CN114524841B - Multifunctional monomer compound, preparation method thereof and photosensitive resin composition - Google Patents
Multifunctional monomer compound, preparation method thereof and photosensitive resin composition Download PDFInfo
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- CN114524841B CN114524841B CN202210147555.3A CN202210147555A CN114524841B CN 114524841 B CN114524841 B CN 114524841B CN 202210147555 A CN202210147555 A CN 202210147555A CN 114524841 B CN114524841 B CN 114524841B
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- 239000000178 monomer Substances 0.000 title claims abstract description 89
- 150000001875 compounds Chemical class 0.000 title claims abstract description 86
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title description 5
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- -1 n-octyl group Chemical group 0.000 claims description 21
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 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 claims description 8
- ODRZRTPUCSZPMS-UHFFFAOYSA-N [hydroxy(2-methylprop-2-enoyloxymethoxy)phosphoryl]oxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCOP(O)(=O)OCOC(=O)C(C)=C ODRZRTPUCSZPMS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 4
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- LOCXTTRLSIDGPS-FVDSYPCUSA-N [(z)-[1-oxo-1-(4-phenylsulfanylphenyl)octan-2-ylidene]amino] benzoate Chemical compound C=1C=C(SC=2C=CC=CC=2)C=CC=1C(=O)C(/CCCCCC)=N\OC(=O)C1=CC=CC=C1 LOCXTTRLSIDGPS-FVDSYPCUSA-N 0.000 claims description 2
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N ethylene glycol diacrylate Substances C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl 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])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000012952 cationic photoinitiator Substances 0.000 claims 1
- 239000012949 free radical photoinitiator Substances 0.000 claims 1
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 15
- 238000003860 storage Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 10
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Chemical compound C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- KOFLVDBWRHFSAB-UHFFFAOYSA-N 1,2,4,5-tetrahydro-1-(phenylmethyl)-5,9b(1',2')-benzeno-9bh-benz(g)indol-3(3ah)-one Chemical compound C1C(C=2C3=CC=CC=2)C2=CC=CC=C2C23C1C(=O)CN2CC1=CC=CC=C1 KOFLVDBWRHFSAB-UHFFFAOYSA-N 0.000 description 1
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
The present disclosure relates to a multifunctional monomer compound having a structure represented by formula (1), a method for preparing the same, and a photosensitive resin composition;
Description
The present application is a divisional application of chinese invention patent application filed on 1 month 17 2017, with application number 201710036388.4 and the invention name "a multifunctional monomer compound, a preparation method thereof and a photosensitive resin composition".
Technical Field
The present disclosure relates to the field of liquid crystal displays, and in particular, to a multifunctional monomer compound, a method for preparing the same, and a photosensitive resin composition.
Background
The color filter is a key device for realizing colorization of the liquid crystal display, and the performance of the color photoresist for preparing the color filter directly influences the display effect of the liquid crystal display. As the color purity of the liquid crystal display is required to be increased, the developing performance of the coating film is reduced as the concentration of the colorant contained in the photosensitive resin composition becomes higher, which requires that the photosensitive resin composition have good developing performance and that the film formed from the resin composition have good storage stability.
In order to improve the development performance of the color photoresist, a few development aids are often added, and small molecular acids or acidic substances are generally used as main materials. However, with the addition of such substances, the dispersion stability of color paste in the color photoresist is affected, and the phenomena of gel, pigment sedimentation and wall hanging appear when serious, even if the color paste is slightly affected, the viscosity of the color photoresist is obviously improved, and the production line coating is affected.
Disclosure of Invention
An object of the present disclosure is to provide a multifunctional monomer compound which can hydrolyze to generate an acid, and a photosensitive resin composition composed thereof has good developing property and storage stability.
In order to achieve the above object, the present disclosure provides a multifunctional monomer compound having a structure represented by formula (1);
wherein R is 1 Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-12 carbon atoms, wherein the substituent in the substituted aryl is alkyl with 1-5 carbon atoms; n is an integer of 1 to 5;
R 2 derived from a hydroxyl group-containing multifunctional acrylate monomer which is at least one selected from pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, and di (methacryloyloxymethylene) hydrogen phosphate.
The present disclosure also provides a method of preparing a multifunctional monomer compound, the method comprising:
contacting an intermediate compound represented by formula (14) with a hydroxy group-containing polyfunctional acrylate monomer under substitution reaction conditions to obtain a polyfunctional monomer compound represented by formula (1);
wherein R is 1 Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-10 carbon atoms, wherein the substituent in the substituted aryl is alkyl with 1-5 carbon atoms; n is an integer of 1 to 5;
R 2 derived from a hydroxyl group-containing multifunctional acrylate monomer which is at least one selected from pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, and di (methacryloyloxymethylene) hydrogen phosphate.
The present disclosure also provides a photosensitive resin composition containing the above-described multifunctional monomer compound, an alkali-soluble resin, a photosensitive monomer, a pigment, and a photoinitiator; the content of the above-mentioned multifunctional monomer compound is 0.5 to 40 parts by weight, the content of the photosensitive monomer is 50 to 300 parts by weight, the content of the pigment is 15 to 300 parts by weight, and the content of the photoinitiator is 0.5 to 40 parts by weight, relative to 100 parts by weight of the alkali-soluble resin.
Through the technical scheme, the multifunctional monomer compound disclosed by the invention can meet water to generate acid in a developing process, promote the development of unexposed parts, ensure the development performance even under the premise of extremely high color purity, and not prolong the production takt of a user; the multifunctional monomer compound can participate in polymerization for the exposed part, and is crosslinked with other polymerizable components in the photoresist composition to form a network structure, so that the stability of the resin cured film is not affected by acid generation, and meanwhile, the compound generated after the hydrolysis of the multifunctional monomer compound contains silicon hydroxyl, so that the adhesive force between the resin cured film and the glass substrate can be increased. Meanwhile, the multifunctional monomer compound does not have acidity, so that the stability of the photoresist is not damaged if the multifunctional monomer compound is not contacted with water in the storage stage, and the storage stability of the color photoresist is remarkably improved compared with that of the color photoresist which generally contains small molecular acid or acidic substances as a developing aid.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The present disclosure provides a multifunctional monomer compound having a structure represented by formula (1);
wherein R is 1 Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-12 carbon atoms, wherein the substituent in the substituted aryl is alkyl with 1-5 carbon atoms; n is an integer of 1 to 5;
R 2 derived from a hydroxyl group-containing multifunctional acrylate monomer which is at least one selected from pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, and di (methacryloyloxymethylene) hydrogen phosphate.
The multifunctional monomer compound disclosed by the invention can be used for generating acid when meeting water in a developing process, promoting the development of unexposed parts, ensuring the development performance even if the color purity is extremely high, and not prolonging the production takt of a user; the multifunctional monomer compound can participate in polymerization for the exposed part, and is crosslinked with other polymerizable components in the photoresist composition to form a network structure, so that the stability of the resin cured film is not affected by acid generation, and the compound generated after the hydrolysis of the multifunctional monomer compound contains silicon hydroxyl groups, so that the adhesive force between the resin cured film and a glass substrate can be increased; meanwhile, the multifunctional monomer compound does not have acidity, so that the stability of the photoresist is not damaged if the multifunctional monomer compound is not contacted with water in the storage stage, and the storage stability of the color photoresist is remarkably improved compared with that of the color photoresist which generally contains small molecular acid or acidic substances as a developing aid.
According to the present disclosure, R 2 Derived from hydroxy-containing multifunctional acrylate monomers means that R 2 Is a group left after the condensation reaction of the hydroxyl-containing polyfunctional acrylate monomer and the silicon hydroxyl group.
According to the present disclosure, the alkyl group having 1 to 10 carbon atoms may be a straight chain alkyl group, a branched chain alkyl group, or a cycloalkyl group, and specifically, may be at least one selected from the group consisting of methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, and neopentyl group; the haloalkyl group having 1 to 10 carbon atoms may be an alkyl group in which at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom, preferably, in the haloalkyl group having 1 to 10 carbon atoms, the halogen atom may be F, cl or Br, more preferably, F, and the number of the halogen atoms may be 1 to 21, preferably 1 to 7; the substituted or unsubstituted aryl group with 6-10 carbon atoms is at least one selected from phenyl, methylphenyl, ethylphenyl, propylphenyl, isopropylphenyl and butylphenyl, the position of the substituent in the methylphenyl, ethylphenyl, propylphenyl, isopropylphenyl and butylphenyl can be at least one of ortho position, para position or meta position, and the number of the substituent is preferably 1-3.
Still further preferred in accordance with the present disclosure is R 1 May be at least one selected from trifluoromethyl, phenyl and p-tolyl. In the above preferred case, the multifunctional monomer compound is hydrolyzed to generate acid more efficiently in the developing step, and the developing performance is improved.
According to the present disclosure, the structure of the multifunctional monomer compound may be one of structures represented by formulae (2) - (13):
the present disclosure also provides a method of preparing a multifunctional monomer compound, the method comprising:
contacting an intermediate compound represented by formula (14) with a hydroxy group-containing polyfunctional acrylate monomer under substitution reaction conditions to obtain a polyfunctional monomer compound represented by formula (1);
wherein R is 1 Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-10 carbon atoms, wherein the substituent in the substituted aryl is alkyl with 1-5 carbon atoms; n is an integer of 1 to 5;
R 2 derived from the hydroxyl group-containing multifunctional acrylate monomer selected from pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, and di (methacryloyl) hydrogen phosphateOxymethylene) esters.
According to the present disclosure, the molar ratio of the intermediate represented by formula (14) to the hydroxyl group-containing multifunctional acrylate monomer may be 1: (0.2-4), preferably 1: (0.3-2); the reaction conditions of the substitution reaction may be: the reaction temperature is 20-80 ℃, the reaction time is 0.5-3h, the preferable reaction conditions can be 40-70 ℃ and the reaction time is 1-2h.
According to the present disclosure, a method for preparing an intermediate compound represented by formula (14) may include: contacting a compound represented by formula (15) with a compound represented by formula (16) under dehydration reaction conditions;
wherein R1 can be alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-10 carbon atoms, and the substituent in the substituted aryl is alkyl with 1-5 carbon atoms;
in order to increase the reaction conversion rate, preferably, the molar ratio of the compound represented by formula (15) to the compound represented by formula (16) may be 1: (0.5-2), more preferably 1: (0.7-1.5); the reaction conditions of the dehydration reaction may be: the reaction temperature is 0-60 ℃, the reaction time is 0.5-3h, and more preferable reaction conditions can be: the reaction temperature is 10-40 ℃ and the reaction time is 1-3h.
The present disclosure also provides a photosensitive resin composition containing the above-described multifunctional monomer compound, an alkali-soluble resin, a photosensitive monomer, a pigment, and a photoinitiator; the content of the above-mentioned multifunctional monomer compound is 0.5 to 40 parts by weight, the content of the photosensitive monomer is 15 to 300 parts by weight, the content of the pigment is 15 to 300 parts by weight, and the content of the photoinitiator is 0.5 to 40 parts by weight, relative to 100 parts by weight of the alkali-soluble resin.
The photosensitive resin composition contains the multifunctional monomer, can meet water acid in a developing process, improves the developing performance of the photosensitive resin composition, and meanwhile, the storage stability of the composition is obviously improved because the composition does not contain an acid compound in a storage stage, and the viscosity change of the photosensitive resin composition is less than 10% when the composition is placed for 6 months at 0-10 ℃. When the photosensitive resin composition is used for preparing the color filter, the development effect is good, the edges of the patterns are free from residual films and scum, and the patterns are complete and are not easy to fall off.
Preferably, the content of the above-mentioned multifunctional monomer compound may be 5 to 30 parts by weight, the content of the photosensitive monomer may be 50 to 260 parts by weight, the content of the pigment may be 60 to 150 parts by weight, and the content of the photoinitiator may be 5 to 30 parts by weight, relative to 100 parts by weight of the alkali-soluble resin.
Wherein the alkali-soluble resin is a resin containing alkali-soluble groups which is well known to the person skilled in the art, and preferably can be acrylic resin and/or acrylic resin, the acid value of the alkali-soluble resin can be 50-200mg/KOH, the molecular weight can be 2000-20000, and the mass content of benzene rings in the alkali-soluble resin can be 7-18%;
the photosensitive monomer can be a monomer compound containing unsaturated double bonds, such as an acrylic ester compound containing unsaturated double bonds, and can be specifically at least one of 1, 6-ethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 3-propoxylated glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;
the photoinitiator may be a cleavage free radical type photoinitiator and/or cationic type photoinitiator, for example at least one of a benzoyl type photoinitiator, benzoin and derivative photoinitiators, an alkyl benzophenone type photoinitiator, an acyl phosphorus oxide photoinitiator, a benzophenone type photoinitiator, a thioxanthone type photoinitiator, a diaryl iodonium salt photoinitiator, a triaryliodonium salt photoinitiator, a ketoxime ester type photoinitiator, an alkyl iodonium salt photoinitiator and a isopropylferrocenium hexafluorophosphate photoinitiator, preferably at least one of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 4' -bis (diethylamino) benzophenone, 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), 1- (6-O-methylbenzoyl-9-ethyl-9. H. -carbazolyl) -ketoxime-O-acetate and ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate.
The pigment may be one or more of red pigment, green pigment, blue pigment, yellow pigment and orange pigment. The specific types of pigments may be well known to those skilled in the art and will not be described in detail herein.
In order to facilitate coating and improve the film forming quality of resin curing, the photosensitive resin composition can contain a solvent and/or an auxiliary agent, wherein the solvent can be at least one of methanol, toluene, xylene, ethanol, chloroform, methylene dichloride, ethyl acetate, butyl acetate, ethylene glycol dimethyl ester, diethylene glycol dimethyl ester, propylene glycol methyl ether acetate, 3-ethyl ether propionate and 1-ethoxy-2-propanol, and the auxiliary agent can be at least one of a sensitizer, a silane coupling agent, a defoaming agent and a leveling agent. The specific types and amounts of the above-described adjuvants may be of a type well known to those skilled in the art, and are not particularly required in the present disclosure.
Further preferably, the photosensitive resin composition may contain a solvent, a silane coupling agent and a leveling agent, the content of the solvent is preferably 100 to 500 parts by weight, the content of the silane coupling agent is preferably 0.1 to 20 parts by weight, and the content of the leveling agent is preferably 0.1 to 20 parts by weight, relative to 100 parts by weight of the alkali-soluble resin.
The photosensitive resin composition of the present disclosure can be used to prepare a photoresist film portion in a color filter (color filter).
The preparation method of the color filter can comprise the following steps: the photosensitive resin composition is coated on a substrate, and the color filter is obtained through the steps of pre-baking, exposure, development and post-baking in sequence.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
Example 1
This example is intended to illustrate the preparation of the polyfunctional monomer compounds of the present disclosure.
1. Preparing a medicine: and the molar ratio of the trifluoromethanesulfonic acid to the dimethyldihydroxy silicon is 2:1, and a plurality of dehydrating agents are used. Using a flask as a reaction container, slowly dripping trifluoromethanesulfonic acid into dimethyldihydroxy silicon at a reaction temperature of 30 ℃ in the presence of titanium tetrachloride serving as a dehydrating agent, continuing to react for 1h after dripping, cooling to room temperature, and taking out to obtain an intermediate compound C1;
2. and (3) dropwise adding dipentaerythritol pentaacrylate into the intermediate compound C1, controlling the molar ratio of the intermediate compound C1 to the dipentaerythritol pentaacrylate to be 1:1, and simultaneously adding a dehydrating agent into the system. Using a flask as a reaction container, wherein the reaction temperature is 60 ℃, continuing to react for 1h after dripping is completed, cooling to room temperature, and taking out to obtain a mixture containing a reaction product;
3. placing the mixture obtained in the step 2 on a reverse phase silica gel column, using ethyl acetate as an eluent, collecting a reaction product, removing the solvent by spin evaporation, and drying to obtain the multifunctional monomer compound A1 of the present example (yield 73%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝0.14(6H，s)，3.71-4.07(16H，t)，5.59-6.27(15H，t))。
example 2
The procedure of example 1 was followed except that trifluoromethanesulfonic acid was replaced with benzenesulfonic acid in equivalent amount to obtain polyfunctional monomer compound A2 of this example (yield 82%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.62-7.86(5H，t)，0.14(6H，s)，3.71-4.07(16H，t)，5.59-6.27(15H，t))。
example 3
The procedure of example 1 was followed except that trifluoromethanesulfonic acid was replaced with an equivalent amount of p-toluenesulfonic acid to obtain a polyfunctional monomer compound A3 of this example (yield 70%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.40-7.74(4H，t)，0.14(6H，s)，2.34(3H，s)，3.71-4.07(16H，t)，5.59-6.27(15H，t))。
example 4
The procedure of example 1 was followed except that dipentaerythritol pentaacrylate was replaced with pentaerythritol triacrylate in equivalent amount to give the polyfunctional monomer compound A4 of this example (yield 75%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝0.14(6H，s)，3.71(2H，s)，4.07(6H，s)，5.59-6.27(9H，t))。
example 5
The procedure of example 2 was followed except that dipentaerythritol pentaacrylate was replaced with pentaerythritol triacrylate in equivalent amount to give the polyfunctional monomer compound A5 of the present example (yield 87%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.62-7.86(5H，t)，0.14(6H，s)，3.71(2H，s)，4.07(6H，s)，5.59-6.27(9H，t))。
example 6
The procedure of example 3 was followed except that dipentaerythritol pentaacrylate was replaced with pentaerythritol triacrylate in equivalent amount to give the polyfunctional monomer compound A6 of the present example (yield 68%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.40-7.74(4H，t)，0.14(6H，s)，2.34(H，s)，3.71(2H，s)，4.07(6H，s)，5.59-6.27(12H，t))。
example 7
The procedure of example 1 was followed except that dipentaerythritol pentaacrylate was replaced with dipentaerythritol tetraacrylate, and the molar ratio of intermediate compound C1 to dipentaerythritol tetraacrylate was controlled to be 1:0.5 to give a polyfunctional monomer compound A7 of the present example (yield 65%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝0.14(12H，s)，3.71-4.07(16H，t)，5.59-6.27(15H，t))。
example 8
The procedure of example 2 was followed except that dipentaerythritol pentaacrylate was replaced with dipentaerythritol tetraacrylate, and the intermediate was controlledThe molar ratio of the bulk compound C1 to dipentaerythritol tetraacrylate was 1:0.5, yielding the multifunctional monomer compound A8 of the present example (yield 59%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.62-7.86(5H，t)，0.14(12H，s)，3.71-4.07(16H，t)，5.59-6.27(12H，t))。
example 9
The procedure of example 3 was employed, except that dipentaerythritol pentaacrylate was replaced with dipentaerythritol tetraacrylate, and the molar ratio of intermediate compound C1 to dipentaerythritol tetraacrylate was controlled to be 1:0.5, to obtain polyfunctional monomer compound A9 of the present example (yield 51%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.40-7.74(4H，t)，0.14(12H，s)，2.34(3H，s)，3.71-4.07(16H，t)，5.59-6.27(12H，t))。
example 10
The procedure of example 1 was followed except that dipentaerythritol pentaacrylate was replaced with equivalent amount of di (methacryloyloxymethylene) hydrogen phosphate to give polyfunctional monomer compound a10 of the present example (yield 77%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝0.14(6H，s)，2.01(6H，s)，6.89(4H，d)，6.40-6.48(4H，t))。
example 11
The procedure of example 2 was followed except that dipentaerythritol pentaacrylate was replaced with equivalent amount of di (methacryloyloxymethylene) hydrogen phosphate to give polyfunctional monomer compound a11 of the present example (yield 73%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.62-7.86(5H，t)，0.14(6H，s)，2.01(6H，s)，6.89(4H，d)，6.40-6.48(4H，t))。
example 12
The procedure of example 3 was followed except that dipentaerythritol pentaacrylate was replaced with equivalent amount of di (methacryloyloxymethylene) hydrogen phosphate to give the polyfunctional monomer compound a12 of the present example (yield 72%; 1 H NMR(400MHz，CDCl 3 ，ppm)，δ＝7.40-7.74(4H，t)，0.14(6H，s)，2.01(6H，s)，2.34(3H，s)，6.89(4H，d)，6.40-6.48(4H，t))。
example 13
This example is for explaining the photosensitive resin composition of the present disclosure.
100 parts by weight of an alkali-soluble resin Sarbox SB400 (available from Sadamma Co.), 167 parts by weight of dipentaerythritol hexaacrylate (available from Sadamma Co.), 80 parts by weight of G36+Y156 pigment (DIC Co.), 20 parts by weight of a photoinitiator OXE-01 (Basf Co.), 20 parts by weight of a polyfunctional monomer compound A1, 267 parts by weight of a solvent propylene glycol methyl ether acetate (Dow Co.), 6.7 parts by weight of a silane coupling agent OFS-6030 (Dow-Corning Co.), and 6.7 parts by weight of a leveling agent EB350 (Sadamma Co.) were uniformly mixed to obtain a photosensitive resin composition R1 of the present example.
Examples 14 to 24
The raw material of example 7 was used except that the polyfunctional monomer compound A1 was replaced with the polyfunctional monomer compounds A2 to a12 of equal weight, respectively, to obtain photosensitive resin compositions R2 to R12.
Example 25
100 parts by weight of an alkali-soluble resin Sarbox SB400 (from Sadamma Co.), 300 parts by weight of dipentaerythritol hexaacrylate (from Sadamma Co.), 200 parts by weight of G36+Y156 pigment (DIC Co.), 40 parts by weight of a photoinitiator OXE-01 (Basf Co.), 40 parts by weight of a polyfunctional monomer compound A1, 500 parts by weight of a solvent propylene glycol methyl ether acetate (Dow Co.), 10 parts by weight of a silane coupling agent OFS-6030 (Dow-Corning Co.) and 10 parts by weight of a leveling agent EB350 (Sadamma Co.) were uniformly mixed to obtain a photosensitive resin composition R13 of the present example.
Example 26
100 parts by weight of an alkali-soluble resin Sarbox SB400 (from Sadamma Co.), 20 parts by weight of dipentaerythritol hexaacrylate (from Sadamma Co.), 15 parts by weight of G36+Y156 pigment (DIC Co.), 0.5 part by weight of a photoinitiator OXE-01 (Basf Co.), 0.5 part by weight of a polyfunctional monomer compound A1, 500 parts by weight of a solvent propylene glycol methyl ether acetate (Dow Co.), 0.1 part by weight of a silane coupling agent OFS-6030 (Dow-Corning Co.), and 0.1 part by weight of a leveling agent EB350 (Sadamma Co.) were uniformly mixed to obtain a photosensitive resin composition R14 of the present example.
Example 27
100 parts by weight of an alkali-soluble resin Sarbox SB400 (available from Sadamma Co.), 180 parts by weight of dipentaerythritol hexaacrylate (available from Sadamma Co.), 80 parts by weight of G36+Y156 pigment (DIC Co.), 20 parts by weight of a photoinitiator OXE-01 (Basf Co.), 6.7 parts by weight of a polyfunctional monomer compound A1, 267 parts by weight of a solvent propylene glycol methyl ether acetate (Dow Co.), 6.7 parts by weight of a silane coupling agent OFS-6030 (Dow-Corning Co.), and 6.7 parts by weight of a leveling agent EB350 (Sadamma Co.) were uniformly mixed to obtain a photosensitive resin composition R15 of the present example.
Example 28
100 parts by weight of an alkali-soluble resin Sarbox SB400 (from Sadamma Co.), 167 parts by weight of dipentaerythritol hexaacrylate (from Sadamma Co.), 80 parts by weight of G36+Y156 pigment (DIC Co.), 20 parts by weight of a photoinitiator OXE-01 (Basf Co.), 267 parts by weight of a solvent propylene glycol methyl ether acetate (Dow Co.), and 20 parts by weight of a polyfunctional monomer compound A1 were taken to obtain a photosensitive resin composition R16 of the present example.
Comparative example 1
The raw material of example 7 was used except that the polyfunctional monomer compound A1 was replaced with dipentaerythritol hexaacrylate in an equal weight to obtain a photosensitive resin composition R17.
Comparative example 2
The raw material of example 7 was used except that the polyfunctional monomer compound A1 was replaced with an equal weight of the developing aid benzoic acid to obtain a photosensitive resin composition R18.
Test examples
Mixing the photosensitive resin compositions R1-R18 uniformly, pre-baking at 100deg.C for 2min, exposing (exposure 60mj/cm 2), developing, and post-baking at 230deg.C for 20min, testing the adhesive force, development time (time required for development) and viscosity change rate of the optical filter containing the cured film of the resin composition, and the results are shown in Table 1;
the adhesive force testing method comprises the following steps: using a hundred-blade knife to scratch the optical filters of the resin composition cured films containing R1-R18 respectively, and counting the number of the falling-off photoresist blocks in Table 1;
viscosity change rate test method: the photosensitive resin compositions R1 to R18 were left at 5℃for 6 months, and the viscosities before and after leaving were measured, respectively, and the calculated viscosity change rates are shown in Table 1;
TABLE 1
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As is clear from table 1, the development performance of the photosensitive resin composition R1 to R16 containing the polyfunctional monomer compound of the present disclosure is significantly improved, and the adhesion of the cured resin to the substrate is also significantly improved, as compared with the photosensitive resin composition R17 of comparative example 1, and the storage stability of the photosensitive resin composition R1 to R16 is significantly improved, as compared with the photosensitive resin composition R18 of comparative example 2 containing the acidic development aid, and as is clear from the comparison of the data of examples 13 and 28 (R1 and R16), in the case where the photosensitive resin composition of the present disclosure preferably further contains the aid, the development of the photosensitive resin is faster, and the adhesion of the cured resin to the substrate is higher.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as being disclosed in the present disclosure.
Claims (11)
1. A polyfunctional monomer compound characterized by having a structure represented by formula (1);
wherein R is 1 Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-12 carbon atoms, wherein the substituent in the substituted aryl is alkyl with 1-5 carbon atoms; n is an integer of 1 to 5;
R 2 derived from a hydroxyl group-containing multifunctional acrylate monomer which is di (methacryloyloxymethylene) hydrogen phosphate.
2. The polyfunctional monomer compound according to claim 1, wherein said alkyl group having 1 to 10 carbon atoms is at least one selected from the group consisting of methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group and neopentyl group;
in the halogenated alkyl with the carbon number of 1-10, the halogen atom is F, cl or Br, and the number of the halogen atom is 1-21;
the substituted or unsubstituted aryl group having 6 to 10 carbon atoms is at least one selected from the group consisting of phenyl, methylphenyl, ethylphenyl, propylphenyl and butylphenyl.
3. The multifunctional monomer compound of claim 2, wherein R 1 Is at least one selected from trifluoromethyl, phenyl and p-tolyl.
4. The multifunctional monomer compound according to claim 1, wherein the structure of the multifunctional monomer compound is one of structures represented by formulas (11) - (13):
5. a method for preparing a multifunctional monomer compound, the method comprising:
contacting an intermediate compound represented by formula (14) with a hydroxy group-containing polyfunctional acrylate monomer under substitution reaction conditions to obtain a polyfunctional monomer compound represented by formula (1);
wherein R is 1 Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-10 carbon atoms, wherein the substituent in the substituted aryl is alkyl with 1-5 carbon atoms; n is an integer of 1 to 5;
R 2 derived from the hydroxy-containing multifunctional acrylate monomer which is di (methacryloyloxymethylene) hydrogen phosphate.
6. The method according to claim 5, wherein a molar ratio of the intermediate represented by the formula (14) to the hydroxyl group-containing multifunctional acrylate monomer is 1: (0.2-4); the reaction conditions of the substitution reaction are as follows: the reaction temperature is 20-80 ℃ and the reaction time is 0.5-3h.
7. The method according to claim 5 or 6, characterized in that the method further comprises: contacting a compound represented by formula (15) with a compound represented by formula (16) under dehydration reaction conditions to obtain an intermediate compound represented by formula (14);
wherein R is 1 Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-10 carbon atoms, wherein the substituent in the substituted aryl is alkyl with 1-5 carbon atoms;
the molar ratio of the compound shown in the formula (15) to the compound shown in the formula (16) is 1: (0.5-2); the reaction conditions of the dehydration reaction are as follows: the reaction temperature is 0-60 ℃ and the reaction time is 0.5-3h.
8. A photosensitive resin composition comprising the polyfunctional monomer compound according to any one of claims 1 to 4, an alkali-soluble resin, a photosensitive monomer, a pigment and a photoinitiator; the multifunctional monomer compound according to any one of claims 1 to 4 is contained in an amount of 0.5 to 40 parts by weight, the photosensitive monomer is contained in an amount of 50 to 300 parts by weight, the pigment is contained in an amount of 15 to 300 parts by weight, and the photoinitiator is contained in an amount of 0.5 to 40 parts by weight, relative to 100 parts by weight of the alkali-soluble resin.
9. The photosensitive resin composition according to claim 8, wherein the alkali-soluble resin is an acrylic resin and/or an acrylic resin, and the photosensitive monomer is at least one of 1, 6-ethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 3-propoxylated glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate;
the photoinitiator is a cleavage free radical photoinitiator and/or a cationic photoinitiator.
10. The photosensitive resin composition according to claim 9, wherein the photoinitiator is at least one of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 4' -bis (diethylamino) benzophenone, 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime), 1- (6-O-methylbenzoyl-9-ethyl-9. H. -carbazole-3-yl) -ethanone oxime-O-acetate, and ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate.
11. The photosensitive resin composition according to claim 8, further comprising a solvent and/or an auxiliary agent, wherein the solvent is at least one of methanol, toluene, xylene, ethanol, chloroform, methylene chloride, ethyl acetate, butyl acetate, ethylene glycol dimethyl ester, diethylene glycol dimethyl ester, propylene glycol methyl ether acetate, 3-ethyl propionate, and 1-ethoxy-2-propanol, and the auxiliary agent is at least one of a sensitizer, a silane coupling agent, an antifoaming agent, and a leveling agent.
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| EP0200141A2 (en) * | 1985-04-26 | 1986-11-05 | Nippon Zeon Co., Ltd. | Photoresist composition |
| CN107936200A (en) * | 2017-11-13 | 2018-04-20 | 清华大学 | Method of modifying, mesoporous material and its application of mesoporous silicon |
| CN110551151A (en) * | 2018-05-30 | 2019-12-10 | 微宏动力系统（湖州）有限公司 | preparation method of phosphate or phosphite ester, electrolyte and secondary battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806604A (en) * | 1987-05-13 | 1989-02-21 | Regents Of The University Of California | Photosensitive calcium chelators |
| US4971871A (en) * | 1988-01-29 | 1990-11-20 | Fuji Photo Film Co., Ltd. | Electrophotographic lithographic printing plate precursor |
| JPH01217468A (en) * | 1988-02-26 | 1989-08-31 | Fuji Photo Film Co Ltd | Planographic printing plate |
| WO1992018907A1 (en) * | 1991-04-15 | 1992-10-29 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor |
| US5558966A (en) * | 1991-07-30 | 1996-09-24 | Fuji Photo Film Co., Ltd. | Electrophotographic light-sensitive material |
| DE69508812T2 (en) * | 1994-01-28 | 1999-11-04 | Shinetsu Chemical Co | Sulfonium salt and chemically amplified positive resist compositions |
-
2017
- 2017-01-17 CN CN202210147555.3A patent/CN114524841B/en active Active
- 2017-01-17 CN CN201710036388.4A patent/CN108314692B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0200141A2 (en) * | 1985-04-26 | 1986-11-05 | Nippon Zeon Co., Ltd. | Photoresist composition |
| CN107936200A (en) * | 2017-11-13 | 2018-04-20 | 清华大学 | Method of modifying, mesoporous material and its application of mesoporous silicon |
| CN110551151A (en) * | 2018-05-30 | 2019-12-10 | 微宏动力系统（湖州）有限公司 | preparation method of phosphate or phosphite ester, electrolyte and secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114524841A (en) | 2022-05-24 |
| CN108314692A (en) | 2018-07-24 |
| CN108314692B (en) | 2022-03-22 |
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