CN114524841A - Multifunctional monomer compound, preparation method thereof and photosensitive resin composition - Google Patents
Multifunctional monomer compound, preparation method thereof and photosensitive resin composition Download PDFInfo
- Publication number
- CN114524841A CN114524841A CN202210147555.3A CN202210147555A CN114524841A CN 114524841 A CN114524841 A CN 114524841A CN 202210147555 A CN202210147555 A CN 202210147555A CN 114524841 A CN114524841 A CN 114524841A
- Authority
- CN
- China
- Prior art keywords
- group
- carbon atoms
- monomer compound
- formula
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 90
- 150000001875 compounds Chemical class 0.000 title claims abstract description 89
- 239000011342 resin composition Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 6
- 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 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- -1 n-octyl group Chemical group 0.000 claims description 23
- 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 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001188 haloalkyl group Chemical group 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
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 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
- 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
- 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
- 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
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000012952 cationic photoinitiator Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 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
- 229910052731 fluorine Inorganic materials 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
- 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
- 238000005336 cracking Methods 0.000 claims 1
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- 239000012949 free radical photoinitiator Substances 0.000 claims 1
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000002378 acidificating effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 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
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 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
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 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
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 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
- 239000002994 raw material Substances 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
- 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010998 test method Methods 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
- 239000005711 Benzoic acid Substances 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
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound 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
- 239000012965 benzophenone Substances 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
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000006165 cyclic alkyl 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
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 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
- 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, a method for preparing the same, and a photosensitive resin composition, the compound having a structure represented by formula (1);
Description
The application is a divisional application of Chinese patent application with application number 201710036388.4, which is filed on 17.1.2017 and the name of which is 'a multifunctional monomer compound and a preparation method thereof and a photosensitive resin composition'.
Technical Field
The disclosure relates to the field of liquid crystal display, in particular to a multifunctional monomer compound, a preparation method thereof 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 used for preparing the color filter directly influences the display effect of the liquid crystal display. As the color purity of liquid crystal displays is required to be improved, the development performance of coating films is reduced when the concentration of a colorant contained in a photosensitive resin composition is increased, and thus the photosensitive resin composition is required to have good development performance and a film formed from the resin composition is required to have good storage stability.
In order to improve the developing performance of the color photoresist, some developing aids, generally including small-molecule acids or acidic substances, are often added. However, with the addition of such substances, the dispersion stability of the color paste in the color photoresist is affected, and the phenomena of gel, pigment sedimentation and wall hanging appear in severe cases, so that the viscosity of the color photoresist is obviously improved even if the color photoresist is slightly affected, and the coating of a production line is affected.
Disclosure of Invention
The present disclosure is directed to a multifunctional monomer compound that can be hydrolyzed to generate acid, and a photosensitive resin composition composed thereof has good developing properties 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 is1Is alkyl with 1-10 carbon atoms, haloalkyl 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;
R2derived from a hydroxyl group-containing polyfunctional acrylate monomer which is at least one selected from the group consisting of pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate and di (methacryloyloxyethyl) hydrogen phosphate.
The present disclosure also provides a method of preparing a multifunctional monomer compound, the method comprising:
contacting the intermediate compound represented by formula (14) with a multifunctional acrylate monomer containing a hydroxyl group under a substitution reaction condition to obtain a multifunctional monomer compound represented by formula (1);
wherein R is1Is alkyl with 1-10 carbon atoms, haloalkyl 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;
R2derived from a hydroxyl group-containing polyfunctional acrylate monomer which is at least one selected from the group consisting of pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate and di (methacryloyloxyethyl) hydrogen phosphate.
The present disclosure also provides a photosensitive resin composition containing the above multifunctional monomer compound, an alkali-soluble resin, a photosensitive monomer, a pigment and a photoinitiator; the content of the multifunctional monomer compound is 0.5-40 parts by weight, the content of the photosensitive monomer is 50-300 parts by weight, the content of the pigment is 15-300 parts by weight, and the content of the photoinitiator is 0.5-40 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 generate acid when meeting water in a developing process, the development of unexposed parts is promoted, the developing performance can be still ensured even on the premise of extremely high color purity, and the production rhythm of a user can not be prolonged; and for the exposed part, the multifunctional monomer compound can participate in polymerization and is crosslinked with other polymerizable components in the photoresist composition to form a network structure, the stability of the resin curing film cannot be influenced by acid production, and meanwhile, the compound generated after hydrolysis of the multifunctional monomer compound contains silicon hydroxyl, so that the adhesive force between the resin curing film and the glass substrate can be increased. Meanwhile, as the multifunctional monomer compound does not have acidity, the stability of the photoresist can not be damaged if the multifunctional monomer compound does not contact water in the storage stage, and the storage stability of the photoresist is obviously improved compared with that of the common color photoresist containing micromolecular acid or acidic substances as developing aids.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a multifunctional monomer compound having a structure represented by formula (1);
wherein R is1Is alkyl with 1-10 carbon atoms, halogenated alkyl with 1-10 carbon atoms or substituted or unsubstituted aryl with 6-12 carbon atoms,the substituent in the substituted aryl is alkyl with 1-5 carbon atoms; n is an integer of 1 to 5;
R2derived from a hydroxyl group-containing polyfunctional acrylate monomer which is at least one selected from the group consisting of pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate and di (methacryloyloxyethyl) hydrogen phosphate.
The multifunctional monomer compound disclosed by the invention can generate acid when meeting water in a developing process, promotes the development of unexposed parts, can still ensure the developing performance even under the premise of extremely high color purity, and cannot prolong the production beat of a user; for the exposed part, the multifunctional monomer compound can participate in polymerization and is crosslinked with other polymerizable components in the photoresist composition to form a network structure, the stability of the resin curing film cannot be influenced by acid production, and the compound generated after hydrolysis of the multifunctional monomer compound contains silicon hydroxyl, so that the adhesive force between the resin curing film and the glass substrate can be increased; meanwhile, as the multifunctional monomer compound does not have acidity, the stability of the photoresist can not be damaged if the multifunctional monomer compound does not contact water in the storage stage, and the storage stability of the photoresist is obviously improved compared with that of the common color photoresist containing micromolecular acid or acidic substances as developing aids.
According to the disclosure, R2Derived from a multifunctional acrylate monomer containing a hydroxyl group means that R2Is the group left after the condensation reaction of the hydroxyl-containing multifunctional 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 cyclic alkyl group, and specifically, may be at least one selected from the group consisting of a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, and a 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 having 6 to 10 carbon atoms is at least one selected from the group consisting of a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, an isopropylphenyl group and a butylphenyl group, the position of the substituent in the methylphenyl group, the ethylphenyl group, the propylphenyl group, the isopropylphenyl group and the butylphenyl group may be at least one of ortho-position, para-position or meta-position, and the number of the substituent is preferably 1 to 3.
Still further preferred, according to the present disclosure, R1May be at least one selected from the group consisting of trifluoromethyl, phenyl and p-tolyl. In the above preferred case, the polyfunctional monomer compound is more efficiently hydrolyzed to generate acid in the developing step, and the developing performance is better.
According to the present disclosure, the structure of the multifunctional monomer compound may be one of the structures represented by formula (2) to formula (13):
the present disclosure also provides a method of preparing a multifunctional monomer compound, the method comprising:
contacting the intermediate compound represented by formula (14) with a multifunctional acrylate monomer containing a hydroxyl group under a substitution reaction condition to obtain a multifunctional monomer compound represented by formula (1);
wherein R is1Is alkyl with 1-10 carbon atoms, haloalkyl 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;
R2derived from the hydroxyl group-containing multifunctional acrylate monomer, the hydroxyl group-containing multifunctional acrylate monomer is at least one selected from pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, and di (methacryloyloxyethyl) hydrogen phosphate.
According to the present disclosure, the molar ratio of the intermediate represented by formula (14) to the hydroxyl-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, and the preferable reaction condition can be 40-70 ℃, and the reaction time is 1-2 h.
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 a dehydration reaction condition;
wherein, R1 can be alkyl with 1-10 carbon atoms, haloalkyl 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 as follows: the reaction temperature is 10-40 ℃, and the reaction time is 1-3 h.
The present disclosure also provides a photosensitive resin composition containing the above multifunctional monomer compound, an alkali-soluble resin, a photosensitive monomer, a pigment and a photoinitiator; the content of the above 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 disclosed by the invention contains the multifunctional monomer, can generate acid when meeting water in a developing process, improves the developing performance of the photosensitive resin composition, and meanwhile, because the composition does not contain an acidic compound in a storage stage, the storage stability of the composition is also obviously improved, and the viscosity change of the photosensitive resin composition is less than 10 percent when the composition is placed at 0-10 ℃ for 6 months. When the photosensitive resin composition is used for preparing a color filter, the developing effect is good, no residual film or scum exists at the edge of a pattern, and the pattern is intact and is not easy to fall off.
Preferably, the above multifunctional monomer compound may be contained in an amount of 5 to 30 parts by weight, the photosensitive monomer may be contained in an amount of 50 to 260 parts by weight, the pigment may be contained in an amount of 60 to 150 parts by weight, and the photoinitiator may be contained in an amount of 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 those skilled in the art, and preferably can be acrylic resin and/or acrylate 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 may be a monomer compound containing an unsaturated double bond, such as an acrylate compound containing an unsaturated double bond, and specifically may be 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 cleavable radical photoinitiator and/or a cationic photoinitiator, such as benzoyl photoinitiator, benzoin and derivative photoinitiator, an alkylbenzene photoinitiator, an acylphosphorus oxide photoinitiator, a benzophenone photoinitiator, a thioxanthone photoinitiator, a diaryliodonium salt photoinitiator, a triaryliodonium salt photoinitiator, a ketoxime ester photoinitiator, an alkyl iodonium salt photoinitiator, and a cumeneferrocene hexafluorophosphate photoinitiator, and is preferably at least one selected from 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. -carbazol-3 yl) -ethanone oxime-O-acetate and at least one of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate.
The pigment can be one or more of red pigment, green pigment, blue pigment, yellow pigment and orange pigment. The specific type of pigment may be well known to those skilled in the art and will not be described further herein.
In order to facilitate coating and improve the quality of a cured film of the resin, the photosensitive resin composition may include a solvent and/or an auxiliary agent, the solvent may be at least one of methanol, toluene, xylene, ethanol, chloroform, dichloromethane, 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 may be at least one of a sensitizer, a silane coupling agent, an antifoaming agent, and a leveling agent. The specific types and amounts of the above-mentioned adjuvants may be those known to those skilled in the art, and are not specifically required in the present disclosure.
Further preferably, the photosensitive resin composition may include a solvent, a silane coupling agent, and a leveling agent, and the solvent is preferably contained in an amount of 100-500 parts by weight, the silane coupling agent is preferably contained in an amount of 0.1-20 parts by weight, and the leveling agent is preferably contained in an amount of 0.1-20 parts by weight, relative to 100 parts by weight of the alkali-soluble resin.
The photosensitive resin composition disclosed by the invention can be used for preparing a photoresist film part in a color filter (color filter).
The preparation method of the color filter can comprise the following steps: and coating the photosensitive resin composition on a substrate, and sequentially carrying out pre-baking, exposure, development and post-baking to obtain the color filter.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
Example 1
This example serves to illustrate the preparation of the multifunctional monomer compounds of the present disclosure.
1. Preparing a medicine: trifluoromethanesulfonic acid, dimethyldihydroxysilicon (molar ratio 2:1) and a plurality of dehydrating agents. Using a flask as a reaction container, slowly dropping trifluoromethanesulfonic acid into dimethyldihydroxy silicon in the presence of titanium tetrachloride as a dehydrating agent at the reaction temperature of 30 ℃, continuing to react for 1h after the dropping is finished, 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, keeping the reaction temperature at 60 ℃, continuing to react for 1h after finishing dripping, cooling to room temperature, and taking out to obtain a mixture containing a reaction product;
3. the mixture of step 2 was placed on a reverse phase silica gel column, and the reaction product was collected using ethyl acetate as an eluent, and the solvent was removed by rotary evaporation and dried to obtain the polyfunctional monomer compound a1 of this example (yield 73%;1H NMR(400MHz，CDCl3，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 an equivalent amount of benzenesulfonic acid, to give the polyfunctional monomer compound a2 of this example (yield 82%;1H NMR(400MHz， CDCl3，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 p-toluenesulfonic acid in an equivalent amount, to give polyfunctional monomer compound a3 of this example (yield 70%;1H NMR(400MHz， CDCl3，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 an equivalent amount, to give the polyfunctional monomer compound a4 of the present example (yield 75%;1H NMR(400MHz，CDCl3，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 an equivalent amount, to give the polyfunctional monomer compound a5 of the present example (yield 87%;1H NMR(400MHz，CDCl3，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
Using the procedure of example 3, except substituting dipentaerythritol pentaacrylate for an equivalent amount of pentaerythritol triacrylate, the procedure of this example was repeated to give the multi-polymerFunctional monomer compound a6 (yield 68%;1H NMR(400MHz，CDCl3，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, the polyfunctional monomer compound a7 of the present example was obtained (yield 65%;1H NMR (400MHz，CDCl3，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 molar ratio of intermediate compound C1 to dipentaerythritol tetraacrylate was controlled to 1:0.5, to obtain polyfunctional monomer compound a8 of this example (yield 59%;1H NMR (400MHz，CDCl3，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 followed, except that dipentaerythritol pentaacrylate was replaced with dipentaerythritol tetraacrylate, and the molar ratio of intermediate compound C1 to dipentaerythritol tetraacrylate was controlled to 1:0.5, to obtain polyfunctional monomer compound a9 of this example (yield 51%;1H NMR (400MHz，CDCl3，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 an equivalent amount of di (methacryloyloxyethyl) hydrogen phosphate to obtain the polyfunctional monomer compound a10 of the present example (yield 77%;1H NMR(400MHz，CDCl3，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 an equivalent amount of di (methacryloyloxyethyl) hydrogen phosphate, to give the polyfunctional monomer compound a11 of the present example (yield 73%;1H NMR(400MHz，CDCl3，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 an equivalent amount of di (methacryloyloxyethyl) hydrogen phosphate to obtain the polyfunctional monomer compound a12 of the present example (yield 72%;1H NMR(400MHz，CDCl3，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 Saedoma), 167 parts by weight of dipentaerythritol hexaacrylate (available from Saedoma), 80 parts by weight of G36+ Y156 pigment (DIC), 20 parts by weight of a photoinitiator OXE-01 (Basf), 20 parts by weight of a polyfunctional monomer compound A1, 267 parts by weight of propylene glycol monomethyl ether acetate (Dow), 6.7 parts by weight of a silane coupling agent OFS-6030 (Dow-Corning), and 6.7 parts by weight of a leveling agent EB350 (available from Saedoma) were mixed uniformly to obtain a photosensitive resin composition R1 of this example.
Examples 14 to 24
Photosensitive resin compositions R2 to R12 were obtained by using the raw materials of example 7 except that the polyfunctional monomer compound A1 was replaced with the polyfunctional monomer compounds A2 to A12 in equal weights, respectively.
Example 25
100 parts by weight of an alkali-soluble resin Sarbox SB400 (available from Saedoma corporation), 300 parts by weight of dipentaerythritol hexaacrylate (available from Saedoma corporation), 200 parts by weight of G36+ Y156 pigment (DIC corporation), 40 parts by weight of a photoinitiator OXE-01(Basf corporation), 40 parts by weight of a polyfunctional monomer compound A1, 500 parts by weight of a solvent propylene glycol methyl ether acetate (Dow corporation), 10 parts by weight of a silane coupling agent OFS-6030(Dow-Corning corporation) and 10 parts by weight of a leveling agent EB350 (available from Saedoma corporation) were mixed uniformly to obtain a photosensitive resin composition R13 of this example.
Example 26
100 parts by weight of an alkali-soluble resin Sarbox SB400 (available from Sartomer Co.), 20 parts by weight of dipentaerythritol hexaacrylate (available from Sartomer 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 (available from Sartomer Co.) were mixed uniformly to obtain a photosensitive resin composition R14 of this example.
Example 27
100 parts by weight of an alkali-soluble resin Sarbox SB400 (available from Saedoma corporation), 180 parts by weight of dipentaerythritol hexaacrylate (available from Saedoma corporation), 80 parts by weight of G36+ Y156 pigment (DIC corporation), 20 parts by weight of a photoinitiator OXE-01(Basf corporation), 6.7 parts by weight of a polyfunctional monomer compound A1, 267 parts by weight of a solvent propylene glycol methyl ether acetate (Dow corporation), 6.7 parts by weight of a silane coupling agent OFS-6030(Dow-Corning corporation) and 6.7 parts by weight of a leveling agent EB350 (available from Saedoma corporation) were mixed uniformly to obtain a photosensitive resin composition R15 of this example.
Example 28
A photosensitive resin composition R16 of this example was obtained by using 100 parts by weight of an alkali-soluble resin Sarbox SB400 (available from Saedoma), 167 parts by weight of dipentaerythritol hexaacrylate (available from Saedoma), 80 parts by weight of G36+ Y156 pigment (DIC), 20 parts by weight of a photoinitiator OXE-01 (Basf), 267 parts by weight of propylene glycol monomethyl ether acetate (Dow) as a solvent, and 20 parts by weight of a polyfunctional monomer compound A1.
Comparative example 1
A photosensitive resin composition R17 was obtained by using the raw materials of example 7 except that the polyfunctional monomer compound A1 was replaced with dipentaerythritol hexaacrylate in an equal weight ratio.
Comparative example 2
A photosensitive resin composition R18 was obtained by using the raw materials of example 7 except that the polyfunctional monomer compound A1 was replaced with an equal weight of benzoic acid as a developing aid.
Test examples
The photosensitive resin compositions R1-R18 were uniformly mixed, subjected to prebaking at 100 ℃ for 2min, exposure (exposure 60mj/cm2), development and postbaking at 230 ℃ for 20min, and tested for the adhesion, development time (time required for complete development) and viscosity change rate of the optical filter comprising the cured film of the resin composition, the results of which are shown in Table 1;
the adhesion test method comprises the following steps: scratching the optical filters of the cured films of the resin compositions containing R1-R18 by using a hundred-grid knife, and counting the number of the peeled photoresist blocks, wherein the number of the peeled photoresist blocks is listed in Table 1;
the viscosity change rate test method comprises the following steps: the photosensitive resin compositions R1-R18 were left at 5 ℃ for 6 months, and the viscosities before and after the leaving were measured, respectively, and the calculated viscosity change rates are shown in Table 1;
TABLE 1
As can be seen from table 1, the photosensitive resin compositions R1 to R16 containing the polyfunctional monomer compound of the present disclosure have significantly improved developing performance and significantly improved adhesion between the cured resin and the substrate, as compared with the photosensitive resin composition R17 of comparative example 1, and the photosensitive resin compositions R1 to R16 containing no acidic developing agent have significantly improved storage stability, as compared with the photosensitive resin composition R18 of comparative example 2 containing an acidic developing agent, and the data comparison between example 13 and example 28(R1 and R16) shows that the development of the photosensitive resin is faster and the adhesion between the cured resin and the substrate is higher when the photosensitive resin composition preferred in the present disclosure further contains an agent.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that the various features described in the foregoing embodiments may be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as disclosed in the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A polyfunctional monomer compound, characterized in that the compound has a structure represented by formula (1);
wherein R is1Is alkyl with 1-10 carbon atoms, haloalkyl 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;
R2derived from a hydroxyl group-containing multifunctional acrylate monomer which is di (methacryloyloxyethyl) hydrogen phosphate.
2. The polyfunctional monomer compound according to claim 1, wherein the alkyl group having 1 to 10 carbon atoms is at least one selected from the group consisting of a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, and a neopentyl group;
in the halogenated alkyl group with 1-10 carbon atoms, the number of halogen atoms is F, Cl or Br, and the number of the halogen atoms 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 a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group and a butylphenyl group.
3. The multi-functional monomer compound of claim 2, wherein R is1Is at least one selected from the group consisting of 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 the structures represented by formula (11) to formula (13):
5. a method of preparing a multifunctional monomer compound, the method comprising:
contacting the intermediate compound represented by formula (14) with a multifunctional acrylate monomer containing a hydroxyl group under a substitution reaction condition to obtain a multifunctional monomer compound represented by formula (1);
wherein R is1Is alkyl with 1-10 carbon atoms, haloalkyl 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；
R2Derived from the hydroxyl group-containing polyfunctional acrylate monomer which is hydrogen di (methacryloyloxyethyl) phosphate.
6. The method of claim 5, wherein the molar ratio of the intermediate of 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 0.5-3 h.
7. The method of claim 5 or 6, further comprising: 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 is1Is alkyl with 1-10 carbon atoms, haloalkyl 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 0.5-3 h.
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 polyfunctional 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, based on 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 acrylate resin, and the photosensitive monomer is at least one of 1, 6-ethyleneglycol 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 at least one of a cracking free radical photoinitiator and/or a cationic photoinitiator, and 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-benzoyl oxime), 1- (6-O-methylbenzoyl-9-ethyl-9. H. -carbazole-3-yl) -ethanone oxime-O-acetate and ethyl 2,4, 6-trimethylbenzoylphenylphosphonate.
10. The photosensitive resin composition according to claim 8, further comprising a solvent and/or an auxiliary, wherein the solvent is at least one selected from 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 is at least one selected from a sensitizer, a silane coupling agent, an antifoaming agent, and a leveling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210147555.3A CN114524841B (en) | 2017-01-17 | 2017-01-17 | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210147555.3A CN114524841B (en) | 2017-01-17 | 2017-01-17 | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition |
| CN201710036388.4A CN108314692B (en) | 2017-01-17 | 2017-01-17 | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710036388.4A Division CN108314692B (en) | 2017-01-17 | 2017-01-17 | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114524841A true CN114524841A (en) | 2022-05-24 |
| CN114524841B CN114524841B (en) | 2024-02-23 |
Family
ID=62891695
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210147555.3A Active CN114524841B (en) | 2017-01-17 | 2017-01-17 | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition |
| CN201710036388.4A Active CN108314692B (en) | 2017-01-17 | 2017-01-17 | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710036388.4A Active CN108314692B (en) | 2017-01-17 | 2017-01-17 | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN114524841B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213446B (en) * | 2021-11-03 | 2022-11-25 | 阜阳欣奕华材料科技有限公司 | Multifunctional monomer, preparation method and application thereof, and photoresist |
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 |
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 |
|---|---|
| CN114524841B (en) | 2024-02-23 |
| CN108314692A (en) | 2018-07-24 |
| CN108314692B (en) | 2022-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6127130B2 (en) | Novel oxime ester fluorene compound, photopolymerization initiator containing the same, and photoresist composition | |
| JP6039859B2 (en) | Novel β-oxime ester fluorene compound, photopolymerization initiator containing the same, and photoresist composition | |
| JP5647738B2 (en) | High-sensitivity carbazole oxime ester photoinitiator, process for its production and use | |
| KR101320243B1 (en) | Photosensitive resin composition, overcoat layer and electronic device using the same | |
| KR102228630B1 (en) | Carbazole multi β-oxime ester derivative compounds and, photopolymerization initiator and photoresist composition containing the same | |
| WO2016154782A1 (en) | Squarylium compounds used for lcd color filters | |
| TWI644903B (en) | Oxime ester derivative compounds, photopolymerization initiator, and photosensitive composition containing the same | |
| KR20140023224A (en) | Photosensitive alkali-soluble resin, method of preparing the same, and color photosensitive resist containing the same | |
| JPWO2020090746A1 (en) | Resin composition, photosensitive resin composition, cured film, method for producing cured film, method for producing pattern cured film and pattern cured film | |
| CN108314692B (en) | Multifunctional monomer compound, preparation method thereof and photosensitive resin composition | |
| TWI603949B (en) | Novel oxime ester biphenyl compound, and photo-initiator and photosensitive resin composition containing the same | |
| KR101928489B1 (en) | Coloring agent compound and coloring composition comprising the same | |
| KR101991903B1 (en) | Carbazole oxime ester derivative compounds and, photopolymerization initiator and photosensitive composition containing the same | |
| KR102232349B1 (en) | Negative-type photosensitive resin composition having high thermoresistance and hardened overcoat layer prepared therefrom | |
| KR20170019413A (en) | Anthraquinone compound used for color filter of lcd | |
| TW201630874A (en) | Novel di-oxime ester compound and photopolymerization initiator and photoresist composition including the same | |
| KR102466525B1 (en) | Novel biphenyl oxime ester compounds, photopolymerization initiator and photoresist composition containing the same | |
| CN115612112B (en) | Organophosphorus macromolecular initiator, preparation method thereof and photocuring composition | |
| US4661611A (en) | Polyfunctional acylsilane crosslinking agents and photocrosslinking systems comprising the same | |
| KR101920357B1 (en) | Novel oxime ester compound and photoresist composition containing the same | |
| KR102509606B1 (en) | Novel quinolinyl beta oxime ester derivative compound, photopolymerization initiator, and photoresist composition containing the same | |
| KR20200081834A (en) | Photosensitive resin composition and insulating film prepared therefrom | |
| CN117891131A (en) | Hydrophobic low-temperature cured resin composition and preparation method and application thereof | |
| KR20200081858A (en) | Photosensitive resin composition and insulating film prepared therefrom | |
| KR20140049717A (en) | Negative-type photosensitive resin composition comprising an organosiloxane polymer and hardened overcoat layer prepared therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |