CN116819891A - Alkali-soluble resin polymer, preparation method thereof and positive photosensitive resin composition - Google Patents
Alkali-soluble resin polymer, preparation method thereof and positive photosensitive resin composition Download PDFInfo
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- CN116819891A CN116819891A CN202310970950.6A CN202310970950A CN116819891A CN 116819891 A CN116819891 A CN 116819891A CN 202310970950 A CN202310970950 A CN 202310970950A CN 116819891 A CN116819891 A CN 116819891A
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- China
- Prior art keywords
- alkali
- soluble resin
- resin polymer
- unsubstituted
- substituted
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 74
- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000004185 ester group Chemical group 0.000 claims abstract description 9
- 125000003368 amide group Chemical group 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 239000000178 monomer Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 26
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 22
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- -1 dihydroxymethyl Chemical group 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- NDMUQNOYNAWAAL-UHFFFAOYSA-N 3-diazo-1,4-dioxonaphthalene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C(=[N+]=[N-])C(S(=O)(=O)O)C(=O)C2=C1 NDMUQNOYNAWAAL-UHFFFAOYSA-N 0.000 claims description 5
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- BEVCCTWDTKAVFR-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 BEVCCTWDTKAVFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 125000002541 furyl group Chemical group 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- JOOOXGGAHUBKTL-UHFFFAOYSA-N 2,6-bis(hydroxymethyl)-4-propan-2-ylphenol Chemical compound CC(C)C1=CC(CO)=C(O)C(CO)=C1 JOOOXGGAHUBKTL-UHFFFAOYSA-N 0.000 description 6
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- XZSZONUJSGDIFI-UHFFFAOYSA-N n-(4-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(O)C=C1 XZSZONUJSGDIFI-UHFFFAOYSA-N 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229940075579 propyl gallate Drugs 0.000 description 4
- 235000010388 propyl gallate Nutrition 0.000 description 4
- 239000000473 propyl gallate Substances 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- FVXCTHJRLASLPG-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)carbamoylamino]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(=O)NC1=CC=C(O)C=C1 FVXCTHJRLASLPG-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- XGQJGMGAMHFMAO-UHFFFAOYSA-N 1,3,4,6-tetrakis(methoxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound COCN1C(=O)N(COC)C2C1N(COC)C(=O)N2COC XGQJGMGAMHFMAO-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- XPLBWKKMTXCTDB-UHFFFAOYSA-N 4-(2-ethyl-5-propan-2-ylphenyl)phenol Chemical compound CCC1=CC=C(C(C)C)C=C1C1=CC=C(O)C=C1 XPLBWKKMTXCTDB-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NUVBSKCKDOMJSU-UHFFFAOYSA-N para-hydroxybenzoic acid ethyl ester Natural products CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QQIKUPYICPQFRN-UHFFFAOYSA-N (2-hydroxy-5-methylphenyl)methanediol Chemical compound CC1=CC=C(O)C(C(O)O)=C1 QQIKUPYICPQFRN-UHFFFAOYSA-N 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- GSOXNLLPTMSRCO-UHFFFAOYSA-N 1,2-dichloro-3,4-diphenylbenzene Chemical compound C=1C=CC=CC=1C1=C(Cl)C(Cl)=CC=C1C1=CC=CC=C1 GSOXNLLPTMSRCO-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- KUMMBDBTERQYCG-UHFFFAOYSA-N 2,6-bis(hydroxymethyl)-4-methylphenol Chemical compound CC1=CC(CO)=C(O)C(CO)=C1 KUMMBDBTERQYCG-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- YNGIFMKMDRDNBQ-UHFFFAOYSA-N 3-ethenylphenol Chemical compound OC1=CC=CC(C=C)=C1 YNGIFMKMDRDNBQ-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 1
- OWTGALWHQDVEKQ-UHFFFAOYSA-N 4-cyclohexyl-2,6-bis(hydroxymethyl)phenol Chemical compound OCC1=C(O)C(CO)=CC(C2CCCCC2)=C1 OWTGALWHQDVEKQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- KOBUWXYJPUFJEW-UHFFFAOYSA-N OC1=C(COC)C=C(S(=O)(=O)C2=CC(=C(C(=C2)COC)O)COC)C=C1COC Chemical compound OC1=C(COC)C=C(S(=O)(=O)C2=CC(=C(C(=C2)COC)O)COC)C=C1COC KOBUWXYJPUFJEW-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VAVZHSBOROHMQD-UHFFFAOYSA-N n-(3-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=CC(O)=C1 VAVZHSBOROHMQD-UHFFFAOYSA-N 0.000 description 1
- PMHOLXNNEPPFNZ-UHFFFAOYSA-N n-(3-hydroxyphenyl)prop-2-enamide Chemical compound OC1=CC=CC(NC(=O)C=C)=C1 PMHOLXNNEPPFNZ-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- POVITWJTUUJBNK-UHFFFAOYSA-N n-(4-hydroxyphenyl)prop-2-enamide Chemical compound OC1=CC=C(NC(=O)C=C)C=C1 POVITWJTUUJBNK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Abstract
The application belongs to the technical field of photosensitive resin compositions, and particularly discloses an alkali-soluble resin polymer which comprises a first repeating unit shown in a formula I and a second repeating unit shown in a formula II,
Description
Technical Field
The application relates to the technical field of photosensitive resin compositions, in particular to an alkali-soluble resin polymer, a preparation method thereof and a positive photosensitive resin composition.
Background
With the demands for higher performance, miniaturization, and weight reduction of electronic devices, higher integration of semiconductor components is advancing, and higher density and higher definition of semiconductor elements, semiconductor packages, printed wiring boards, and the like constituting the semiconductor components are advancing. As a surface protective film or an interlayer insulating film for a semiconductor device, the comprehensive properties thereof are being continuously updated, for example, a low curing temperature is achieved, and at the same time, high photosensitivity, high resolution, excellent heat resistance, good tensile properties and the like can be maintained.
In the existing positive resin composition, if the acid sensitive groups are adopted to improve the solubility difference before and after exposure to improve the contrast of the pattern, the small molecules decomposed by the acid sensitive structure can influence the mechanical strength after curing. The method adopts the mixed use of the resin with larger molecular weight and the resin with smaller molecular weight to improve the dissolution rate during development and improve the pattern morphology after development, but the addition of the resin with smaller molecular weight can further reduce the thermal stability of film formation, and the original performance can not be maintained after high-temperature treatment, so that the heat resistance after curing can be influenced.
Disclosure of Invention
The present application has for its object to overcome the above-mentioned drawbacks of the prior art by providing a novel alkali-soluble resin polymer, a process for producing the same, and a positive photosensitive resin composition.
To achieve the above and other related objects, the present application provides the following technical solutions.
In a first aspect, the present application provides an alkali-soluble resin polymer comprising a first repeating unit represented by formula I and a second repeating unit represented by formula II,
the R1 is selected from a hydrogen atom, a substituted or unsubstituted C1-C16 hydrocarbon group, a substituted or unsubstituted C1-C16 alkoxy group and a substituted or unsubstituted C1-C16 ester group;
the R2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C16 unsaturated bond-containing ester group, a substituted or unsubstituted C1-C16 unsaturated bond-containing amide group and a substituted or unsubstituted C1-C16 unsaturated bond-containing ureido group;
the X is selected from a substituted or unsubstituted C1-C24 ester ring and a substituted or unsubstituted C6-C25 aryl;
the Y is selected from substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C5-C25 furyl;
said n 1 、n 2 、n 3 And n 4 Each independently selected from integers from 1 to 3, and 2+.n1+n2+.4, 2+.n3+n4+.4.
Preferably, R1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, wherein R 'and R' are each independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl.
Further, the R2 is selected from at least one of the following structural formulas:
the Rb is 1 、Rb 2 And Rb 3 Independently selected from hydrogen atom and C1-C6 alkyl, a is selected from integer of 1-6.
Further, the R2 is selected from at least one of the following structures:
further, at least one of the following technical characteristics is also included:
a1 The molar ratio of hydroxyl groups to ring functional groups in the alkali-soluble resin polymer is 0.7-2.0; preferably, the ratio is 0.8-1.5;
a2 The alkali-soluble resin polymer has a weight average molecular weight of 5000 to 30000; preferably, the weight average molecular weight is 5000 to 30000, more preferably 7000 to 25000;
a3 X) is selected from one of the following structures:
the RX1 is selected from one of a connecting bond, -CH2-, -CO-, -O-, -SO2, -C (CH 3) 2-and C (CF 3) 2-;
preferably, the X is selected from one of the following structures:
a5 Y is selected from one of the following structures:
the RY1, RY2 and RY3 are respectively and independently selected from C1-C16 alkyl and C1-C16 alkoxy;
the RY4 and RY5 are independently selected from hydrogen atom, C1-C16 alkyl and C6-C25 aryl, RY4 and RY5 can form a C4-C16 ring;
the RY6, RY7 and RY8 are independently selected from hydrogen atoms, C1-C16 alkyl groups and C1-C16 alkoxy groups.
Preferably, Y is selected from one of the following structures:
the RY6, RY7 and RY8 are each independently selected from C1-C5 alkyl groups.
The second aspect of the present application provides a method for preparing an alkali-soluble polymer, comprising the steps of: adding a monomer shown in a formula I-1, a monomer shown in a formula II-1, a compound monomer containing an X group structure, a catalyst and a reaction solvent into a reactor, and polymerizing at 80-150 ℃; then adding a compound monomer containing a Y group structure, polymerizing at 80-150 ℃, and purifying to prepare the alkali-soluble resin polymer; the reactor can be a reaction bottle connected with a fractionating tower and a distillation device.
The R1 is selected from a hydrogen atom, a substituted or unsubstituted C1-C16 hydrocarbon group, a substituted or unsubstituted C1-C16 alkoxy group and a substituted or unsubstituted C1-C16 ester group; the R2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C16 unsaturated bond-containing hydrocarbon group, a substituted or unsubstituted C1-C16 unsaturated bond-containing amide group and a substituted or unsubstituted C1-C16 unsaturated bond-containing ureido group;
wherein the compound monomer containing the X group structure is a monomer containing diether, dihydroxymethyl or halogenated alkyl structure derived from X or a monomer containing polyunsaturated bonds derived from X;
the compound monomer containing the Y group structure is a diether or dimethylol structure monomer derived from Y or an aldehyde structure monomer derived from Y.
Preferably, the monomer shown in the formula I-1 is at least one selected from methylphenol, dimethylphenol, resorcinol, phloroglucinol, pyrogallic acid, propyl gallate and cardanol.
Preferably, the monomer of formula II-1 is selected from at least one of 4-hydroxystyrene, 3-hydroxystyrene, 2- (N '- (4-hydroxyphenyl) ureido) ethyl methacrylate, 2- (N' - (3-hydroxyphenyl) ureido) ethyl acrylate, N- (4-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylate, N- (4-hydroxyphenyl) acrylate, N- (3-hydroxyphenyl) methacrylate, N- (3-hydroxyphenyl) acrylate, 2- (methacryloyloxy) ethyl 4-hydroxybenzoate, 2- (acryloyloxy) ethyl 4-hydroxybenzoate, 2- (methacryloyloxy) ethyl 3-hydroxybenzoate, and 2- (acryloyloxy) ethyl 3-hydroxybenzoate.
The monomer containing diether, dihydroxymethyl or halogenated alkyl structure derived from X is at least one selected from 4,4 '-di (methoxymethyl) diphenyl ether, diphenyl dimethyl ether, paraxylylene dimethyl ether, 4' -di (hydroxymethyl) diphenyl ether, paraxylylene alcohol, diphenyl paradimethanol, diphenyl dichlorobenzene and paradichlorobenzene.
The polyunsaturated monomer derived from X is dicyclopentadiene.
The diether or dimethylol structure derived from Y is at least one selected from the group consisting of 2, 6-bis (methoxymethyl) hydroxymethyl-4-methylphenol, 2, 6-bis (methoxymethyl) hydroxymethyl-4-isopropylphenol, 2, 6-bis (methoxymethyl) hydroxymethyl-4-tert-butylphenol, 2, 6-bis (methoxymethyl) hydroxymethyl-4-tert-amylphenol, 2, 6-bis (methoxymethyl) hydroxymethyl-4-cyclopentylphenol, 2, 6-bis hydroxymethyl-4-cyclohexylphenol, 2, 6-bis (methoxymethyl) hydroxymethyl-4-cyclohexylphenol and the like.
The monomer of aldehyde group structure derived from Y is selected from at least one of furfural, salicylaldehyde and anisaldehyde.
Further, at least one of the following technical features is also included:
b1 The catalyst is at least one selected from p-toluenesulfonic acid, hydrochloric acid, oxalic acid and dilute sulfuric acid;
b2 The reaction solvent is at least one selected from gamma-butyrolactone, diethylene glycol monomethyl ether and dimethyl sulfoxide, and the reaction solvents are proton or aprotic polar solvents with boiling points higher than 150 ℃.
b3 When the product is prepared as a solid, the purification steps include washing, precipitation and filtration; when the product is prepared as a solution, the purification step includes extraction, distillation.
The third aspect of the present application provides a positive photosensitive resin composition comprising the above alkali-soluble polymer.
Further, photoacid generator, thermal crosslinking agent, silane coupling agent and organic solvent are included.
Further, the composition comprises the following components in parts by mass:
preferably, the composition comprises the following components in parts by mass:
further, at least one of the following technical characteristics is also included:
c1 The photoacid generator is a phenolic diazonaphthoquinone sulfonate, preferably, the phenolic diazonaphthoquinone sulfonate is an ester of polyhydroxy aromatic compound and diazonaphthoquinone sulfonyl chloride.
Preferably, the polyhydroxy aromatic compound is selected from the group consisting of alpha, alpha '-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1-tris (4-hydroxyphenyl) ethane and 2,3, 4' -tetrahydroxybenzophenone, bisphenol A, bisphenol AF, 4', at least one of 4' -methylenetriphenol, 1, 2-tetrakis (4-hydroxyphenyl) ethane, and mixtures thereof;
the diazonaphthoquinone sulfonyl chloride is selected from 2,1, 5-diazonaphthoquinone sulfonyl chloride or 2,1, 4-diazonaphthoquinone sulfonyl chloride.
Further preferably, the phenolic diazonaphthoquinone sulfonate is at least one selected from the group consisting of an ester of α, α, α '-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene with 2,1, 5-diazonaphthoquinone sulfonyl chloride, an ester of 1, 1-tris (4-hydroxyphenyl) ethane with 2,1, 5-diazonaphthoquinone sulfonyl chloride, and an ester of 2,3, 4' -tetrahydroxybenzophenone with 2,1, 5-diazonaphthoquinone sulfonyl chloride.
c2 The thermal crosslinking agent is selected from the following two conditions: firstly, the compound contains hydroxymethyl or alkyl oxygen active groups, and secondly, the compound contains urea, melamine or phenolic frameworks.
Preferably, the thermal crosslinking agent is selected from at least one of the following structures:
c3 The silane coupling agent is at least one selected from alkoxy silane coupling agents containing epoxy groups, ureido groups, secondary amines, tertiary amines, amides or mercapto groups;
preferably, the silane coupling agent is at least one selected from 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane.
c4 The organic solvent is at least one selected from gamma-butyrolactone, dimethyl sulfoxide, propylene glycol monomethyl ether acetate and ethyl lactate;
compared with the prior art, the application has the beneficial effects that:
the alkali-soluble resin polymer contains unsaturated bond ester groups, unsaturated bond amide groups and unsaturated bond urea groups, has heating reactivity, and is beneficial to improving the performance of the resin after solidification; the molar ratio of hydroxyl to the ring functional group in the alkali-soluble resin polymer is 0.5-2.0, so that a better alkali dissolution rate can be obtained, a pattern with high contrast is obtained, when the ratio is more than 0.5, the phenolic hydroxyl can react with the developing solution in a sufficient amount to provide a better alkali dissolution performance, and when the ratio is less than 2.0, the polymer shows a certain hydrophobicity, and a better developing and film-retaining rate can be obtained.
The preparation method of the alkali-soluble resin can not only obtain the resin with higher weight average molecular weight, but also avoid the gel phenomenon in the reaction process, and the product has higher yield which is more than or equal to 85%;
the photosensitive resin composition containing the alkali-soluble resin polymer can be cured at a temperature ranging from 170 ℃ to 200 ℃ to obtain a cured film with a film thickness of 1 to 20um, and the cured film has a high resolution pattern, a glass transition temperature and a tensile strength.
Detailed Description
Unless otherwise indicated, implied from the context, or common denominator in the art, all parts and percentages in the present application are based on weight and the test and characterization methods used are synchronized with the filing date of the present application. Where applicable, the disclosure of any patent, patent application, or publication referred to in this disclosure is incorporated herein by reference in its entirety, and the equivalent patents are incorporated herein by reference, especially with respect to the definitions of synthetic techniques, product and process designs, polymers, comonomers, initiators or catalysts, etc. in the art, as disclosed in these documents. If the definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present application, the definition of the term provided in the present application controls.
The numerical ranges in the present application are approximations, so that it may include the numerical values outside the range unless otherwise indicated. The numerical range includes all values from the lower value to the upper value that increase by 1 unit, provided that there is a spacing of at least 2 units between any lower value and any higher value. For example, if a component, physical or other property (e.g., molecular weight, melt index, etc.) is recited as being 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing values less than 1 or containing fractions greater than 1 (e.g., 1.1,1.5, etc.), then 1 unit is suitably considered to be 0.0001,0.001,0.01, or 0.1. For a range including units less than 10 (e.g., 1 to 5), 1 unit is generally considered to be 0.1 these are merely specific examples of what is intended to be expressed, and all possible combinations of values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this disclosure. The numerical ranges within the present application provide, inter alia, the calcium-containing filler content, the stirring temperature, and various features and properties of these components.
As used with respect to chemical compounds, the singular includes all isomeric forms and vice versa unless explicitly stated otherwise (e.g., "hexane" includes all isomers of hexane, either individually or collectively). In addition, unless explicitly stated otherwise, the use of the terms "a," "an," or "the" include plural referents.
The terms "comprises," "comprising," "including," and their derivatives do not exclude the presence of any other component, step or process, and are not related to whether or not such other component, step or process is disclosed in the present application. For the avoidance of any doubt, all use of the terms "comprising", "including" or "having" herein, unless expressly stated otherwise, may include any additional additive, adjuvant or compound. Rather, the term "consisting essentially of … …" excludes any other component, step or process from the scope of any of the terms recited below, except as necessary for operability. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. The term "or" refers to the listed individual members or any combination thereof unless explicitly stated otherwise.
Examples
The following will describe embodiments of the present application in detail, and the embodiments and specific operation procedures are given by implementing the present application on the premise of its technical solution, but the scope of protection of the present application is not limited to the following embodiments.
The measurement methods in examples and comparative examples are as follows:
resolution measuring method
The method comprises the steps of forming a photosensitive film with a specific film thickness on a 4-inch silicon wafer by using a spin coating method, adjusting the rotating speed, baking the photosensitive film on a contact hot plate at 120 ℃ for 4 minutes, performing pattern exposure by using an ultraviolet mercury lamp exposure machine with the power of 200W, performing incremental exposure every 10mJ according to the exposure quantity, developing the wafer in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, and confirming the minimum pattern size which can be obtained as a resolution judgment. Resolution is less than or equal to 5um, and is excellent; resolution is greater than 5um but less than or equal to 10um, good; resolution is greater than 10um, poor.
Method for measuring glass transition temperature
The resin composition was cast on a glass plate to form a film, which was then cured in an oven at a constant temperature of 80℃for 1 hour at a heating rate of 5℃per minute from a temperature of 200℃and maintained for 1 hour, and then cooled to room temperature at 5℃per minute, and the glass plate was immersed in deionized water at 80℃for 30 minutes to release the film, and dried in the oven at 150℃for 30 minutes to obtain a cured film having a film thickness of 10. Mu.m. The cured film was partially taken and placed in a thermo-mechanical analyzer (TMA) and analyzed at a temperature rise rate of 5 ℃/min to obtain a glass transition temperature (Tg). Tg is more than or equal to 200 ℃, and is excellent; tg is less than 200 ℃ but equal to or greater than 170 ℃; tg is less than 170℃poor.
Method for measuring tensile strength
The tensile bars were cut from the cured film obtained in the above step, and after being left to stand at 23℃for 12 hours or more in an environment of 50% relative humidity, the tensile strength was measured by using a universal tensile tester. Tensile strength is more than or equal to 120MPa, and is excellent; tensile strength is less than 120MPa but more than or equal to 90MPa, and good; the tensile strength is less than 90MPa, and the difference is small.
The following are the various components used in the examples and comparative examples
1. Alkali-soluble resin Polymer A
Synthesis of alkali-soluble resin Polymer A1
Resorcinol (44.04 g,0.4 mol), 4' -bis (methoxymethyl) diphenyl ether (51.66 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (96 g) were charged into a four-necked flask connected to a fractionating column and a distillation apparatus, and the mixture was distilled into a flask 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-bis-hydroxymethyl-4-isopropyl phenol (19.63 g,0.1 mol) and diethylene glycol monomethyl ether (173 g) are prepared into a solution, the solution is added into a reaction system, stirring is continued for 3 hours at 80-150 ℃, tetrahydrofuran (192 g) is added after cooling to room temperature, stirring is carried out for 30 minutes, washing and precipitating are carried out in deionized water, filtering is carried out, drying is carried out at 50 ℃ in a vacuum oven, solid powder is obtained, the alkali-soluble resin polymer A1 has the mass of 89g, the yield is 90%, the weight average molecular weight is 8800, and the molar ratio of hydroxyl groups to cyclic groups is 1.0.
Synthesis of alkali-soluble resin Polymer A2
Propyl gallate (63.66 g,0.3 mol), N- (4-hydroxyphenyl) methacrylamide (17.72 g,0.1 mol), 4' -bis (methoxymethyl) diphenyl ether (51.66 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (133 g) and N were placed in a four-necked flask connected to a fractionating column and a distillation apparatus 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-Dihydroxymethyl-4-isopropylphenol (19.63 g,0.1 mol) and diethylene glycol monomethyl ether (233 g) were formulated as a solutionAdding the solution into a reaction system, continuously stirring for 3 hours at 80-150 ℃ for reaction, cooling to room temperature, adding tetrahydrofuran (254 g) and stirring for 30 minutes, washing in deionized water, precipitating, filtering, drying in a vacuum oven at 50 ℃ to obtain solid powder, wherein the mass of the alkali-soluble resin polymer A2 is 106g, the yield is 89%, the weight average molecular weight is 8600, and the molar ratio of hydroxyl groups to cyclic groups is 1.2.
Synthesis of alkali-soluble resin Polymer A3
Propyl gallate (63.66 g,0.3 mol) N- (4-hydroxyphenyl) methacrylamide (17.72 g,0.1 mol), 4' -bis (methoxymethyl) diphenyl ether (51.66 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (133 g) were charged into a four-necked flask connected to a fractionating column and a distillation apparatus, and the mixture was distilled into N 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-bis (methoxymethyl) -4-isopropyl phenol (22.43 g,0.1 mol) and diethylene glycol monomethyl ether (230 g) are prepared into a solution, the solution is added into a reaction system, stirring is continued for 3 hours at 80-150 ℃, tetrahydrofuran (259 g) is added after cooling to room temperature and stirring is carried out for 30 minutes, washing and precipitating are carried out in deionized water, filtering is carried out, and drying is carried out at 50 ℃ in a vacuum oven to obtain solid powder, wherein the alkali-soluble resin polymer A3 has the mass of 112g, the yield is 92%, the weight average molecular weight is 11000, and the molar ratio of hydroxyl groups to cyclic groups is 1.2.
Synthesis of alkali-soluble resin Polymer A4
Propyl gallate (63.66 g,0.3 mol), 2- (N '- (4-hydroxyphenyl) ureido) ethyl methacrylate (26.43 g,0.1 mol), 4' -bis (methoxymethyl) diphenyl ether (51.66 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (142 g) were charged into a four-necked flask connected to a fractionating column and a distillation apparatus, and the mixture was distilled into a flask 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-bis-hydroxymethyl-4-isopropyl phenol (19.63 g,0.1 mol) and diethylene glycol monomethyl ether (235 g) are prepared into a solution, the solution is added into a reaction system, stirring is continued for 3 hours at 80-150 ℃ for reaction, tetrahydrofuran (269 g) is added after cooling to room temperature, stirring is carried out for 30 minutes, washing and precipitation are carried out in deionized water, filtering is carried out, and vacuum drying is carried outDrying at 50℃in a box to obtain a solid powder, the alkali-soluble resin polymer A4 was 110g in mass, 93% in yield, and the molar ratio of the hydroxyl group to the cyclic group was 1.2 in weight average molecular weight of 9500.
Synthesis of alkali-soluble resin Polymer A5
Into a four-necked flask connected to a fractionating column and a distillation apparatus, pyrogallic acid (37.83 g,0.3 mol), 2- (N '- (4-hydroxyphenyl) ureido) ethyl methacrylate (26.43 g,0.1 mol), 4' -bis (methoxymethyl) diphenyl ether (51.66 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (116 g), and a catalyst system for the distillation of the same were introduced 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-bis-hydroxymethyl-4-isopropyl phenol (19.63 g,0.1 mol) and diethylene glycol monomethyl ether (200 g) are prepared into a solution, the solution is added into a reaction system, the reaction is continuously carried out at 80-150 ℃ for 3 hours, tetrahydrofuran (226 g) is added after the temperature is reduced to room temperature, the solution is stirred for 30 minutes, the solution is washed in deionized water, filtered after precipitation, and dried at 50 ℃ in a vacuum oven to obtain solid powder, the alkali-soluble resin polymer A5 has the mass of 85g, the yield is 92%, the weight average molecular weight Mw is 9300, and the molar ratio of hydroxyl groups to cyclic groups is 1.2.
Synthesis of alkali-soluble resin Polymer A6
Into a four-necked flask connected to a fractionating column and a distillation apparatus, pyrogallic acid (37.83 g,0.3 mol), N- (4-hydroxyphenyl) methacrylamide (17.72 g,0.1 mol), biphenyldimethyl ether (48.46 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (104 g), and N 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-bis-hydroxymethyl-4-isopropyl phenol (19.63 g,0.1 mol) and diethylene glycol monomethyl ether (184 g) are prepared into a solution, the solution is added into a reaction system, the reaction is continuously carried out at 80-150 ℃ for 3 hours, and finally, after cooling to room temperature, 206g of tetrahydrofuran is added, the solution is stirred for 30 minutes, the solution is washed in deionized water, filtered after precipitation, and dried in a vacuum oven at 50 ℃ to obtain solid powder, alkali-soluble resin polymer A6, the mass is 83g, the yield is 93%, the weight average molecular weight is 7800, and the molar ratio of hydroxyl groups to cyclic groups is 1.2.
Synthesis of alkali-soluble resin Polymer A7
Resorcinol (44.04 g,0.4 mol), dicyclopentadiene (26.44 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (70 g) and N were charged into a four-necked flask connected to a fractionating column and a distillation apparatus 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-bis-hydroxymethyl-4-isopropyl phenol (19.63 g,0.1 mol) and diethylene glycol monomethyl ether (140 g) are prepared into a solution, the solution is added into a reaction system, stirring is continued for 3 hours at 80-150 ℃, after cooling to room temperature, 150g of tetrahydrofuran is added, stirring is carried out for 30 minutes, washing and precipitation are carried out in deionized water, filtering is carried out, drying is carried out at 50 ℃ in a vacuum oven, solid powder is obtained, the alkali-soluble resin polymer A7 has a mass of 67g, the yield is 91%, the weight average molecular weight is 13200, and the molar ratio of hydroxyl groups to cyclic groups is 1.3.
Synthesis of alkali-soluble resin Polymer A8
Resorcinol (44.04 g,0.4 mol), diphenyl dimethyl ether (48.46 g,0.2 mol), p-toluenesulfonic acid (2 g), diethylene glycol monomethyl ether (70 g) were charged into a four-necked flask connected to a fractionating column and a distillation apparatus, and the mixture was distilled into a flask having a four-necked flask 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; 2, 6-bis (hydroxymethyl) -4-methylphenol (16.82 g,0.1 mol) and diethylene glycol monomethyl ether (163 g) are prepared into a solution, the solution is added into a reaction system, the reaction is continuously carried out at 80-150 ℃ for 3 hours, tetrahydrofuran (182 g) is added after the temperature is reduced to room temperature, the solution is stirred for 30 minutes, the solution is washed in deionized water, filtered after precipitation, and dried at 50 ℃ in a vacuum oven to obtain solid powder, alkali-soluble resin polymer A8 with the mass of 81g, the yield of 87% and the weight average molecular weight of 9800, and the molar ratio of hydroxyl groups to cyclic groups of 1.0.
Synthesis of alkali-soluble resin Polymer A9
Resorcinol (44.04 g,0.4 mol), paraxylylenediamine (7.63 g,0.055 mol), paratoluenesulfonic acid (2 g), diethylene glycol monomethyl ether (52 g) were charged into a four-necked flask connected to a fractionating column and a distillation apparatus, and N was a mixture of 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; will be2, 6-bis-hydroxymethyl-4-methylphenol (16.82 g,0.1 mol) and diethylene glycol monomethyl ether (108 g) are prepared into a solution, the solution is added into a reaction system, the reaction is continuously carried out at 80-150 ℃ for 3 hours, finally tetrahydrofuran (114 g) is added after the temperature is reduced to room temperature, the solution is stirred for 30 minutes, the solution is washed in deionized water, filtered after precipitation, and dried at 50 ℃ in a vacuum oven to obtain solid powder, alkali-soluble resin polymer A9, the mass is 81g, the yield is 90%, the weight average molecular weight is 7600, and the molar ratio of hydroxyl groups to cyclic groups is 1.3.
Synthesis of alkali-soluble resin Polymer A10
Resorcinol (44.04 g,0.4 mol), paraxylylenediamine (7.63 g,0.055 mol), paratoluenesulfonic acid (2 g), diethylene glycol monomethyl ether (52 g) were charged into a four-necked flask connected to a fractionating column and a distillation apparatus, and N was a mixture of 2 Heating to 50 ℃ under the protection of atmosphere, stirring until the solid is completely dissolved, and stirring and reacting for 3 hours at 80-150 ℃; furfural (9.61 g,0.1 mol) and diethylene glycol monomethyl ether (91 g) are prepared into a solution, the solution is added into a reaction system, stirring is continued for 3 hours at 80-150 ℃ for reaction, finally, 102g of tetrahydrofuran is added after cooling to room temperature, stirring is carried out for 30 minutes, washing and precipitating are carried out in deionized water, filtering is carried out, drying is carried out in a vacuum oven at 50 ℃ to obtain solid powder, the alkali-soluble resin polymer A10 has the mass of 73g, the yield is 88%, the weight average molecular weight is 9200, and the molar ratio of hydroxyl groups to cyclic groups is 1.1.
Synthesis of alkali-soluble resin Polymer A11
M-cresol (32.4 g,0.3 mol), p-cresol (21.6 g,0.2 mol), paraformaldehyde (10.5 g) and salicylaldehyde (12.2 g,0.1 mol) are dissolved in propylene glycol monomethyl ether (300 g), oxalic acid (10 g) is added, the mixture is stirred and reacted for 8 to 12 hours at 80 to 100 ℃, the mixture is washed and precipitated in a precipitator configured by water and methanol 1:1, the precipitate is filtered, and the solid powder is obtained by drying in a vacuum oven at 50 ℃ and the alkali-soluble resin polymer A11 has the mass of 68.9g, the weight average molecular weight of 8500 and the molar ratio of hydroxyl groups to cyclic groups of 1.0.
2. Synthesis of photoacid generator B
Photoacid generator B1
6.76g of 2,1, 5-diazonaphthoquinone sulfonyl chloride, 42.45 g of ALPHA, ALPHA' -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene are dissolved in 150g of dioxane, 20g of triethylamine is added, the mixture is reacted for 12 to 24 hours at the temperature of-20 to 50 ℃, and 39.29g of yellow solid B1 is obtained after filtration, precipitation in a precipitator prepared by water and methanol 1:1 and drying.
Photoacid generator B2
5.41g of 2,1, 5-diazonaphthoquinone sulfonyl chloride, 30.64g of 1, 1-tris (4-hydroxyphenyl) ethane are dissolved in 150g of dioxane, 16g of triethylamine is added, the mixture is reacted for 12 to 24 hours at a temperature of between-20 and 50 ℃, and the mixture is filtered, precipitated in a precipitator prepared by water and methanol in a 1:1 ratio and dried to obtain 28.18 yellow solid B2.
Photoacid generator B3
8.12g of 2,1, 4-diazonaphthoquinone sulfonyl chloride and 24.62g of 2,3, 4' -tetrahydroxybenzophenone are dissolved in 150g of dioxane, 24g of triethylamine is added, the mixture is reacted for 12 to 24 hours at the temperature of between 20 ℃ below zero and 50 ℃, and 21.37g of yellow solid B3 is obtained after filtration, precipitation in a precipitator prepared by water and methanol in a 1:1 ratio and drying.
3. Thermal crosslinking agent:
thermal crosslinking agent C1: tetramethoxymethyl glycoluril
Thermal crosslinking agent C2:3,3', 5' -Tetramethoxymethyl Biphenyl alcohol
Thermal crosslinking agent C3: bis [3, 5-bis (methoxymethyl) -4-hydroxyphenyl ] sulfone
4. Coupling agent
3- (2, 3-epoxypropoxy) propyl trimethoxysilane (KH 560)
5. Solvent(s)
Gamma-butyrolactone
Example 1
The above alkali-soluble resin polymer A1 (100 parts by mass), photoacid generator B1 (20 parts by mass), thermal crosslinking agent C1 (tetramethoxymethyl glycoluril, 10 parts by mass) and silane coupling agent KH560 (2 parts by mass) were dissolved in γ -butyl lactone (185 parts by mass), to prepare a positive photosensitive resin composition, and the resolution of the cured pattern and the glass transition temperature and tensile strength of the cured film were evaluated. The evaluation results are shown in Table 1.
Example 2
The difference from example 1 is that the thermal crosslinking agent C1 was changed to the thermal crosslinking agent C2, and the evaluation results are shown in Table 1.
Example 3
The difference from example 1 is that the thermal crosslinking agent C1 was changed to the thermal crosslinking agent C3, and the evaluation results are shown in Table 1.
Example 4
The difference from example 1 is that photoacid generator B1 was changed to photoacid generator B2, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 5
The difference from example 1 is that photoacid generator B1 was changed to photoacid generator B3, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 6
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A2, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 7
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A3, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 8
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A4, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 9
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A5, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 10
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A6, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 11
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A7, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 12
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A8, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 13
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer A9, and the rest was unchanged, and the evaluation results are shown in table 1.
Example 14
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer a10, and the rest was unchanged, and the evaluation results are shown in table 1.
Comparative example 1
The difference compared with example 1 is that the thermal crosslinking agent C1 was not included, the rest was unchanged, and the evaluation results are shown in Table 1.
Comparative example 2
The difference compared with example 6 is that the thermal crosslinking agent C1 was not included, the rest was unchanged, and the evaluation results are shown in Table 1.
Comparative example 3
The difference compared with example 9 is that the thermal crosslinking agent C1 was not included, the rest was unchanged, and the evaluation results are shown in Table 1.
Comparative example 4
The difference from example 1 is that the alkali-soluble resin polymer A1 was changed to the alkali-soluble resin polymer a11, and the rest was unchanged, and the evaluation results are shown in table 1.
Resolution of the cured patterns of examples 1 to 14 and comparative examples 1 to 4 described above, and glass transition temperature and tensile strength of the cured films.
TABLE 1
| Sequence number | Resin composition | Component B | Component C | Resolution ratio | Tg | Tensile Strength |
| Example 1 | A1 | B1 20 parts of | C1 10 parts of | Excellent (excellent) | Good grade (good) | Excellent (excellent) |
| Example 2 | A1 | B1 20 parts of | C2，10 parts of | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Example 3 | A1 | B1 20 parts of | C3 10 parts of | Good grade (good) | Excellent (excellent) | Excellent (excellent) |
| Example 4 | A1 | B2 20 parts of | C1 10 parts of | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Example 5 | A1 | B3 20 parts of | C1 10 parts of | Good grade (good) | Excellent (excellent) | Excellent (excellent) |
| Example 6 | A2 | B1 20 parts of | C1 10 parts of | Good grade (good) | Excellent (excellent) | Excellent (excellent) |
| Example 7 | A3 | B1 20 parts of | C1 10 parts of | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Example 8 | A4 | B1 20 parts of | C1 10 parts of | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Example 9 | A5 | B1 20 parts of | C1 10 parts of | Excellent (excellent) | Excellent (excellent) | Excellent (excellent) |
| Example 10 | A6 | B1 20 parts of | C1 10 parts of | Good grade (good) | Excellent (excellent) | Excellent (excellent) |
| Example 11 | A7 | B1 20 parts of | C1 10 parts of | Excellent (excellent) | Good grade (good) | Excellent (excellent) |
| Example 12 | A8 | B1 20 parts of | C1 10 parts of | Good grade (good) | Good grade (good) | Excellent (excellent) |
| Example 13 | A9 | B1 20 parts of | C1 10 parts of | Excellent (excellent) | Good grade (good) | Good grade (good) |
| Example 14 | A10 | B1 20 parts of | C1 10 parts of | Excellent (excellent) | Good grade (good) | Good grade (good) |
| Comparative example 1 | A1 | B1 20 parts of | - | Good grade (good) | Difference of difference | Difference of difference |
| Comparative example 2 | A2 | B1 20 parts of | - | Good grade (good) | Good grade (good) | Good grade (good) |
| Comparative example 3 | A5 | B1 20 parts of | - | Good grade (good) | Good grade (good) | Good grade (good) |
| Comparative example 4 | A11 | B1 20 parts of | C1 10 parts of | Good grade (good) | Good grade (good) | Good grade (good) |
As is clear from Table 1, examples 1 to 14 and comparative examples 1 to 4, the alkali-soluble resin polymer synthesized according to the present application was used in combination with a thermal crosslinking agent in a positive photosensitive resin composition, and the resulting cured pattern was excellent in resolution, glass transition temperature and tensile strength. Wherein, compared with the examples 1, 6 and 9, the comparative examples 1-3 lack thermal crosslinking agents, and the mechanical properties after curing are obviously inferior; comparative example 4 in comparison with example 1, the resolution, glass transition temperature, tensile strength properties were inferior with the same formulation composition in order to use the conventional resin monomer structure and synthesis process.
The positive photosensitive resin composition can be cured at 170-200 ℃ to obtain a cured film with a film thickness of 1-20 um, and the cured film is processed to form a film with high resolution patterns and good glass transition temperature and tensile strength, and can be used for metal insulation layers, surface protection layers, stress buffer layers and the like of semiconductor elements, packaging substrates, printed circuit boards and display panels.
Claims (10)
1. An alkali-soluble resin polymer comprising a first repeating unit represented by formula I and a second repeating unit represented by formula II,
the R1 is selected from a hydrogen atom, a substituted or unsubstituted C1-C16 hydrocarbon group, a substituted or unsubstituted C1-C16 alkoxy group and a substituted or unsubstituted C1-C16 ester group;
the R2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C16 unsaturated bond-containing ester group, a substituted or unsubstituted C1-C16 unsaturated bond-containing amide group and a substituted or unsubstituted C1-C16 unsaturated bond-containing ureido group;
the X is selected from a substituted or unsubstituted C1-C24 ester ring and a substituted or unsubstituted C6-C25 aryl;
the Y is selected from substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C5-C25 furyl.
Said n 1 、n 2 、n 3 And n 4 Each independently selected from integers of 1 to 3, and 2.ltoreq.n 1 +n 2 ≦4，2≦n 3 +n 4 ≦4。
2. The alkali-soluble resin polymer according to claim 1, wherein R2 is selected from at least one of the following structural formulas:
the Rb1, rb2 and Rb3 are respectively and independently selected from hydrogen atoms and C1-C6 alkyl groups, and a is selected from integers of 1-6.
3. The alkali-soluble resin polymer according to claim 2, wherein R2 is selected from at least one of the following structures:
4. the alkali-soluble resin polymer according to any one of claims 1 to 3, further comprising at least one of the following technical features:
a1 The molar ratio of hydroxyl groups to ring functional groups in the alkali-soluble resin polymer is 0.7-2.0;
a2 The alkali-soluble resin polymer has a weight average molecular weight of 5000 to 30000;
a3 X) is selected from one of the following structures:
the RX1 is selected from the group consisting of a bond, -CH 2 -、-CO-、-O-、-SO 2 、--C(CH 3 ) 2 -and C (CF) 3 ) 2 -one of the following;
a4 Y is selected from one of the following structures:
the RY1, RY2 and RY3 are respectively and independently selected from C1-C16 alkyl and C1-C16 alkoxy;
the RY4 and RY5 are respectively and independently selected from hydrogen atoms, C1-C16 alkyl groups and C6-C25 aryl groups, and the RY4 and the RY5 can form a C4-C16 ring;
the RY6, RY7 and RY8 are independently selected from hydrogen atoms, C1-C16 alkyl groups and C1-C16 alkoxy groups.
5. A method for producing the alkali-soluble resin polymer as claimed in any one of claims 1 to 4, comprising the steps of: adding a monomer shown in a formula I-1, a monomer shown in a formula II-1, a compound monomer containing an X group structure, a catalyst and a reaction solvent into a reactor, and polymerizing at 80-150 ℃; then adding a compound monomer containing a Y group structure, polymerizing at 80-150 ℃, and purifying to prepare the alkali-soluble resin polymer;
wherein the compound monomer containing the X group structure is a monomer containing diether, dihydroxymethyl or halogenated alkyl structure derived from X or a monomer containing polyunsaturated bonds derived from X;
the compound monomer containing the Y group structure is a diether or dimethylol structure monomer derived from Y or an aldehyde structure monomer derived from Y.
6. The method for producing an alkali-soluble resin polymer as claimed in claim 5, further comprising at least one of the following technical features:
b1 The catalyst is at least one selected from p-toluenesulfonic acid, hydrochloric acid, oxalic acid and dilute sulfuric acid;
b2 The reaction solvent is at least one selected from gamma-butyrolactone, diethylene glycol monomethyl ether and dimethyl sulfoxide;
b3 When the product is prepared as a solid, the purification steps include washing, precipitation and filtration; when the product is prepared as a solution, the purification step includes extraction, distillation.
7. A positive photosensitive resin composition comprising the alkali-soluble polymer according to any one of claims 1 to 4.
8. The positive-type photosensitive resin composition according to claim 7, further comprising a photoacid generator, a thermal crosslinking agent, a silane coupling agent and an organic solvent.
9. The positive photosensitive resin composition according to claim 8, wherein the positive photosensitive resin composition comprises the following components in parts by mass:
10. the positive-working photosensitive resin composition according to claim 8 or 9, further comprising at least one of the following technical features:
c1 The photoacid generator is phenolic diazonaphthoquinone sulfonate; preferably, the phenolic diazonaphthoquinone sulfonate is an ester of polyhydroxy aromatic compound and diazonaphthoquinone sulfonyl chloride;
c2 The thermal crosslinking agent is selected from the following two conditions: the compound contains hydroxymethyl or alkyl oxygen active groups, and the compound contains urea, melamine or phenol skeletons;
c3 The silane coupling agent is at least one selected from alkoxy silane coupling agents containing epoxy groups, ureido groups, secondary amines, tertiary amines, amides or mercapto groups;
c4 The organic solvent is at least one selected from gamma-butyrolactone, dimethyl sulfoxide, propylene glycol monomethyl ether acetate and ethyl lactate.
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