after exposing, caused by environment
Pollution problem is more serious.CN 1794087A discloses a kind of self-sensitizing negative polyimide resin, and the resin is in main chain and side
Photosensitive group is introduced on chain simultaneously, obtains the polyimide material of better photosensitivity and resolution ratio, but it is organic there are still that need to use
The problem of solvent development.CN 101055420A discloses the polyimide resin of a kind of alkali soluble, the resin using hydroxyl or
The end-capping reagent of carboxyl introduces hydroxy or carboxy in resinous terminal part, forms alkaline bleach liquor soluble polyimide resin, adds
Photoacid generator make exposure generate acid after exposure bake in catalytic crosslinking, but this kind of polyimide resin itself and be free of photosensitive base
Group, and will lead to the acid that exposure generates using photoacid generator and remain in glue film, there is the hidden danger of corrosion to device.
Summary of the invention
The embodiment of the present invention provides a kind of alkali soluble negative photosensitive polyimide resin combination, it is intended to solve polyamides Asia
Polyimide resin develops film loss greatly, the problem of performance difference.The present invention is not required to the Anhua Gao Wenreya, lightsensitivity height, high resolution,
Thermal stability and endurance are good, humidity resistance is good, good to each substrate adhesive force, and inorganic alkali solution can be used as development
Liquid.
The embodiments of the present invention are implemented as follows, a kind of alkali soluble negative photosensitive polyimide resin combination, including such as
Under component according to the mass fraction: 30 parts~60 parts alkali soluble negative photosensitive polyimide copolymers, 1.5 parts~15 parts propylene
Acid esters system monomer, 1 part~4 parts photoinitiators, 90 parts~220 parts organic solvents and 0.05 part~0.3 part surfactant；
The structural formula of the alkali soluble negative photosensitive polyimide copolymer is as shown in Equation 1:
Wherein: x=5~80, R are the segment with carboxyl and unsaturated double-bond, wherein A1For the fluorine-containing aromatic with ethylmercapto group
Race's diamine unit, A2For benzophenone dianhydride units, A3For the dianhydride units of main chain group containing chalcone, A4For the diamines containing loop coil
Unit.
Further, the alkali soluble negative photosensitive polyimide copolymer is by the fluorinated aromatic two with ethylmercapto group
Amine, the diamines containing loop coil, the dianhydride of main chain group containing chalcone, benzophenone dianhydride, 4- hydroxyl phthalic anhydride and unsaturated acid anhydride copolymerization
It obtains.
Preferably, the structural formula of the fluorinated aromatic diamines with ethylmercapto group is as shown in formula two:
Wherein: R1For
Preferably, the structural formula of the diamines containing loop coil is as shown in formula three:
Wherein R2It is preferably following structure for spirane structure:
Preferably, the structural formula of the dianhydride of main chain group containing chalcone is as shown in formula four:
Wherein X is (CH2)n, 2≤n >=8.
Preferably, the unsaturated acid anhydride is one of following:
Wherein R3、R4For H or-(CH3)n1, 1 < n1<8。
Preferably, the preparation method of the alkali soluble negative photosensitive polyimide copolymer, includes the following steps:
A, by the fluorinated aromatic diamines with ethylmercapto group, 2:1 is placed in N- crassitude in molar ratio with benzophenone dianhydride
In ketone, the diamines of anamorphic zone imide structure is reacted；
B, by the dianhydride of diamines and the main chain group containing chalcone containing loop coil, 1:2 is placed in N- crassitude in molar ratio
In ketone, the dianhydride of anamorphic zone imide structure is reacted；
C, in molar ratio by the dianhydride of the diamines of step a anamorphic zone imide structure and step b anamorphic zone imide structure
1:1-1.5:1 react after be added 4- hydroxyl phthalic anhydride, react anamorphic zone terminal hydroxy group photoactive polyamide acid solution；It is described
The molar ratio of diamines with imide structure and the 4- hydroxyl phthalic anhydride is 5:1；
D, acetic anhydride/anhydrous pyridine is added into the photoactive polyamide acid solution with terminal hydroxy group of step c, carries out chemistry
After imidization dehydration, products therefrom is placed in repeated precipitation in precipitating reagent, is filtered, washed, dries, it is photosensitive poly- to obtain terminal hydroxy group
Acid imide；The mass ratio of the acetic anhydride and the anhydrous pyridine is 100:1；
E, the terminal hydroxy group light-sensitive polyimide of step d is dissolved in polar solvent, unsaturated acid anhydride is added, reaction obtains
Alkali soluble negative photosensitive polyimide copolymer；The molar ratio of the unsaturated acid anhydride and the terminal hydroxy group light-sensitive polyimide
For 1:1.
The precipitating reagent is methanol, ethyl alcohol or ultrapure water.The polar solvent is N-Methyl pyrrolidone.
Further, the acrylate monomer is preferably laurel acid methacrylate, Glycidyl methacrylate
Glyceride, isobornyl (methyl) acrylate, bicyclic pentane methyl acrylate, 3- hydroxyl -2,2- dimethyl propyl -3-
Hydroxyl -2,2- dimethyl propyl ester diacrylate, tricyclic decane dimethanol dipropyl dilute acid ester, neopentylglycol diacrylate, the third oxygen
Change neopentylglycol diacrylate, ethoxylated bisphenol A diacrylate, three (2- ethoxy) isocyanuric acid triacrylates, three
Hydroxymethyl-propane three (methyl) acrylate, pentaerythritol triacrylate and ethoxyquin trimethylolpropane tris (methyl) third
One of olefin(e) acid ester or at least two mixtures that combine in any proportion.
Further, the photoinitiator is preferably α-α-diethoxy acetophenone, 2- hydroxy-2-methyl-phenyl third
Ketone-1,1- hydroxy-cyciohexyl Benzophenone, 2- hydroxy-2-methyl-are to ethoxy ether phenylacetone-1,2- methyl-1-(4- first
Sulfenyl phenyl) -2- morpholine -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) butanone, 4- benzoyl -
4 '-methyldiphenyl thioethers, isopropyl thioxanthone anthracene, 2,4- diethyl thioxanthone and bis- [2,6- bis- fluoro- 3- (1H- pyrrole radicals -1)
Phenyl] titanium cyclopentadienyl one kind or at least two mixtures that combine in any proportion.
Further, the organic solvent is preferably N-Methyl pyrrolidone, cyclohexanone, dimethylformamide, diformazan
One of yl acetamide and gamma-butyrolacton or at least two mixed solvents that mix in any proportion.
Further, the surfactant is preferably dimethyl silicone polymer, polyether polyester modified organic silicon oxygen
Alkane, alkyl-modified organosiloxane or esters of acrylic acid levelling agent.
The embodiment of the present invention, which is also provided, forms pattern with the alkali soluble negative photosensitive polyimide resin combination
Method includes the following steps:
1) the alkali soluble negative photosensitive polyimide resin combination is coated on substrate, forms photosensitive film layer；
2) by the resulting photosensitive film layer of step 1) in 90 DEG C~120 DEG C progress prebake conditions 1min~5min, formation is done photosensitive
Film；
3) the resulting dry light-sensitive surface of step 2) is exposed and is developed, form photocuring pattern；
4) solidify after carrying out the resulting photocuring pattern of step 3) in 150 DEG C~250 DEG C.
Further, the step 3) light exposure is 50mJ/cm2~150mJ/cm2, developer solution be NaOH solution or
KOH solution, developing time 30s~90s.
Advantageous effects of the invention: the present invention is not required to the Anhua Gao Wenreya, lightsensitivity height, high resolution, heat
Stability and endurance are good, humidity resistance is good, good to each substrate adhesive force, and inorganic alkali solution can be used as developer solution,
Solve the problems, such as that polyimide resin development film loss is big, performance is poor.Alkali soluble negative photosensitive polyimide tree is prepared
Oil/fat composition, it is few by development film loss to form photocuring pattern, high resolution, thermal stability and endurance is good, humidity resistance
Well, adhesive force is good.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to this hair
It is bright to be further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
The present invention introduces photosensitive group by the Molecular Design of polyimides in strand: chalcone group,
Unsaturated double-bond in ketone carbonyl and end-capping reagent, makes it have light sensitivity；End-capping reagent is being done using 4- hydroxyl phthalic anhydride, is making main chain
End phenolic hydroxy group imports unsaturated acid anhydride after the dehydration of sub- Anhua, reacts with the phenolic hydroxyl group of main chain terminal and generates carboxyl, makes
Its negative photosensitive polyimide for forming alkali soluble, is added acrylate monomer crosslinking agent and photoinitiator, polyimides exist
When exposure, α-hydrogen friendship on 2+2 cycloaddition reaction, ketone carbonyl and diamines ortho position can occur for the chalcone group on main chain
Connection and the crosslinking of unsaturated double-bond etc., then solidification keeps cross-linking reaction more abundant afterwards.
In this application, the acrylate monomer is preferably laurel acid methacrylate, Glycidyl methacrylate
Glyceride, isobornyl (methyl) acrylate, bicyclic pentane methyl acrylate, 3- hydroxyl -2,2- dimethyl propyl -3-
Hydroxyl -2,2- dimethyl propyl ester diacrylate, tricyclic decane dimethanol dipropyl dilute acid ester, neopentylglycol diacrylate, the third oxygen
Change neopentylglycol diacrylate, ethoxylated bisphenol A diacrylate, three (2- ethoxy) isocyanuric acid triacrylates, three
Hydroxymethyl-propane three (methyl) acrylate, pentaerythritol triacrylate and ethoxyquin trimethylolpropane tris (methyl) third
One of olefin(e) acid ester or at least two mixtures that combine in any proportion.
In this application, the photoinitiator is preferably α-α-diethoxy acetophenone, 2- hydroxy-2-methyl-phenyl third
Ketone-1,1- hydroxy-cyciohexyl Benzophenone, 2- hydroxy-2-methyl-are to ethoxy ether phenylacetone-1,2- methyl-1-(4- first
Sulfenyl phenyl) -2- morpholine -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) butanone, 4- benzoyl -
4 '-methyldiphenyl thioethers, isopropyl thioxanthone anthracene, 2,4- diethyl thioxanthone and bis- [2,6- bis- fluoro- 3- (1H- pyrrole radicals -1)
Phenyl] titanium cyclopentadienyl one kind or at least two mixtures that combine in any proportion.
In this application, the organic solvent is preferably N-Methyl pyrrolidone, cyclohexanone, dimethylformamide, diformazan
One of yl acetamide and gamma-butyrolacton or at least two mixed solvents that mix in any proportion.
In this application, the surfactant is preferably dimethyl silicone polymer, polyether polyester modified organic silicon oxygen
Alkane, alkyl-modified organosiloxane or esters of acrylic acid levelling agent.
In this application, the acid value of the alkali soluble negative photosensitive polyimide copolymer is 50~150 (KOHmg/g),
Its acid value can control by adjusting the molar ratio of end-capping reagent 4- hydroxyl phthalic anhydride and unsaturated acid anhydride, to reach control development
The purpose of time and development effect.Its molecular weight can be adjusted by end-capping reagent 4- hydroxyl phthalic anhydride, preferably 5000~
Between 200000, molecular weight is too small, and properties do not reach requirement, and molecular weight is too big, then influences film effect.
The dosage of the alkali soluble negative photosensitive polyimide copolymer is 30 parts~60 parts, if being lower than 30 parts, is influenced
Film-formation result and various performances, if being higher than 60 parts, intolerant to developer solution.
The dosage of the acrylate monomer be 1.5 parts~15 parts, if be lower than 1.5 parts, be unfavorable for it is full cross-linked,
Intolerant to development, if being higher than 5 parts, developing time is lengthened, development effect is influenced.
The photoinitiator is that one kind can be in ultraviolet region (250~420nm) or at visible region (400~800nm)
The energy for absorbing certain wavelength, generates free radicals or cation etc. causes the compound of monomer polymerization crosslinking curing.Its dosage is
1 part~4 parts, in the content range, photosensitive polymer combination can be made full cross-linked under suitable light exposure, it will not
Appearance is crosslinked insufficient or photoinitiator due to photoinitiator deficiency excessively and there is a phenomenon where migrate.
The preparation method of the alkali soluble negative photosensitive polyimide resin combination is as follows: by alkali soluble negative light-sensitive
Polyimide solution, acrylate monomer and photoinitiator are dissolved in organic solvent, and surfactant is added, stirs evenly.
It is formed by photocuring pattern and is not required to the Anhua Gao Wenreya, lightsensitivity height, high resolution, thermal stability and resistance to
The property changed is good, humidity resistance is good, good to each substrate adhesive force, and inorganic alkali solution can be used as developer solution, can be used for integrating
Route multilayer wiring, the insulating layer of multichip module, chip protection film and circuit package etc..
The present invention has better photosensitivity and resolution ratio, and the high thermal stability with polyimide material, high resistance system
Number, low-k, low thermal coefficient of expansion, excellent endurance and mechanical property etc., while after overexposure, non-exposed area
It can be developed with inorganic alkali solution, can be widely used for the fields such as Aeronautics and Astronautics, electronics.
Embodiment one
Under dry nitrogen air-flow, yellow light, 10mmol is substantially soluble in 350mlN- with the fluorinated aromatic diamines of ethylmercapto group
In methyl pyrrolidone, it is slowly added to 5mmol benzophenone dianhydride under constant stirring, is stirred to react 20h in 0 DEG C, obtains with amine
Base blocks ternary oligomer A-1.
Under dry nitrogen air-flow, yellow light, the diamines by 5mmol containing spirane structure is substantially soluble in 350mlN- crassitude
In ketone, it is slowly added to the dianhydride of 10mmol main chain group containing chalcone under constant stirring, is stirred to react 20h in 0 DEG C, obtains
Ternary oligomer A-2 is blocked with acid anhydrides.
At room temperature, 9mmol polyamic acid solution A-2 is added in 10mmol polyamic acid solution A-1, is stirred in 0 DEG C
Reaction 3h is mixed, 2mmol4- hydroxyl phthalic anhydride is added, in room temperature reaction 6h, acetic anhydride 40g/ anhydrous pyridine 0.4g is added, is warming up to
50 DEG C, reaction 2h is cooled to room temperature after reaction, is poured into pure water and is precipitated, and is washed repeatedly 3 times, and 60 DEG C of vacuum drying obtain
To terminal hydroxy group light-sensitive polyimide solid PI-A.
It takes 5mmolPI-A to be dissolved in 200g N-Methyl pyrrolidone, 0.0004g p methoxy phenol is added, it is lasting to stir
Be warming up to 60 DEG C, be added with the equimolar unsaturated acid anhydride of PI-A, be continuously heating to 75~80 DEG C, monitoring system acid value works as acid
Value is between 50~150 (KOHmg/g).And when stablizing constant, stop reaction, it is cooling, obtain the negative light-sensitive polyamides with carboxyl
Imide liquor PI-B, solid content about 30%.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-B solution 50g, and 0.75g lauric acid is added
Methacrylate, 0.475g α-α-diethoxy acetophenone, 80g N-Methyl pyrrolidone and 0.08g polydimethylsiloxanes
Alkane is uniformly mixed, obtains alkali soluble negative photosensitive polyimide resin combination.
The method for forming photocuring pattern: alkali soluble negative photosensitive polyimide resin combination obtained above is used
Spin coater is applied on ITO and glass, after 120 DEG C of baking 1min, is obtained the film of 3um or so, is then given under high-pressure sodium lamp
With above-mentioned film 80mJ/cm2Light exposure, with the 40s that develops under 0.8% NaOH solution room temperature, 230 DEG C of subsequent hot plate solidifications
30min。
Embodiment two
The preparation of alkali soluble negative photosensitive polyimide resin is the same as embodiment 1.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-B solution 50g, and 3.75g methyl-prop is added
Olefin(e) acid ethylene oxidic ester, 0.685g 2- hydroxy-2-methyl-phenylacetone -1,80g cyclohexanone and 0.08g polyether polyester are modified
Organosiloxane is uniformly mixed, obtains alkali soluble negative photosensitive polyimide resin combination.Form the side of photocuring pattern
Method is the same as embodiment 1.
Embodiment three
The preparation of alkali soluble negative photosensitive polyimide resin is the same as embodiment 1.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-B solution 42g, and 3.75g isoborneol is added
Base (methyl) acrylate, 0.585g 1- hydroxy-cyciohexyl Benzophenone, 80g dimethylformamide and 0.08g is alkyl-modified has
Organic siloxane is uniformly mixed, obtains alkali soluble negative photosensitive polyimide resin combination.The method for forming photocuring pattern
With embodiment 1.
Example IV
The preparation of alkali soluble negative photosensitive polyimide resin is the same as embodiment 1.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-B solution 33g, and 0.75g bicyclic penta is added
Alkylmethacrylate, 0.455g 2- hydroxy-2-methyl-are to ethoxy ether phenylacetone -1,80g dimethyl acetamide
And 0.08g esters of acrylic acid levelling agent, it is uniformly mixed, obtains alkali soluble negative photosensitive polyimide resin combination.Form light
The method of cured pattern is the same as embodiment 1.
Embodiment five
The preparation of alkali soluble negative photosensitive polyimide resin is the same as embodiment 1.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-B solution 80g, and 4.35g 3- hydroxyl-is added
2,2- dimethyl propyl -3- hydroxyl -2,2- dimethyl propyl ester diacrylate, 0.685g 4- benzoyl -4 '-methyldiphenyl sulphur
Ether, 80g gamma-butyrolacton and 0.08g dimethyl silicone polymer are uniformly mixed, obtain alkali soluble negative photosensitive polyimide resin
Composition.The method of photocuring pattern is formed with embodiment 1.
Comparative example 1
Under dry nitrogen air-flow, yellow light, 10mmol is substantially soluble in 350mlN- with the fluorinated aromatic diamines of ethylmercapto group
In methyl pyrrolidone, it is slowly added to 5mmol benzophenone dianhydride under constant stirring, is stirred to react 20h in 0 DEG C, obtains with amine
Base end-capped with phthalic anhydride solution A -1.
Under dry nitrogen air-flow, yellow light, the diamines by 5mmol containing spirane structure is substantially soluble in 350mlN- crassitude
In ketone, it is slowly added to the dianhydride of 10mmol main chain group containing chalcone under constant stirring, is stirred to react 20h in 0 DEG C, obtains
The polyamic acid solution A-2 blocked with acid anhydrides.
At room temperature, 9mmol polyamic acid solution A-2 is added in 10mmol polyamic acid solution A-1, is stirred in 0 DEG C
Reaction 3h is mixed, 2mmol4- hydroxyl phthalic anhydride is added, reacts 6h at room temperature, acetic anhydride 40g/ anhydrous pyridine 0.4g, heating is added
To 50 DEG C, reaction 2h is cooled to room temperature after reaction, is poured into pure water and is precipitated, and is washed repeatedly 3 times, 60 degree of vacuum drying,
Obtain terminal hydroxy group light-sensitive polyimide solid PI-A.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-A solid 15g, and 0.75g lauric acid is added
Methacrylate, 0.475g α-α-diethoxy acetophenone, 80g N-Methyl pyrrolidone and 0.08g polydimethylsiloxanes
Alkane is uniformly mixed, obtains alkali soluble negative photosensitive polyimide resin combination.The method for forming photocuring pattern: will be above-mentioned
Obtained alkali soluble negative photosensitive polyimide resin combination is applied on ITO and glass with spin coater, is toasted at 120 DEG C
After 1min, the film of 3um or so is obtained, then gives above-mentioned film 80mJ/cm under high-pressure sodium lamp2Light exposure, use
Develop 40s under 0.8% NaOH solution room temperature, 230 DEG C of solidification 30min of subsequent hot plate.
Comparative example 2
The preparation of alkali soluble negative photosensitive polyimide resin is the same as comparative example 1.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-A solid 24g, and 4.35g methyl-prop is added
Olefin(e) acid ethylene oxidic ester, 0.685g 2- hydroxy-2-methyl-phenylacetone -1,80g cyclohexanone and 0.08g polyether polyester are modified
Organosiloxane is uniformly mixed, obtains alkali soluble negative photosensitive polyimide resin combination.Form the side of photocuring pattern
Method is the same as embodiment 1.
Comparative example 3
The preparation of alkali soluble negative photosensitive polyimide resin is the same as embodiment 1.
The preparation of alkali soluble negative photosensitive polyimide resin combination: taking PI-B solution 50g, and 0.36g isoborneol is added
Base (methyl) acrylate, 0.47g 1- hydroxy-cyciohexyl Benzophenone, 80g dimethylformamide and 0.08g is alkyl-modified has
Organic siloxane is uniformly mixed, obtains alkali soluble negative photosensitive polyimide resin combination.The method for forming photocuring pattern
With embodiment 1.
To 1~embodiment of embodiment 5 and 1~comparative example of comparative example 3 carry out it is following evaluate, as a result as shown in table 1.
1, the evaluation of sensitivity
By exposure region residual film ratio be development before 50% when required light exposure on the basis of degree measurement sensitivity.
2, the evaluation of resolution ratio
It is measured with the minimum dimension of the pattern film formed when sensitometry.
3, the evaluation of adhesive force
Lattice method will be drawn referring to GB/T9286-98 and evaluates its adhesive force through cured pattern film later, specific evaluation side
Method is as follows:
5B: the edge of notch is completely smooth, and grid edge does not have any peeling.
4B: having small pieces peeling in the intersection of notch, and actual spoilage is no more than 5% in the area Hua Ge.
3B: the edge and/or intersection of notch, which have, to be peeled off, and area is greater than 5%, but less than 15%.
2B: part peeling or whole large stretch of peeling and/or person's partial grid are peeled off by full wafer along notching edge.It is peeled off
Area be more than 15%, but less than 35%.
1B: the peeling/of notching edge sheet or some grids partly or entirely peel off, and area is greater than the area Hua Ge
35%, but it is no more than 65%.
0B: the area 0B that falls off is more than 1B
5B with ++ indicate, 3B~4B with+indicate, 3B or less with-indicate.
4, the evaluation of transmitance
By the pattern film of formation, using the transmitance of 400~700nm of spectrophotometric determination pattern film, transmitance is
90% or more with ++ indicate；80%~90% with+indicate；Not up to 80% survey with-indicate.
5, the evaluation of heat resistance
Through cured polyimide pattern film later, baking 1h Thickness Variation is smaller at a high temperature of 300 DEG C, heat resistance
It is better, on the contrary it is poorer.Thickness Variation 85% or more with ++ indicate；75%~85% with+indicate；Lower than 75% with-indicate.
6, the evaluation of endurance
Polyimide pattern film cured after warp is soaked in the nitration mixture of nitric acid, hydrochloric acid and phosphoric acid (45 DEG C/30min)
After take out, whether pure water is cleaned, deform, be swollen or fall off using micro- sem observation photocuring pattern, then with 3M tape pull three
It is secondary.
Photocuring pattern is soaked in 5% potassium hydroxide aqueous solution (30 DEG C/30min) to take out afterwards, pure water is cleaned, benefit
Whether deformed, be swollen or fallen off with micro- sem observation photocuring pattern, then three times with 3M tape pull.
Pattern does not change, and tape pull do not fall with ++ indicate；Pattern does not change, there is small part after tape pull
Fall glue, with+indicate；Pattern deformation is swollen or falls off, with-indicate.
7, resistance to thermochromism
After pattern film after 4 are evaluated by transmitance toasts 1h at a high temperature of 300 DEG C, measured using spectrophotometric
Determine the transmitance of 400~700nm of pattern film, transmitance variation is smaller, and resistance to thermochromism is better.Change rate below 5% with
++ indicate, change rate 5%~15% with+indicate, change rate 15% or more with-indicate.
From table 1 it follows that the alkali soluble negative photosensitive polyimide resin combination of the embodiment of the present invention 1~5,
Since end group contains unsaturated double-bond and carboxyl, sensitivity and resolution ratio all with higher, and also it is adhesive force, transmitance, heat-resisting
Property, endurance and resistance to thermochromism are all preferable.Although other performances of the composition of comparative example 1~2 are all preferable, due to
End group does not contain unsaturated double-bond and carboxyl, therefore sensitivity is very slow, and pattern can not be showed in NaOH solution, comparative example 3 by
It is very little in the acrylate monomer of addition, cause its sensitivity too slow, and other performances are also relatively poor.
The evaluation result of 1 1~embodiment of embodiment 5 of table and 1~comparative example of comparative example 3
The present invention is not required to the Anhua Gao Wenreya, lightsensitivity height, high resolution, thermal stability and endurance is good, wet-heat resisting
Property is good, good to each substrate adhesive force, and inorganic alkali solution can be used as developer solution, solves polyimide resin development
Big, performance difference problem is lost in film.Alkali soluble negative photosensitive polyimide resin combination is prepared, forms photocuring figure
Case is few by development film loss, and high resolution, thermal stability and endurance are good, humidity resistance is good, adhesive force is good.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of alkali soluble negative photosensitive polyimide resin combination, which is characterized in that including as follows according to the mass fraction
Component: 30 parts~60 parts alkali soluble negative photosensitive polyimide copolymers, 1.5 parts~15 parts acrylate monomers, 1 part~4
Part photoinitiator, 90 parts~220 parts organic solvents and 0.05 part~0.3 part surfactant；The alkali soluble negative light-sensitive
The structural formula of polyimide copolymer is as shown in Equation 1:
Wherein: x=5~80, R are the segment with carboxyl and unsaturated double-bond, wherein A1For the fluorinated aromatic diamines with ethylmercapto group
Unit, A2For benzophenone dianhydride units, A3For the dianhydride units of main chain group containing chalcone, A4For the diamine unit containing loop coil.
2. alkali soluble negative photosensitive polyimide resin combination according to claim 1, which is characterized in that the theobromine
Molten negative photosensitive polyimide copolymer contains chalcone by the fluorinated aromatic diamines with ethylmercapto group, the diamines containing loop coil, main chain
Dianhydride, benzophenone dianhydride, 4- hydroxyl phthalic anhydride and the unsaturated acid anhydride of group are copolymerized to obtain.
3. alkali soluble negative photosensitive polyimide resin combination according to claim 2, which is characterized in that the band second
The structural formula of the fluorinated aromatic diamines of sulfenyl is as shown in formula two:
Wherein: R1For
4. alkali soluble negative photosensitive polyimide resin combination according to claim 2, which is characterized in that described to contain spiral shell
The structural formula of the diamines of ring is as shown in formula three:
Wherein R2It is preferably following structure for spirane structure:
5. alkali soluble negative photosensitive polyimide resin combination according to claim 2, which is characterized in that the main chain
The structural formula of the dianhydride of the group containing chalcone is as shown in formula four:
Wherein X is (CH2)n, 2≤n >=8.
6. alkali soluble negative photosensitive polyimide resin combination according to claim 2, which is characterized in that the insatiable hunger
It is one of following with acid anhydrides:
Wherein R3、R4For H or-(CH3)n1, 1 < n1<8。
7. alkali soluble negative photosensitive polyimide resin combination according to claim 2, which is characterized in that the theobromine
The preparation method of molten negative photosensitive polyimide copolymer, includes the following steps:
A, by the fluorinated aromatic diamines with ethylmercapto group, 2:1 is placed in N-Methyl pyrrolidone in molar ratio with benzophenone dianhydride,
React the diamines of anamorphic zone imide structure；
B, by the dianhydride of diamines and the main chain group containing chalcone containing loop coil, 1:2 is placed in N-Methyl pyrrolidone in molar ratio,
React the dianhydride of anamorphic zone imide structure；
C, by the dianhydride of the diamines of step a anamorphic zone imide structure and step b anamorphic zone imide structure 1:1- in molar ratio
1.5:1 react after be added 4- hydroxyl phthalic anhydride, react anamorphic zone terminal hydroxy group photoactive polyamide acid solution；The band acyl is sub-
The molar ratio of the diamines of amine structure and the 4- hydroxyl phthalic anhydride is 5:1；
D, acetic anhydride/anhydrous pyridine is added into the photoactive polyamide acid solution with terminal hydroxy group of step c, carries out chemical imidization
After dehydration, products therefrom is placed in repeated precipitation in precipitating reagent, is filtered, washed, dries, obtains terminal hydroxy group light-sensitive polyimide；
The mass ratio of the acetic anhydride and the anhydrous pyridine is 100:1；
E, the terminal hydroxy group light-sensitive polyimide of step d is dissolved in polar solvent, unsaturated acid anhydride is added, reaction obtains alkali soluble
Negative photosensitive polyimide copolymer；The molar ratio of the unsaturated acid anhydride and the terminal hydroxy group light-sensitive polyimide is 1:1.
8. alkali soluble negative photosensitive polyimide resin combination according to claim 7, which is characterized in that the precipitating
Agent is methanol, ethyl alcohol or ultrapure water；The polar solvent is N-Methyl pyrrolidone.
9. alkali soluble negative photosensitive polyimide resin combination according to claim 1, which is characterized in that the propylene
Acid esters system monomer is laurel acid methacrylate, glycidyl methacrylate, isobornyl (methyl) acrylate, double
Pentamethylene methyl acrylate, 3- hydroxyl -2,2- dimethyl propyl -3- hydroxyl -2,2- dimethyl propyl ester diacrylate, tricyclic certain herbaceous plants with big flowers
Alkane dimethanol dipropyl dilute acid ester, neopentylglycol diacrylate, the third oxidation neopentylglycol diacrylate, ethoxylated bisphenol A bis-
Acrylate, three (2- ethoxy) isocyanuric acid triacrylates, trimethylolpropane tris (methyl) acrylate, pentaerythrite
One of triacrylate and ethoxyquin trimethylolpropane tris (methyl) acrylate or at least two groups in any proportion
The mixture of conjunction；The photoinitiator is α-α-diethoxy acetophenone, 2- hydroxy-2-methyl-phenylacetone -1,1- hydroxyl -
Phenylcyclohexyl ketone, 2- hydroxy-2-methyl-are to ethoxy ether phenylacetone-1,2- methyl-1-(4- methyl mercapto phenyl)-2-
Morpholine -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) butanone, 4- benzoyl -4 '-methyldiphenyl sulphur
Ether, isopropyl thioxanthone anthracene, 2,4- diethyl thioxanthone and the one of bis- [2,6- bis- fluoro- 3- (1H- pyrrole radicals -1) phenyl] titanium cyclopentadienyls
Kind or at least two mixtures that combine in any proportion；The organic solvent is N-Methyl pyrrolidone, cyclohexanone, dimethyl
One of formamide, dimethyl acetamide and gamma-butyrolacton or at least two mixed solvents that mix in any proportion；It is described
Surfactant is dimethyl silicone polymer, polyether polyester azo polyether polyeste, alkyl-modified organosiloxane or acrylic acid
Esters levelling agent.
10. forming pattern with the described in any item alkali soluble negative photosensitive polyimide resin combinations of claim 1-9
Method, which comprises the steps of:
1) the alkali soluble negative photosensitive polyimide resin combination is coated on substrate, forms photosensitive film layer；
2) the resulting photosensitive film layer of step 1) is formed into dry light-sensitive surface in 90 DEG C~120 DEG C progress prebake conditions 1min~5min；
3) the resulting dry light-sensitive surface of step 2) is exposed and is developed, form photocuring pattern；The light exposure is 50mJ/cm2
~150mJ/cm2, developer solution is NaOH solution or KOH solution, developing time 30s~90s；
4) solidify after carrying out the resulting photocuring pattern of step 3) in 150 DEG C~250 DEG C.
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| TWI748695B (en) * | 2020-10-20 | 2021-12-01 | 律勝科技股份有限公司 | Curable composition for inkjet, cured product and flexible printed circuit board |
| CN114106326A (en) * | 2021-12-07 | 2022-03-01 | 广东粤港澳大湾区黄埔材料研究院 | Photosensitive resin, photoresist and preparation method and application thereof |
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| CN117964897A (en) * | 2024-01-10 | 2024-05-03 | 上海八亿时空先进材料有限公司 | Alkali-soluble resin and its application |
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| CN113388107A (en) * | 2021-06-09 | 2021-09-14 | 广东工业大学 | Photosensitive polyimide resin, polyimide photocuring coating and preparation method thereof |
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| CN114957662B (en) * | 2022-06-21 | 2023-02-03 | 广东工业大学 | A low-temperature curing negative photosensitive polyimide composition and its preparation method |
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