CN117417476B - Modified polyacrylic resin, preparation method thereof and photoresist - Google Patents
Modified polyacrylic resin, preparation method thereof and photoresist Download PDFInfo
- Publication number
- CN117417476B CN117417476B CN202311749194.0A CN202311749194A CN117417476B CN 117417476 B CN117417476 B CN 117417476B CN 202311749194 A CN202311749194 A CN 202311749194A CN 117417476 B CN117417476 B CN 117417476B
- Authority
- CN
- China
- Prior art keywords
- formula
- monomer
- polyacrylic resin
- structure shown
- modified polyacrylic
- 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.)
- Active
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 105
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims description 77
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 125000006727 (C1-C6) alkenyl group Chemical group 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- MUUOUUYKIVSIAR-UHFFFAOYSA-N 2-but-3-enyloxirane Chemical compound C=CCCC1CO1 MUUOUUYKIVSIAR-UHFFFAOYSA-N 0.000 claims description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- DNPFOADIPJWGQH-UHFFFAOYSA-N octan-3-yl prop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C=C DNPFOADIPJWGQH-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- CYBBVWAMDGYJKH-UHFFFAOYSA-N pyren-1-yl 2-methylprop-2-enoate Chemical compound C1=C2C(OC(=O)C(=C)C)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 CYBBVWAMDGYJKH-UHFFFAOYSA-N 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 35
- 229920005989 resin Polymers 0.000 abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052802 copper Inorganic materials 0.000 abstract description 34
- 239000010949 copper Substances 0.000 abstract description 34
- 238000009713 electroplating Methods 0.000 abstract description 20
- 239000004743 Polypropylene Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 15
- 229920001155 polypropylene Polymers 0.000 abstract description 15
- 238000011161 development Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- 239000003513 alkali Substances 0.000 description 13
- 230000035945 sensitivity Effects 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 125000005577 anthracene group Chemical group 0.000 description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- MJYSISMEPNOHEG-UHFFFAOYSA-N anthracen-9-ylmethyl 2-methylprop-2-enoate Chemical compound C1=CC=C2C(COC(=O)C(=C)C)=C(C=CC=C3)C3=CC2=C1 MJYSISMEPNOHEG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000004026 adhesive bonding Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 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
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-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
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N propylene glycol methyl ether Substances COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Abstract
The invention relates to the technical field of photoresist, in particular to modified polyacrylic resin, a preparation method thereof and photoresist. The modified polyacrylic resin comprises a structural unit shown in a formula I, a structural unit shown in a formula II, a structural unit shown in a formula III, a structural unit shown in a formula IV and a structural unit shown in a formula V. The modified polypropylene resin can be used as film forming resin in negative electroplating mask photoresist, after development, the mask layer can present a groove pattern with small top opening and large bottom opening, so that a copper grid line with a positive trapezoid cross section can be formed in the groove through electroplating in the follow-up process, when the mask layer is removed, photoresist stripping liquid is easy to diffuse into the mask layer around the copper grid line, and photoresist stripping residue is small.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to modified polyacrylic resin, a preparation method thereof and photoresist.
Background
The method improves the photoelectric conversion efficiency of the photovoltaic cell and reduces the electricity cost of the photovoltaic cell, and is a target for development of the photovoltaic industry. As the energy conversion efficiency of the currently mainstream passive emitter back field point contact cells (PERCs) on the market approaches a limit, heterojunction technology (HJT) -based photovoltaic cells with higher photoelectric conversion efficiency, lower photoattenuation and silicon wafer usage cost gradually move to industrialization, and are expected to replace the market status of PERC cells in the next few years. Currently, one of the key technical bottlenecks that the industrialization of HJT photovoltaic cells needs to break through is electrode metallization of the cell surface. The HJT battery is easy to generate the change of the crystal form of the internal material of the battery in the high-temperature treatment process to cause the failure, and the electrode grid line on the surface of the battery is mainly manufactured by brushing low-temperature silver paste on the surface of the battery and sintering at the temperature of not higher than 250 ℃. However, low temperature silver paste is expensive and low temperature silver paste technology and supply are almost entirely held in the hands of foreign manufacturers, at any time facing outage risks. In addition, the sintering temperature of the low-temperature silver paste is low, so that macropores among silver particles in the manufactured silver electrode grid line cannot be eliminated, and the internal resistance of the electrode is increased to cause the increase of the internal power loss of the battery.
Copper electroplating technology based on photoetching patterning is a main means for realizing micropattern metallization. The metal lines obtained by low-temperature copper plating have conductivity equivalent to that of pure copper, and can obtain high metal line aspect ratio. At present, the copper grid line electrode is manufactured on the HJT battery piece by adopting the copper electroplating technology to replace the traditional silver electrode so as to achieve the desilverization of the HJT battery, and the silver removal method is considered to be the optimal scheme for achieving the aim of reducing the cost and improving the efficiency of the HJT battery.
The copper grid line is manufactured on the surface of the HJT battery by adopting an electrolytic copper plating process, which mainly comprises four basic links: (1) Introducing a copper seed layer on the surface of a transparent conductive oxide layer (TCO) of the cell; (2) Coating photoresist on the surface of the copper seed layer, and obtaining a patterned mask layer through steps of pre-baking, exposure, development and the like, wherein the position where the copper grid line needs to be formed is a hollowed-out groove on the patterned mask layer, and the position where the copper grid line does not need to be formed is completely shielded by the mask layer; (3) Immersing the battery in a copper electroplating solution, and depositing copper in the groove on the patterned mask layer by reducing copper ions in the electroplating solution to form a copper grid line; (4) And removing the mask layer and the copper seed layer which is not blocked by the copper grid line on the battery piece, and carrying out electrotinning treatment on the surface of the electrode of the copper grid line so as to prevent the electrode from oxidizing. In the four links, the patterned mask plays a leading role in controlling the size and the appearance of the final copper grid line, so that the photoresist selection for manufacturing the patterned mask is particularly important.
At present, the electroplating mask photoresist for manufacturing the copper grid line in the HJT battery field has fewer products and generally has the problem of photoresist removal residue.
Disclosure of Invention
Based on the above, the present invention provides a modified polyacrylic resin, a preparation method thereof and a photoresist to solve the above problems.
The first aspect of the invention provides a modified polyacrylic resin, which has the following technical scheme:
a modified polyacrylic resin comprising a structural unit having a formula I, a structural unit having a formula II, a structural unit having a formula III, a structural unit having a formula IV, and a structural unit having a formula V:
formula I->Formula II->Formula III->Formula IV->A formula V;
formula I is selected from formula I-1 or formula I-2:
formula I-1->Formula I-2;
wherein R is 1 Selected from C 1-6 Alkenyl, -CH 2 OR 1a or-CH 2 OC(O)R 1a ；
R 1a Selected from C 1-6 Alkenyl groups;
R 2 selected from H or C 1-3 An alkyl group;
R 3 each occurrence is independently selected from H or C 1-3 An alkyl group;
R 4 selected from C 1-3 Alkenyl groups;
R 5 selected from C 1-6 Alkyl or one of the following substituents:
；
R 6 selected from H or C 1-3 An alkyl group;
m, r, q, n and p represent the molar fractions satisfying the following conditions:
1) The ratio of m, n, p and q is 5 (0.5-2): (2-4): (0.5-2);
2) r accounts for 2% -6% of the sum of m, n, p and q.
The second aspect of the invention provides a preparation method of modified polyacrylic resin, which has the following technical scheme:
a preparation method of modified polyacrylic resin comprises the following steps:
copolymerizing monomers to obtain polyacrylic resin, wherein the monomers comprise a monomer with a structure shown in a formula ii, a monomer with a structure shown in a formula iii, a monomer with a structure shown in a formula iv and/or a monomer with a structure shown in a formula v;
reacting a compound having a structure represented by formula i-1 or i-2 with the polyacrylic resin to prepare a modified polyacrylic resin;
formula i-1->Formula i-2->Formula ii->Formula iii->Iv (iv)Formula v;
wherein R is 1 Selected from C 1-6 Alkenyl, -CH 2 OR 1a or-CH 2 OC(O)R 1a ；
R 1a Selected from C 1-6 Alkenyl groups;
R 2 selected from H or C 1-3 An alkyl group;
R 3 each occurrence is independently selected from H or C 1-3 An alkyl group;
R 4 selected from C 1-3 Alkenyl groups.
R 5 Selected from C 1-6 Alkyl or one of the following substituents:
；
R 6 selected from H or C 1-3 An alkyl group;
and satisfies the following conditions:
(1) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula iii is 5 (0.5-2);
(2) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula iv is 5 (0.5-2);
(3) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula v is 5 (2-4);
(4) The mole number of the compound having the structure shown in formula i-1 accounts for 2% -6% of the total mole number of the monomer having the structure shown in formula ii, the monomer having the structure shown in formula iii, the monomer having the structure shown in formula iv and the monomer having the structure shown in formula v;
(5) The number of moles of the compound having the structure represented by formula i-2 is 2% -6% of the total number of moles of the monomer having the structure represented by formula ii, the monomer having the structure represented by formula iii, the monomer having the structure represented by formula iv and the monomer having the structure represented by formula v.
The third aspect of the present invention provides a photoresist comprising the modified polyacrylic resin, a photoactive monomer, a photoinitiator, and a solvent.
Compared with the traditional scheme, the invention has the following beneficial effects:
according to the invention, anthracene groups with light absorption effect are introduced into the polymer, and groups with hydroxyl groups and double bonds are grafted on a part of carboxyl groups. The modified polypropylene resin can be used as a film forming resin in negative electroplating mask photoresist, the photoresist containing the film forming resin has higher light absorption performance, and when the photoresist layer is subjected to patterned exposure, the photoresist layer can show the trend of decreasing the activity of a photoinitiator from the surface of the photoresist layer to the adhesive bonding surface along the thickness direction of the photoresist layer, so that the crosslinking strength of the photoresist layer from the surface of the photoresist layer to the adhesive bonding surface along the thickness direction is gradually reduced. Since the crosslinking strength of the adhesive layer in the thickness direction is related to the alkali solubility, the following are specifically: the higher the crosslinking strength, the worse the alkali solubility, the lower the crosslinking strength, and the better the alkali solubility. After development, the mask layer can present a groove pattern with small top opening and large bottom opening, so that a copper grid line with a positive trapezoid cross section can be formed in the groove through electroplating later, when the mask layer is removed, photoresist removing liquid is easy to diffuse into the mask layer around the copper grid line, and photoresist removing residues are small; and the larger the photo-initiator activity difference of the photoresist layer along the thickness direction is, the larger the opening size difference of the top opening and the bottom opening of the formed groove is, the smaller photoresist removing residue is, and the negative photoresist containing the modified polypropylene resin can form the groove with the larger opening difference of the top opening and the bottom opening, so that the residual of the mask layer in the subsequent photoresist removing process is reduced. In addition, the minimum size of the top opening of the groove formed by the negative photoresist containing the modified polypropylene resin can reach 15 mu m, and the resolution is high. Meanwhile, the contact area between the bottom of the regular trapezoid copper grid line and the seed layer is large, so that the adhesion between the grid line and the surface of the battery piece is improved, and the problem of grid line lodging is avoided. In addition, another advantage of incorporating anthracene groups on polypropylene resins is: and is more beneficial to the dispersion of the light absorber in the photoresist system. In addition, compared with a photoresist system added with a small molecular light absorber, the photoresist formed by the polypropylene resin containing anthracene groups can avoid the problem that the small molecular light absorber dissolves out in the electroplating solution to pollute the electroplating solution. In addition, another advantage of introducing double bonds on polypropylene resins is: the double bond has photosensitivity and can participate in free radical polymerization, thereby being beneficial to improving the exposure sensitivity of the photoresist and reducing the exposure energy required by the patterning of the photoresist.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention and to more fully understand the present invention and its advantageous effects, the following brief description will be given with reference to the accompanying drawings, which are required to be used in the description of the embodiments. It is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a polyacrylic resin P01 of example 1;
FIG. 2 is an infrared spectrum of the polyacrylic resin P01 of example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the modified polypropylene resin P01m of example 1;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the polyacrylic resin P01c of comparative example 1;
FIG. 5 is an infrared spectrum of the polyacrylic resin P01c of comparative example 1;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the modified polyacrylic resin P01cm of comparative example 1;
fig. 7 is a topography under an electron microscope of a masking layer formed using a photoresist formulated with the modified polyacrylic resin of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
in the present invention, a selection range in reference to "and/or", "and/or" includes any one of two or more of the items listed in relation to each other, as well as any and all combinations of the items listed in relation to each other, including any two of the items listed in relation to each other, any more of the items listed in relation to each other, or all combinations of the items listed in relation to each other. It should be noted that when at least three items are connected by a combination of at least two conjunctions selected from the group consisting of "and/or", "and/or", it is to be understood that the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly also includes technical solutions that are all connected by "logical or". For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
In the present invention, the terms "plurality", "plural", "multiple", and the like are used in terms of the number of the terms "plurality", "multiple", and the like, and are not particularly limited, but are greater than 2 or equal to 2 in number. For example, "one or more" means one kind or two or more kinds.
In the present invention, reference to "optional", "optional" refers to the presence or absence of the "optional" or "optional" means either of the "with" or "without" side-by-side arrangements. If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the present invention, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
Aiming at the problem that photoresist residues are removed in a mask layer formed by electroplating mask photoresist for manufacturing a copper grid line in the HJT battery field, the inventor performs the following analysis: in the copper electroplating process, copper is mainly deposited in a groove formed by photoetching patterning, if the opening at the top of the groove is large and the opening at the bottom of the groove is small, the profile of a deposited copper grid line can form an inverted trapezoid, and the narrow space formed by the left and right outer sides of the inverted trapezoid and the bottom seed layer can cause difficult diffusion of photoresist removing liquid for removing a mask layer later, so that the problem of residual removing of the mask layer is caused. If the photoresist capable of manufacturing the vertical groove is selected, the beveling phenomenon at the bottom of the groove is difficult to avoid, so that the subsequent glue clamping condition is caused, and the problem of mask layer residue is also caused. Based on the above, to obtain the copper grid line electrode with functionality and convenience in construction on the surface of the HJT battery, it is necessary to ensure that the top opening of the trench formed by the patterned mask layer is small and the bottom opening is large, i.e. the cross section of the mask layer needs to be in an inverted trapezoid shape and the cross section of the copper grid line formed by the mask layer is in a positive trapezoid shape. The electroplating mask photoresist mainly comprises film forming resin, photoactive monomer, photoinitiator, solvent, pigment and filler and the like. Among them, the film-forming resin plays a decisive role in various performances of the mask layer, such as latitude, sensitivity, film-removing time, etc. Based on the above, the first aspect of the present invention provides a modified polyacrylic resin, which can be used as a film forming resin of a negative electroplating mask photoresist to solve the problem of photoresist stripping residue of a mask layer.
In some embodiments, the modified polyacrylic resin includes a structural unit having a formula I, a structural unit having a formula II, a structural unit having a formula III, a structural unit having a formula IV, and a structural unit having a formula V:
formula I->Formula II->Formula III->Formula IV->A formula V;
formula I is selected from formula I-1 or formula I-2:
formula I-1->Formula I-2;
wherein R is 1 Selected from C 1-6 Alkenyl, -CH 2 OR 1a or-CH 2 OC(O)R 1a ；
R 1a Selected from C 1-6 Alkenyl groups;
R 2 selected from H or C 1-3 An alkyl group;
R 3 each occurrence is independently selected from H or C 1-3 An alkyl group;
R 4 selected from C 1-3 Alkenyl groups;
R 5 selected from C 1-6 Alkyl or one of the following substituents:
；
R 6 selected from H or C 1-3 An alkyl group;
m, r, q, n and p represent the molar fractions satisfying the following conditions:
1) The ratio of m, n, p and q is 5 (0.5-2): (2-4): (0.5-2);
2) r accounts for 2% -6% of the sum of m, n, p and q.
In the above embodiment, anthracene groups having a light absorbing effect are introduced into the polymer, and groups having a hydroxyl group and a double bond are grafted on a part of the carboxyl groups. The modified polypropylene resin can be used as a film forming resin in negative electroplating mask photoresist, the photoresist containing the film forming resin has higher light absorption performance, and when the photoresist layer is subjected to patterned exposure, the photoresist layer can show a trend of decreasing the activity of a photoinitiator from the surface of the photoresist layer to the adhesive bonding surface along the thickness direction of the photoresist layer, so that the crosslinking strength of the photoresist layer from the surface of the photoresist layer to the adhesive bonding surface along the thickness direction is gradually reduced. Since the crosslinking strength of the adhesive layer in the thickness direction is related to the alkali solubility, the following are specifically: the higher the crosslinking strength, the worse the alkali solubility, the lower the crosslinking strength, and the better the alkali solubility. After development, the mask layer can present a groove pattern with small top opening and large bottom opening, so that a copper grid line with a positive trapezoid cross section can be formed in the groove through electroplating later, when the mask layer is removed, photoresist removing liquid is easy to diffuse into the mask layer around the copper grid line, and photoresist removing residues are small; and the larger the photo-initiator activity difference of the photoresist layer along the thickness direction is, the larger the opening size difference of the top opening and the bottom opening of the formed groove is, the smaller photoresist removing residue is, and the negative photoresist containing the modified polypropylene resin can form the groove with the larger opening difference of the top opening and the bottom opening, so that the residual of the mask layer in the subsequent photoresist removing process is reduced. In addition, the minimum size of the top opening of the groove formed by the negative photoresist containing the modified polypropylene resin can reach 15 mu m, and the resolution is high. Meanwhile, the contact area between the bottom of the regular trapezoid copper grid line and the seed layer is large, so that the adhesion between the grid line and the surface of the battery piece is improved, and the problem of grid line lodging is avoided. In addition, another advantage of incorporating anthracene groups on polypropylene resins is: and is more beneficial to the dispersion of the light absorber in the photoresist system. In addition, compared with a photoresist system added with a small molecular light absorber, the photoresist formed by the polypropylene resin containing anthracene groups can avoid the problem that the small molecular light absorber dissolves out in the electroplating solution to pollute the electroplating solution. In addition, another advantage of introducing double bonds on polypropylene resins is: the double bond has photosensitivity and can participate in free radical polymerization, thereby being beneficial to improving the exposure sensitivity of the photoresist and reducing the exposure energy required by the patterning of the photoresist.
Alternatively, R 1 One of the following substituents is selected:
。
R 1 contains double bonds which are photosensitive and can participate in free radical polymerization.
Optionally, the weight average molecular weight of the modified polyacrylic resin is 10000 g/mol-50000 g/mol.
The modified polyacrylic resin can be solid and is alkali-soluble photosensitive modified polyacrylic resin. The solubility of the modified polyacrylic resin in an alkaline solution can be controlled by adjusting the amount of ungrafted carboxyl groups in the resin.
The second aspect of the present invention provides a method for preparing a modified polyacrylic resin, by which the modified polyacrylic resin can be prepared, and in some embodiments, the method for preparing a modified polyacrylic resin includes the steps of:
copolymerizing monomers to obtain polyacrylic resin, wherein the monomers comprise a monomer with a structure shown in a formula ii, a monomer with a structure shown in a formula iii, a monomer with a structure shown in a formula iv and/or a monomer with a structure shown in a formula v;
reacting a compound having a structure represented by formula i-1 or i-2 with the polyacrylic resin to prepare a modified polyacrylic resin;
formula i-1->Formula i-2->Formula ii->Formula iii->Iv (iv)Formula v;
wherein R is 1 Selected from C 1-6 Alkenyl, -CH 2 OR 1a or-CH 2 OC(O)R 1a ；
R 1a Selected from C 1-6 Alkenyl groups;
R 2 selected from H or C 1-3 An alkyl group;
R 3 each occurrence is independently selected from H or C 1-3 An alkyl group;
R 4 selected from C 1-3 Alkenyl groups.
R 5 Selected from C 1-6 Alkyl orOne of the following substituents:
；
R 6 selected from H or C 1-3 An alkyl group;
and satisfies the following conditions:
(1) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula iii is 5 (0.5-2);
(2) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula iv is 5 (0.5-2);
(3) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula v is 5 (2-4);
(4) The mole number of the compound having the structure shown in formula i-1 accounts for 2% -6% of the total mole number of the monomer having the structure shown in formula ii, the monomer having the structure shown in formula iii, the monomer having the structure shown in formula iv and the monomer having the structure shown in formula v;
(5) The number of moles of the compound having the structure represented by formula i-2 is 2% -6% of the total number of moles of the monomer having the structure represented by formula ii, the monomer having the structure represented by formula iii, the monomer having the structure represented by formula iv and the monomer having the structure represented by formula v.
The preparation method comprises the steps of firstly preparing the polypropylene resin through monomer copolymerization, wherein the monomer comprises an anthracene group, and then grafting the epoxy micromolecule containing double bonds on hydroxyl groups to prepare the modified polyacrylic resin, and the process steps are convenient for large-scale production.
Alternatively, R 1 One of the following substituents is selected:
。
optionally, the conditions under which the monomers are copolymerized further include: mixing the monomer, the polymerization initiator and the solvent.
Alternatively, the polymerization initiator is Azobisisobutyronitrile (AIBN).
Optionally, the solvent is selected from one of diethylene glycol dimethyl ether, tetramethylene, propylene glycol methyl ether acetate, diethylene glycol monobutyl ether, and dibasic acid ester mixture.
It is understood that the monomer and the polymerization initiator may be mixed first and then the mixed solution may be added to the solvent.
Optionally, the copolymerization is carried out under nitrogen blanket.
Optionally, the reaction temperature of the copolymerization reaction is 85-95 ℃ and the reaction time is 3-6 hours.
Alternatively, the monomer having the structure shown in formula ii is selected from methacrylic acid or acrylic acid.
Alternatively, the monomer having the structure shown in formula iii is selected from 9-anthracenemethyl methacrylate.
Alternatively, the compound having the structure shown in formula i-1 is selected from allyl alcohol glycidyl ether, glycidyl acrylate, epoxybutene, 1, 2-epoxy-5-hexene, 2-methoxy-2-vinyl ethylene oxide or glycidyl methacrylate.
Alternatively, the compound having the structure represented by formula i-2 is selected from 1, 2-epoxy-4-vinylcyclohexane.
Alternatively, monomer methyl methacrylate, butyl methacrylate, hexyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, 2-oxo-2- [ (5-oxo-4-oxatricyclo [4.2.1.0 ] methacrylate having the structure shown in formula iv 3,7 ]Nonan-2-yl) oxy]Ethyl ester, 1-ethylhexyl acrylate or 1-pyrenyl methacrylate.
Alternatively, the monomer having the structure shown in formula v is selected from styrene.
Alternatively, the conditions for reacting the compound having the structure represented by formula i-1 or i-2 with the polyacrylic resin include: a catalyst is added.
Optionally, the catalyst is selected from one or more of dimethylaniline, dimethylbenzylamine and triphenylphosphine.
Alternatively, the conditions for reacting the compound having the structure represented by formula i-1 or i-2 with the polyacrylic resin include: adding polymerization inhibitor.
Optionally, the polymerization inhibitor is selected from one or more of hydroquinone, di-tert-butyl hydroquinone and p-hydroxyanisole.
Optionally, the conditions for reacting the compound having the structure represented by formula i-1 or i-2 with the polyacrylic resin further include: the reaction temperature is controlled to be 90-150 ℃ and the reaction time is controlled to be 8-13 hours.
In a third aspect, the present invention provides a photoresist, which in some embodiments comprises the modified polyacrylic resin described above, a photoactive monomer, a photoinitiator, and a solvent.
Optionally, the modified polyacrylic resin accounts for 30-50% of the photoresist by mass.
Optionally, the photoactive monomer is selected from one or more of isobornyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and trimethylolpropane triacrylate.
Optionally, the photoactive monomer accounts for 5% -20% of the photoresist by mass.
Optionally, the photoinitiator is selected from one or more of benzil dimethyl ether, 1-hydroxy-cyclohexylbenzophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylphenyl) butanone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-isopropylthioxanthone, 2-chlorothioxanthone and 2-ethylanthraquinone.
Optionally, the photoinitiator accounts for 1% -5% of the mass of the photoresist.
Optionally, the solvent is selected from one or more of diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, 2-heptanone, cyclohexanone, N-methylpyrrolidone, ethyl lactate and ethyl acetate.
Optionally, the solvent accounts for 30-50% of the photoresist by mass.
Optionally, a pigment filler is also included in the photoresist. Optionally, the pigment and filler accounts for 1% -5% of the mass of the photoresist.
Optionally, the pigment and filler is selected from one or more of titanium blue, titanium green, malachite green, and colorless crystal violet.
The following examples and comparative examples are further illustrated by the fact that the materials used, unless otherwise indicated, are commercially available and that the equipment used, unless otherwise indicated, are commercially available and that the processes involved, unless otherwise indicated, are routine selections by those skilled in the art.
Example 1
The embodiment provides a modified polyacrylic resin and a preparation method thereof, and the steps are as follows:
step 1, 45.6 g (0.53 mol) of methacrylic acid, 10.6 g (0.106 mol) of methyl methacrylate, 33.1 g (0.318 mol) of styrene, 29.3 g of 9-anthracenemethyl methacrylate (0.106 mol) and 4 g of Azobisisobutyronitrile (AIBN) were mixed and added dropwise to a 250 mL flask containing 108.6 g of diethylene glycol dimethyl ether at a temperature of 90 ℃. After the addition was complete, the reaction mixture was kept at 90 ℃ and stirred for 1.5 hours. A solution containing AIBN of 0.3 g and diethylene glycol dimethyl ether of 10 g was added to the reaction mixture, which was then heated to 95 ℃ with stirring and held for 3 hours, followed by cooling to room temperature, to obtain a solution containing polyacrylic resin P01.
P01
The nuclear magnetic resonance hydrogen spectrum characterization result of the polyacrylic resin P01 is shown in FIG. 1, the infrared spectrum characterization result is shown in FIG. 2, and the weight average molecular weight of the polyacrylic resin P01 is 20,000 g/mol.
Step 2, heating the solution containing the polyacrylic resin P01 obtained in the step 1 to 95 ℃, adding a catalyst of dimethylaniline 0.2 g, a polymerization inhibitor of di-tert-butylhydroquinone 0.2 g and glycidyl methacrylate 9.04 g (0.0636 mol), mechanically mixing for half an hour, and heating to 120 ℃ for reaction for 10 hours. Then the reaction liquid is dripped into n-heptane to obtain a precipitate, and the precipitate is filtered and air-blast dried to obtain the product, namely the modified polyacrylic resin P01m.
P01m
The nuclear magnetic resonance hydrogen spectrum of the modified polyacrylic resin P01m is shown in FIG. 3, and the weight average molecular weight of the modified polyacrylic resin P01m is 21,000 g/mol.
Example 2
This example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 1, except that the amount of glycidyl methacrylate added was 6.03. 6.03 g (0.0424 mol), and the weight-average molecular weight of the resulting modified polyacrylic resin was 21,000 g/mol.
Example 3
This example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 1, except that glycidyl methacrylate was added in an amount of 3.01. 3.01 g (0.0212 mol), and the weight-average molecular weight of the resulting modified polyacrylic resin was 20,500 g/mol.
Example 4
This example provides a modified polyacrylic resin and a method for producing the same, substantially as in example 1, except that the amount of methyl methacrylate-9-anthracene-methyl ester added was 43.936 g (0.159 mol), and the weight-average molecular weight of the resulting modified polyacrylic resin was 23,000 g/mol.
Example 5
This example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 1, except that hydroxyethyl methacrylate of 13.8 g (0.106 mol) is used instead of methyl methacrylate of 10.6 g (0.106 mol), and the weight average molecular weight of the resulting modified polyacrylic resin is 21,000 g/mol.
Comparative example 1
This comparative example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 1, with the main difference that 9-anthracenemethyl methacrylate is not added, and the steps are as follows:
step 1, 45.6 g (0.53 mol) of methacrylic acid, 10.6 g (0.106 mol) of methyl methacrylate, 33.1 g of styrene (0.318 mol) and 4 g of Azobisisobutyronitrile (AIBN) were mixed and added dropwise to a 250 mL flask containing 108.6 g of diethylene glycol dimethyl ether at a temperature of 90 ℃. After the addition was complete, the reaction mixture was stirred at 90 ℃ for 1.5 hours. A solution of 0.3 g AIBN in 10 g of diglyme was added to the reaction mixture, then heated to 95 ℃ for 3 hours with stirring, and then cooled to room temperature, obtaining a solution containing polyacrylic resin P01 c.
P01c
The polyacrylic resin P01c was subjected to nuclear magnetic resonance hydrogen spectrum characterization, the results are shown in FIG. 4, the results are shown in FIG. 5, and the weight average molecular weight of the polyacrylic resin P01c is 21,000 g/mol.
And 2, heating the solution containing the polyacrylic resin P01c obtained in the step 1 to 95 ℃, adding a catalyst of dimethylaniline 0.2 g, a polymerization inhibitor of di-tert-butylhydroquinone 0.2 g and glycidyl methacrylate 9.04 g (0.0636 mol), heating to 120 ℃ after half an hour, and reacting 10 h. Then the reaction liquid is dripped into n-heptane to obtain a precipitate, and the precipitate is filtered and air-blown to be dried, thus obtaining the product, namely the modified polyacrylic resin P01cm.
P01cm
The modified polyacrylic resin P01cm was characterized by nuclear magnetic resonance hydrogen spectrum, and the result is shown in FIG. 6, wherein the weight average molecular weight of the modified polyacrylic resin P01cm is 22,000 g/mol.
Comparative example 2
This comparative example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 2, except that 9-anthracenemethyl methacrylate is not added, and the weight average molecular weight of the obtained modified polyacrylic resin is 22,000 g/mol.
Comparative example 3
This comparative example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 3, except that 9-anthracenemethyl methacrylate is not added, and the weight average molecular weight of the obtained modified polyacrylic resin is 22,000 g/mol.
Comparative example 4
This example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 1, except that methacrylic acid-9-anthracenemethyl ester was added in an amount of 8.787 g (0.0318 mol), and the weight-average molecular weight of the resulting modified polyacrylic resin was 21,000 g/mol.
Comparative example 5
This comparative example provides a modified polyacrylic resin and a method for producing the same, substantially as in example 1, with the main difference that the addition amount 73.227 g (0.265 mol) of 9-anthracenemethyl methacrylate was found to be 26,000 g/mol in weight-average molecular weight of the resulting modified polyacrylic resin.
Comparative example 6
This comparative example provides a modified polyacrylic resin and a method for producing the same, which are substantially the same as in example 1, with the main difference that glycidyl methacrylate is added in an amount of 1.51. 1.51 g (0.0106 mol). The weight average molecular weight of the resulting modified polyacrylic resin was 21,000 g/mol.
Comparative example 7
This comparative example provides a modified polyacrylic resin and a method for producing the same, substantially as in example 1, with the main difference that the added amount of glycidyl methacrylate was 12.06. 12.06 g (0.0848 mol), and the weight average molecular weight of the resulting modified polyacrylic resin was 23,000 g/mol.
The modified polyacrylic resins of the above examples and comparative examples were used as film-forming resins, and 40% of film-forming resin, 10% of isobornyl acrylate, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone 5%, 40% of diethylene glycol dimethyl ether as solvent and 5% of phthalocyanine blue were mixed in the following mass percentages to prepare photoresists.
The alkali solubility, exposure sensitivity, and pattern morphology of the modified polyacrylic resins of examples and comparative examples and photoresists prepared from the modified polyacrylic resins were evaluated by the following methods. The specific method comprises the following steps:
(1) Alkali solubility evaluation of modified polyacrylic resin
The modified polyacrylic resins prepared in examples and comparative examples were mixed with propylene glycol methyl ether acetate, respectively, to prepare mixed solutions. And coating the mixed solution on the surface of a silicon wafer by using a spin coater, and baking at the temperature of 75 ℃ for 10min to remove the volatile solvent, thereby obtaining the photoresist film. The thickness of the photoresist film is controlled within the range of 13-17 mu m, and the thickness of the film is measured by a film thickness meter and is recorded as delta. Immersing the adhesive film in 1wt% of Na 2 CO 3 In the aqueous solution, the time t required for the film to dissolve completely was recorded. The alkali dissolution rate of the modified polyacrylic resin is calculated as shown in formula 1:
[ formula 1 ]
。
The alkali solubility of the modified polyacrylic resins of the above examples and comparative examples can be evaluated according to the following grades:
i: the alkali dissolution rate is above 1000A/s;
II: the alkali dissolution rate is more than 500A/s and less than 1000A/s;
III: the alkali dissolution rate is below 500A/s.
(2) Evaluation of sensitivity to exposure of photoresists formulated from modified polyacrylic resins
The modified polyacrylic resins prepared in examples and comparative examples were formulatedThe photoresist was coated on a silicon wafer using a screen printing method, and air-drying was performed at 75 ℃ for 10min to remove volatile solvents, thereby obtaining a photoresist film. The photoresist film thickness was measured using a film thickness meter. The result is recorded as delta 1 . Then, the photoresist layer is subjected to exposure treatment under different exposure energies. Subsequently, 1wt% Na was used 2 CO 3 The aqueous solution was subjected to spray development of the exposed film for 60 seconds. And then the deionized water is used for washing and drying the silicon wafer. The thickness of the residual photoresist film layer on the silicon wafer was measured by a film thickness meter, and the obtained result was recorded as delta 2 . The thickness change rate (i.e., film retention rate) of the photoresist film after exposure development is calculated as shown in formula 2:
[ formula 2 ]
。
And drawing an exposure energy vs. film retention rate curve (namely a contrast curve of the photoresist) of the photoresist according to the measured result. And carrying out normalized film thickness treatment on the drawn contrast curve of the photoresist, and drawing a tangent line aiming at a region with linear change in the contrast curve, wherein the exposure energy of the photoresist corresponding to the intersection point of the tangent line and an area curve extension line with the film retention rate close to 100% and kept constant in the contrast curve is the exposure sensitivity of the photoresist.
The above exposure sensitivity of the photoresists formulated of the modified polyacrylic resins prepared in examples and comparative examples can be evaluated according to the following grades:
a: the exposure sensitivity range is below 5 mJ;
b: the exposure sensitivity range is below 10mJ and above 5 mJ;
c: the exposure sensitivity range is more than 10 mJ.
(3) Photoetching pattern morphology evaluation method for photoresist prepared from modified polyacrylic resin
Photolithography prepared from the modified polyacrylic resins prepared in examples and comparative examples above was performed using a screen printing methodThe photoresist was coated on a silicon wafer and air-dried at 75 deg.c for 10min to remove volatile solvents, thereby obtaining a photoresist film. Then, using a mask plate with a line pattern, exposing the photoresist film under the condition that the exposure energy is less than 15 mJ. Thereafter 1wt% Na was used 2 CO 3 The aqueous solution was subjected to spray development of the exposed film for 60 seconds. And then the deionized water is used for washing and drying the silicon wafer, so as to obtain the photoresist pattern with the groove pattern.
The width of the narrowest trench formed in the photoresist pattern was measured using an optical microscope and recorded as the resolution of the photoresist. And observing the profile of the photoresist pattern lines by using a field emission scanning electron microscope. The morphology of the photoresist was evaluated according to the following scale:
o: the resolution of the photoresist is less than or equal to 15 mu m, and the profile of the line formed by the photoresist presents an inverted trapezoid shape.
Delta: the resolution of the photoresist is more than 15 mu m, but the lines formed by the photoresist have an inverted trapezoid shape, or the resolution of the photoresist is less than or equal to 15 mu m, but the line profile formed by the photoresist cannot have the inverted trapezoid shape
X: resolution of the photoresist is greater than 15 μm and line profile formed by the photoresist cannot show inverted trapezoid shape
Note that: the line profile shows an inverted trapezoid shape, namely, the top opening of the trench of the mask layer is small, and the bottom opening is large, see fig. 7. A copper grid line with a positive trapezoid cross section can be formed in the groove through electroplating.
The results of the above tests are shown in Table 1
TABLE 1
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (11)
1. A modified polyacrylic resin, comprising a structural unit represented by formula I, a structural unit represented by formula II, a structural unit represented by formula III, a structural unit represented by formula IV, and a structural unit represented by formula V:
；
formula I is selected from formula I-1 or formula I-2:
；
wherein R is 1 Selected from C 1-6 Alkenyl, -CH 2 OR 1a or-CH 2 OC(O)R 1a ；
R 1a Selected from C 1-6 Alkenyl groups;
R 2 selected from H or C 1-3 An alkyl group;
R 3 each occurrence is independently selected from H or C 1-3 An alkyl group;
R 4 selected from C 1-3 Alkenyl groups;
R 5 selected from C 1-6 Alkyl or one of the following substituents:
；
R 6 selected from H or C 1-3 Alkyl group；
m, r, q, n and p represent the molar fractions satisfying the following conditions:
1) The ratio of m, n, p and q is 5 (0.5-2): (2-4): (0.5-2);
2) r accounts for 2% -6% of the sum of m, n, p and q.
2. The modified polyacrylic resin of claim 1, wherein R 1 One of the following substituents is selected:
。
3. the modified polyacrylic resin according to claim 1 or 2, wherein the modified polyacrylic resin has a weight average molecular weight of 10000g/mol to 50000g/mol.
4. The preparation method of the modified polyacrylic resin is characterized by comprising the following steps:
copolymerizing monomers to obtain polyacrylic resin, wherein the monomers comprise a monomer with a structure shown in a formula ii, a monomer with a structure shown in a formula iii, a monomer with a structure shown in a formula iv and a monomer with a structure shown in a formula v;
reacting a compound having a structure represented by formula i-1 or i-2 with the polyacrylic resin to prepare a modified polyacrylic resin;
；
wherein R is 1 Selected from C 1-6 Alkenyl, -CH 2 OR 1a or-CH 2 OC(O)R 1a ；
R 1a Selected from C 1-6 Alkenyl groups;
R 2 selected from H or C 1-3 An alkyl group;
R 3 each occurrence is independently selected from HOr C 1-3 An alkyl group;
R 4 selected from C 1-3 Alkenyl groups;
R 5 selected from C 1-6 Alkyl or one of the following substituents:
；
R 6 selected from H or C 1-3 An alkyl group;
and satisfies the following conditions:
(1) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula iii is 5 (0.5-2);
(2) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula iv is 5 (0.5-2);
(3) The molar ratio of the monomer with the structure shown in the formula ii to the monomer with the structure shown in the formula v is 5 (2-4);
(4) The mole number of the compound having the structure shown in formula i-1 accounts for 2% -6% of the total mole number of the monomer having the structure shown in formula ii, the monomer having the structure shown in formula iii, the monomer having the structure shown in formula iv and the monomer having the structure shown in formula v;
(5) The number of moles of the compound having the structure represented by formula i-2 is 2% -6% of the total number of moles of the monomer having the structure represented by formula ii, the monomer having the structure represented by formula iii, the monomer having the structure represented by formula iv and the monomer having the structure represented by formula v.
5. The method for producing a modified polyacrylic resin according to claim 4, wherein the monomer having the structure represented by formula ii is selected from methacrylic acid and acrylic acid.
6. The method for producing a modified polyacrylic resin according to claim 4, wherein the compound having a structure represented by formula i-1 is selected from allyl alcohol glycidyl ether, glycidyl acrylate, epoxybutene, 1, 2-epoxy-5-hexene, 2-methoxy-2-vinyl ethylene oxide or glycidyl methacrylate.
7. The method for producing a modified polyacrylic resin according to claim 4, wherein the compound having a structure represented by formula i-2 is selected from 1, 2-epoxy-4-vinylcyclohexane.
8. The method for producing a modified polyacrylic resin according to claim 4, wherein the monomer having the structure represented by formula iv is selected from the group consisting of methyl methacrylate, butyl methacrylate, hexyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, 2-oxo-2- [ (5-oxo-4-oxatricyclo [ 4.2.1.0) 3,7 ]Nonan-2-yl) oxy]Ethyl ester, 1-ethylhexyl acrylate or 1-pyrenyl methacrylate.
9. The method for producing a modified polyacrylic resin according to any one of claims 4 to 8, wherein the conditions under which the compound having the structure represented by formula i-1 or i-2 is reacted with the polyacrylic resin include: a catalyst is added.
10. The method for producing a modified polyacrylic resin according to claim 9, wherein the catalyst is one or more selected from the group consisting of dimethylaniline, dimethylbenzylamine and triphenylphosphine.
11. A photoresist comprising the modified polyacrylic resin of any one of claims 1 to 3, a photoactive monomer, a photoinitiator, and a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311749194.0A CN117417476B (en) | 2023-12-19 | 2023-12-19 | Modified polyacrylic resin, preparation method thereof and photoresist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311749194.0A CN117417476B (en) | 2023-12-19 | 2023-12-19 | Modified polyacrylic resin, preparation method thereof and photoresist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117417476A CN117417476A (en) | 2024-01-19 |
| CN117417476B true CN117417476B (en) | 2024-03-26 |
Family
ID=89532958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311749194.0A Active CN117417476B (en) | 2023-12-19 | 2023-12-19 | Modified polyacrylic resin, preparation method thereof and photoresist |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117417476B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1376450A (en) * | 1970-12-26 | 1974-12-04 | Asahi Chemical Ind | Photopolymerizable compositions and elements containing them |
| CN1239557A (en) * | 1997-10-08 | 1999-12-22 | 克拉瑞特国际有限公司 | Antireflection or light-absorbing coating compsn. and polymer therefor |
| CN1847274A (en) * | 2006-04-19 | 2006-10-18 | 苏州华飞微电子材料有限公司 | Filming copolymer resin containing silicon coupler and its organic antiflecting coating |
| JP2012198408A (en) * | 2011-03-22 | 2012-10-18 | Fujifilm Corp | Colored radiation-sensitive composition, formation method of pattern, color filter and manufacturing method of color filter, and solid state image sensor |
| CN103733134A (en) * | 2011-08-10 | 2014-04-16 | 国际商业机器公司 | Developable bottom antireflective coating compositions for negative resists |
| JP2015063623A (en) * | 2013-09-25 | 2015-04-09 | 東レ・ファインケミカル株式会社 | (meth)acrylic acid-based copolymer, negative photosensitive resin composition, and cured product of the same |
| CN114957532A (en) * | 2022-05-26 | 2022-08-30 | 广东粤港澳大湾区黄埔材料研究院 | Polymer resin for electron beam photoresist and preparation method thereof |
| CN116355126A (en) * | 2022-12-26 | 2023-06-30 | 广东粤港澳大湾区黄埔材料研究院 | Electron beam photoresist film-forming resin, and preparation method and application thereof |
| CN116400565A (en) * | 2023-04-10 | 2023-07-07 | 广东粤港澳大湾区黄埔材料研究院 | Photoresist composition, application and anti-reflection photoresist layer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101285641B1 (en) * | 2005-08-25 | 2013-07-12 | 닛산 가가쿠 고교 가부시키 가이샤 | Lithographic coated-type underlayer film forming composition containing vinylnaphthalene resin derivative |
| KR100712999B1 (en) * | 2006-03-29 | 2007-05-02 | 주식회사 하이닉스반도체 | Organic anti-reflective coating polymer, organic anti-reflective coating composition comprising it and photoresist pattern forming method using it |
| JP6454324B2 (en) * | 2013-04-03 | 2019-01-16 | ブルーワー サイエンス アイ エヌ シー． | High etch resistant polymer blocks used in block copolymers for induced self-assembly |
| US11192971B2 (en) * | 2019-03-11 | 2021-12-07 | Toshiba Memory Corporation | Pattern forming material, composition for pattern formation, pattern forming method and method of manufacturing semiconductor device |
-
2023
- 2023-12-19 CN CN202311749194.0A patent/CN117417476B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1376450A (en) * | 1970-12-26 | 1974-12-04 | Asahi Chemical Ind | Photopolymerizable compositions and elements containing them |
| CN1239557A (en) * | 1997-10-08 | 1999-12-22 | 克拉瑞特国际有限公司 | Antireflection or light-absorbing coating compsn. and polymer therefor |
| CN1847274A (en) * | 2006-04-19 | 2006-10-18 | 苏州华飞微电子材料有限公司 | Filming copolymer resin containing silicon coupler and its organic antiflecting coating |
| JP2012198408A (en) * | 2011-03-22 | 2012-10-18 | Fujifilm Corp | Colored radiation-sensitive composition, formation method of pattern, color filter and manufacturing method of color filter, and solid state image sensor |
| CN103733134A (en) * | 2011-08-10 | 2014-04-16 | 国际商业机器公司 | Developable bottom antireflective coating compositions for negative resists |
| JP2015063623A (en) * | 2013-09-25 | 2015-04-09 | 東レ・ファインケミカル株式会社 | (meth)acrylic acid-based copolymer, negative photosensitive resin composition, and cured product of the same |
| CN114957532A (en) * | 2022-05-26 | 2022-08-30 | 广东粤港澳大湾区黄埔材料研究院 | Polymer resin for electron beam photoresist and preparation method thereof |
| CN116355126A (en) * | 2022-12-26 | 2023-06-30 | 广东粤港澳大湾区黄埔材料研究院 | Electron beam photoresist film-forming resin, and preparation method and application thereof |
| CN116400565A (en) * | 2023-04-10 | 2023-07-07 | 广东粤港澳大湾区黄埔材料研究院 | Photoresist composition, application and anti-reflection photoresist layer |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis of a Photo-Patternable Cross-linked Epoxy System Containing Photodegradable Carbonate Units for Deep UV Lithography";Geun Huh等;《Journal of Applied Polymer Science》;20090701;第114卷;第2093-2100页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117417476A (en) | 2024-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102169994B (en) | Negative electrode base member | |
| CN101051186B (en) | Negative photosensitive resin composition | |
| CN108628101A (en) | Electron beam lithography glue composition and preparation method | |
| CN104614940B (en) | A kind of photosensitive polymer combination and its application | |
| JP2010153362A (en) | Photosensitive conductive paste, electrode formed using it, plasma display panel, and method for manufacturing photosensitive conductive paste | |
| CN111100237A (en) | High-refractive-index alkaline water soluble resin, preparation method and high-refractive-index photoresist | |
| JP2017027029A (en) | Coloring photosensitive composition | |
| CN117417476B (en) | Modified polyacrylic resin, preparation method thereof and photoresist | |
| CN102214497B (en) | Conductive paste and conductive pattern | |
| CN111983892A (en) | Photoinduction anti-oxygen polymerization inhibition femtosecond laser photoresist and preparation method thereof | |
| US8221958B2 (en) | Photosensitive paste and sintered layer | |
| CN115141304B (en) | High-refraction film-forming resin containing triphenylmethyl ester structure and photoresist composition | |
| JP3474724B2 (en) | Cyanoethyl group-containing graft polymer | |
| KR20170031854A (en) | Photo-curable resin composition | |
| CN115494697A (en) | Chemically amplified photoresist and preparation and use method thereof | |
| JP5515466B2 (en) | Electron emission source paste, electron emission source and electron emission device using the same | |
| CN101750886A (en) | Photosensitive resin composite and preparation method of color optical filter | |
| CN101759371B (en) | Glass powder with surface modification, electric conduction slurry containing glass powder and surface modification method | |
| CN111040093B (en) | Photosensitive resin and preparation method and application thereof | |
| JP2018129292A (en) | Black photosensitive resin composition, organic light-emitting element derived therefrom, quantum dot light-emitting element, and display device | |
| JP4338819B2 (en) | Photosensitive resin laminate | |
| CN109960109B (en) | Dispersing agent, photosensitive resin composition and application of dispersing agent and photosensitive resin composition | |
| JP2006278221A (en) | Photosensitive black paste for all together calcination, and manufacturing method of pdp front substrate using this paste | |
| CN116224716A (en) | Photoresist for preparing HJT solar cell copper grid and preparation method thereof | |
| CN112578632A (en) | Photosensitive resin composition and photoresist |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |