CN104614940A - Photosensitive resin composition and application thereof - Google Patents
Photosensitive resin composition and application thereof Download PDFInfo
- Publication number
- CN104614940A CN104614940A CN201510061684.0A CN201510061684A CN104614940A CN 104614940 A CN104614940 A CN 104614940A CN 201510061684 A CN201510061684 A CN 201510061684A CN 104614940 A CN104614940 A CN 104614940A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- methyl
- acrylate
- cycloalkyl
- independently
- 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
- 239000011342 resin composition Substances 0.000 title abstract 5
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 125000006850 spacer group Chemical group 0.000 claims abstract description 8
- -1 oxime ester Chemical class 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003086 colorant Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 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 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003607 modifier Substances 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
- 229950002366 nafoxidine Drugs 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 7
- 230000006978 adaptation Effects 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 239000000049 pigment Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000003605 opacifier Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000549 coloured material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
- C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
- C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- 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
-
- 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
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Abstract
The invention discloses a photosensitive resin composition. The photosensitive resin composition comprises ultraviolet photosensitive prepolymer resin, an active diluent monomer, an oxime ether photoinitiator represented by the formula (I), and a colouring agent. The photosensitive resin composition has the good exposure sensibility and developing property; on the premise of low amount of a light-screening agent, or low exposure amount, a cured pattern is complete, clear to develop and high in resolution ratio; the adaptation between the cured pattern and a substrate is excellent; and the photosensitive resin composition has very good application prospects in the aspects of optical colour filters, light spacers, rib barriers and the like.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of photosensitive polymer combination and in the optical colour filters such as colour television set, liquid crystal display cells, solid-state image pickup and camera and light spacer (phtospacer) and rib grid (rib) etc. in application.
Background technology
Photosensitive composite adds Photoepolymerizationinitiater initiater and obtains in the polymerizable compound with unsaturated link, makes its polymerizing curable mainly through irradiation energy ray, and it plays decisive role in the production of optical colour filter.In recent years, along with the raising that people require quality of life, also more and more higher to the requirement of LCDs image sharpness, this has the features such as resolution is high, good with substrate adaptation, the residue that develops is few with regard to needing the photosensitive composite for the formation of color filter image.In actual use, in the pixel that optical concentration is high and resin bottom system, often the painted material content such as pigment, carbon black is higher, and the increase of coloured material concentration can have a negative impact to resolution, substrate adaptation, development residue, not only need to improve the exposure in exposure process or prolonging exposure time, but also the precision of color filter can be reduced.
Summary of the invention
In view of the foregoing, the object of the present invention is to provide a kind of new photosensitive polymer combination, (namely it have good exposure sensitivity, ISO) and developability, when system contains opacifier or exposure dose is very low, after solidification, pattern is complete and develop clear, and resolution is high, with substrate excellent adhesion.
To achieve these goals, following technical scheme is adopted.
A kind of photosensitive polymer combination, is characterized in that, comprise following component:
(A) 20-60 mass parts ultraviolet photosensitive resin resin;
(B) 10-40 mass parts activity diluting monomer;
(C) 1-5 mass parts light trigger, this light trigger is selected from one or more the combination in oxime ester lightlike initiating agent shown in formula (I),
Wherein,
X, Y represent carbonyl (-CO-) or singly-bound independently of one another;
A represents N, O, S or CH;
R
1can be sky or represent hydrogen, C
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl or C
4-C
20alkyl-cycloalkyl;
R
2and R
3represent hydrogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl, C
4-C
20alkyl-cycloalkyl, C
7-C
20aralkyl or C
2-C
20heterocyclic radical ,-OR
11,-COR
11,-COOR
11,-SR
11,-SO
2r
11or-CONR
11r
12, wherein R
11and R
12represent hydrogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl, C
4-C
20alkyl-cycloalkyl, C
7-C
20aralkyl or C
2-C
20heterocyclic radical; Optionally, R
2and R
3in hydrogen can be selected from-OR
21,-COR
21,-SR
21,-NR
22r
23,-CONR
22r
23,-NR
22-OR
23,-NCOR
22-OCOR
23,-C (=N-OR
21)-R
22,-C (-N-OCOR
21)-R
22, CN, halogen atom ,-CR
21=CR
22r
23,-CO-CR
21=CR
22r
23, group in carboxyl and epoxy radicals replaces, wherein R
21, R
22and R
23represent hydrogen, C independently of one another
1-C
20alkyl, C
6-C
30aryl, C
7-C
30aralkyl or C
2-C
20heterocyclic radical; Optionally, R
11, R
12, R
21, R
22and R
23in methylene can by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond interrupt 1-5 time; Above-mentioned substituent moieties can have branched building block, also can be naphthenic base, and above-mentioned substituent alkyl end also can be unsaturated link, and R
11, R
12, and R
21, R
22, R
23also can be connected to form ring arbitrarily each other.
R
4and R
5represent C independently of one another
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl, C
4-C
20alkyl-cycloalkyl, C
3-C
20heteroaryl, C
6-C
20aryl; Optionally, the group that the hydrogen in these groups can be selected from halogen, phenyl, nitro, hydroxyl, carboxyl, sulfonic group, amino, cyano group and alkoxy replaces;
R
6and R
7represent hydrogen or nitro independently of one another.
(D) colorant of 0-50 mass parts.
Another object of the present invention is to provide above-mentioned photosensitive polymer combination preparing the application in colored filter film, black matrix", light spacer and rib grid.
In photosensitive composite of the present invention, component (C) light trigger and component (A), (B) and (D) have good suitability.Composition has very high light sensitivity, just can well crosslinking curing under very low exposure dose, and solidification effect is splendid.The smooth zero defect of the film edge be made up of said composition, does not have scum silica frost, and pattern is complete clear, and hardness is high.The optical filter optical clarity made is high, not light leak, complete making, and precision is good, smooth, durable under very low exposure dose.Meanwhile, composition of the present invention still makes the elite clone of light spacer, black matrix" and rib grid.
Detailed Description Of The Invention
Above-mentioned photosensitive polymer combination of the present invention has ISO and good developability, resolution high and with substrate excellent adhesion, be applicable to very much in order to prepare the black matrix" (BM) of high light-proofness, fine and the color filter of high-quality and liquid crystal indicator, and also can be applied in light spacer and rib grid etc.
Photosensitive polymer combination of the present invention comprises component (A)-(D), below will be described in more details each component.
In the description of the invention, except as otherwise noted, term " ... (methyl) acrylic acid ... " ex hoc genus anne statement all relate to " ... acrylic acid ... " " ... methacrylic acid ... " two kinds of situations.
< component (A) ultraviolet photosensitive resin resin >
In photosensitive polymer combination of the present invention, component (A) preferably uses the Epocryl with carboxyl, as at least one in the homopolymer of (methyl) acrylic acid, itaconic acid, crotonic acid and partial esterification maleic acid or multipolymer, one or more the potpourri more preferably in epoxy acrylic ester prepolymer, acrylic ester prepolymer, polyurethane acrylate prepolymer, aliphatic urethane acrylate prepolymer, aromatic urethane acrylate prepolymer, polyester acrylic ester prepolymer.
Further preferably, component (A) ultraviolet photosensitive resin resin is one or more homopolymer in methacrylic acid, (methyl) methyl acrylate, (methyl) benzyl acrylate, (methyl) ethyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) i-butyl base ester or multipolymer.
As weight-average molecular weight (Mw) the preferably 5000-250000 of the polymkeric substance that component (A) uses, be more preferably 10000-50000.
Component (A) consumption in photosensitive polymer combination is preferably 25-60 mass parts, is more preferably 40-50 mass parts.
< component (B) activity diluting monomer >
In photosensitive polymer combination of the present invention, aptly, component (B) activity diluting monomer is one or more acrylic ester monomer, and described acrylic ester monomer is preferred: (methyl) acrylate of the aklylene glycol such as ethylene glycol, propylene glycol; (methyl) acrylate of the poly alkylene glycol such as polyglycol, polypropylene glycol; Poly-(methyl) acrylate of the above polyvalent alcohols of ternary such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol or its dicarboxylic acid modifier; Oligomeric (methyl) acrylate such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin; (methyl) acrylate etc. of the two terminal hydroxyl fluidized polymers such as two terminal hydroxyl polyisoprene, two terminal hydroxyl polycaprolactones, the poly-1,3-butadiene of two terminal hydroxyls.
Further preferably, component (B) activity diluting monomer is one or more the mixing in trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three ((methyl) acryloyloxyethyl) phosphate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.
Component (B) consumption in photosensitive polymer combination is preferably 15-40 mass parts, is more preferably 25-35 mass parts.
< component (C) light trigger >
One or more combination in oxime ester lightlike initiating agent shown in component (C) light trigger preferred formula (II),
Wherein,
R
1represent hydrogen, C
1-C
10straight or branched alkyl, C
3-C
10naphthenic base, C
4-C
15cycloalkyl-alkyl or C
4-C
15alkyl-cycloalkyl;
R
2and R
3represent hydrogen, C independently of one another
1-C
10straight or branched alkyl, C
3-C
15naphthenic base, C
4-C
15cycloalkyl-alkyl, C
4-C
15alkyl-cycloalkyl, C
7-C
15aralkyl or C
2-C
15heterocyclic radical ,-OR
11,-COR
11,-COOR
11,-SR
11,-SO
2r
11,-CONR
11r
12, wherein R
11and R
12represent hydrogen, C independently of one another
1-C
10straight or branched alkyl, C
3-C
15naphthenic base, C
4-C
15cycloalkyl-alkyl, C
4-C
15alkyl-cycloalkyl, C
7-C
15aralkyl or C
2-C
15heterocyclic radical; Optionally, R
2and R
3in hydrogen can be selected from-OR
21,-COR
21,-SR
21,-NR
22r
23,-CONR
22r
23,-NR
22-OR
23,-NCOR
22-OCOR
23,-C (=N-OR
21)-R
22,-C (-N-OCOR
21)-R
22,-CN, halogen atom ,-CR
21=CR
22r
23,-CO-CR
21=CR
22r
23, carboxyl and epoxy radicals group replace, wherein R
21, R
22and R
23represent hydrogen atom, C independently of one another
1-C
20alkyl, C
6-C
15aryl, C
7-C
15aralkyl or C
2-C
15heterocyclic radical; Optionally, R
11, R
12, R
21, R
22and R
23in methylene can by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond interrupt 1-5 time; Above-mentioned substituent moieties can have branched building block, also can be naphthenic base, and above-mentioned substituent alkyl end also can be unsaturated link, and R
11, R
12and R
21, R
22, R
23also can be connected to form ring arbitrarily each other;
R
4and R
5represent C independently of one another
1-C
10straight or branched alkyl, C
3-C
15naphthenic base, C
4-C
15cycloalkyl-alkyl, C
4-C
15alkyl-cycloalkyl, C
3-C
15heteroaryl or C
6-C
15aryl;
R
6and R
7represent hydrogen or nitro independently of one another.
Further preferably, in oxime ester lightlike initiating agent shown in formula (II):
R
1represent C
1-C
8straight or branched alkyl, particularly methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 6-methylheptyl;
R
2and R
3represent C independently of one another
3-C
5straight or branched alkyl ,-O-CH
2-R
31,-CH
2-O-R
31,-CH
2-S-R
31,-CH
2-OCO-CH
2-R
31,-CO-CH
2-R
31,-CH
2-CH
2-R
31, or-OCO-R
31, wherein R
31represent C
4-C
6naphthenic base or heterocyclic radical; Particularly preferably, described straight or branched alkyl is selected from n-pro-pyl, normal-butyl, isobutyl, R
31representative ring amyl group, cyclohexyl, 2-furyl, 2-tetrahydrofuran base or 1-nafoxidine base; Further, R
2and R
3in at least one be above-mentioned containing R
31group;
R
4and R
5represent C independently of one another
1-C
5straight or branched alkyl, particularly methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl;
R
6and R
7represent hydrogen or nitro independently of one another.
More specifically, one or more the combination of the light trigger described in component (C) preferably in compound shown in having structure:
< component (D) colorant >
Photosensitive polymer combination of the present invention can contain component (D) colorant further.Without limitation, by containing colorant, composition of the present invention can be used for the color filter forming liquid crystal display; And when using opacifier as colorant, composition can be used for the black-face picture tube formed in the color filter of display device.
Kind for component (D) colorant is not particularly limited, and can be color index (colorindex) (C.I.; The Society of Dyers and Colourists society issues) in be classified into those compounds of pigment (Pigment), preferably there is the colorant of following C.I. sequence number:
C.I. pigment yellow 1 (below because " C.I. pigment yellow " is identical so only record sequence number), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185,
C.I. pigment orange 1 (below because " C.I. pigment orange " is identical so only record sequence number), 5,13,14,16,17,24,34,36,38,40,43,46,49,51,55,59,61,63,64,71,73;
C.I. pigment violet 1 (below because " C.I. pigment violet " is identical so only record sequence number), 19,23,29,30,32,36,37,38,39,40,50;
C.I. paratonere 1 (below because " C.I. paratonere " is identical so only record sequence number), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265,
C.I. pigment blue 1 (below because " C.I. alizarol saphirol " is same so only record sequence number), 2,15,15:3,15:4,15:6,16,22,60,64,66;
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37;
C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment brown 26, C.I. pigment brown 28;
C.I. pigment black 1, C.I. pigment black 7.
When selecting opacifier as colorant, preferably use black pigment as opacifier.As black pigment, can enumerate: carbon black, titanium black (titanium black), the metal oxide of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc., composite oxides, metal sulfide, metal sulfate or metal carbonate etc.In these black pigments, preferably using the carbon black with high light-proofness, can be the common carbon blacks such as channel black, furnace black, thermal black, lamp black carbon black, preferably uses the channel black of light-proofness excellence; Also can use resin-coating carbon black.In addition, in order to adjust the tone of carbon black, can be suitable for adding organic pigment listed above as auxiliary pigment.Practice shows, even if the black pigment using light-proofness high in photosensitive polymer combination of the present invention, also can show extraordinary developability and pattern integrity.
Other optional components > of <
According to product application needs, in photosensitive polymer combination of the present invention, also optionally add other auxiliary agent conventional in this area, include but not limited to sensitizer, spreading agent, surfactant, solvent etc.
< preparations and applicatio >
Mix after each component being taken according to quantity, can obtain photosensitive polymer combination of the present invention, this belongs to known technology routinely to those skilled in the art.
The present invention also aims to provide above-mentioned photosensitive polymer combination preparing the application in colored filter film, black matrix", light spacer and rib grid.
Photosensitive composite is utilized to prepare the technology of RGB, BM, light spacer etc. known by those skilled in the art by photocuring and photoetching process.Generally include following steps:
I) photosensitive polymer combination is dissolved in suitable organic solvent, mixes, obtain liquid composition;
Ii) utilize coating machine, such as spin coater, coiling rod coating machine, axle coating machine or spray coating machine etc., be uniformly coated on liquid composition on substrate;
Iii) carrying out front baking dries dry, except desolventizing;
Iv) mask plate is attached on sample exposes, the unexposed area of development removing subsequently;
V) carry out rear baking, obtain the photoresist dry film with desired shape.
Photoresist film containing black pigment is exactly black matrix" BM, and the photoresist film containing red, green, blue look pigment is exactly corresponding R, G, B photoresistance.
Embodiment
The invention will be further described by the following examples, but should not be understood as limiting the scope of the invention.
preparation embodiment
According to the listed formula of table 1, the photosensitive polymer combination of preparation embodiment 1-8 and comparative example 1-4, the structure of the light trigger A1-A4 wherein in comparative example 1-4 is as follows:
Table 1
The photosensitive polymer combination prepared is dissolved in the solvent propylene glycol monomethyl ether acetate (PGMEA) of 100 mass parts, mixes, form fluid composition;
Utilize spin coater by fluid composition coating on the glass substrate, then at 100 DEG C, dry 5min, except desolventizing, forms the film that thickness is 8 μm; For obtaining the film of above-mentioned thickness, coating procedure can be once complete also can carry out several times;
Substrate with film is cooled to room temperature, encloses mask plate, and employing LED light source (according to Vata LED UV solidifying radiation device, maximum illumination intensity 400mW/cm
2), film is exposed under the Ultraviolet radiation of 370-420nm wavelength by the gap of mask plate;
At 25 DEG C of temperature, use the NaOH aqueous development of 1%, then use milli-Q water, air-dry;
Finally, after in the baking oven of 240 DEG C, toast 30min, obtain the pattern of mask plate transfer.
performance evaluation
1, exposure sensitivity evaluation
By residual film ratio after the development of light irradiation zone in step of exposure 90% or more minimum exposure amount be evaluated as exposure demand, exposure demand less expression sensitivity is higher.
2, developability and pattern integrity evaluation
Pattern on substrate is observed, to evaluate developability and pattern integrity by scanning electron microscope (SEM).
Developability is according to following standard evaluation:
Zero: do not observe residue at unexposed portion;
◎: observe a small amount of residue at unexposed portion, but residual quantity can accept;
●: observe obvious residue at unexposed portion.
Pattern integrity is according to following standard evaluation:
△: do not observe pattern defect;
: observing fraction pattern has fewer defects;
▲: obviously observe many pattern defects.
3, hardness evaluation
Evaluate with reference to GB/T 6739-1996 " hardness of film pencil determination method ".Use film pencil scratch hardness instrument, observe paint film scratch marks, to have no the pencil hardness of pencil for film of cut.
4, adhesion evaluation
With reference to GB9286-88 " cross cut test of paint and varnish paint film ", by drawing lattice Evaluation on the experiment method film adhesive quality.Be divided into 0-5 level (totally 6 grades) according to destructiveness, be wherein preferably 0 grade, face does not have any one little lattice to come off; 5 grades is extreme difference, and face creates serious peeling off.
Evaluation result is as shown in table 2.
Table 2
From the results shown in Table 2, the optical filter photoresistance obtained by the composition of embodiment 1-8 has good developability and pattern integrity, and adhesion and hardness aspect are also higher than general initiating agent, and comparative example 1-4 obvious Shortcomings in these areas.It is significant to note that, embodiment 1-8 exposure dose equal to 45mJ/cm
2, well below comparing embodiment 1-4, show extremely excellent luminous sensitivity.
In sum, photosensitive polymer combination of the present invention shows very excellent application performance, has broad application prospects.
Claims (9)
1. a photosensitive polymer combination, is characterized in that, comprises following component:
(A) 20-60 mass parts ultraviolet photosensitive resin resin;
(B) 10-40 mass parts activity diluting monomer;
(C) 1-5 mass parts light trigger, this light trigger is selected from one or more the combination in oxime ester lightlike initiating agent shown in formula (I),
Wherein,
X, Y represent carbonyl (-CO-) or singly-bound independently of one another;
A represents N, O, S or CH;
R
1can be sky or represent hydrogen, C
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl or C
4-C
20alkyl-cycloalkyl;
R
2and R
3represent hydrogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl, C
4-C
20alkyl-cycloalkyl, C
7-C
20aralkyl or C
2-C
20heterocyclic radical ,-OR
11,-COR
11,-COOR
11,-SR
11,-SO
2r
11or-CONR
11r
12, wherein R
11and R
12represent hydrogen, C independently of one another
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl, C
4-C
20alkyl-cycloalkyl, C
7-C
20aralkyl or C
2-C
20heterocyclic radical; Optionally, R
2and R
3in hydrogen can be selected from-OR
21,-COR
21,-SR
21,-NR
22r
23,-CONR
22r
23,-NR
22-OR
23,-NCOR
22-OCOR
23,-C (=N-OR
21)-R
22,-C (-N-OCOR
21)-R
22, CN, halogen atom ,-CR
21=CR
22r
23,-CO-CR
21=CR
22r
23, group in carboxyl and epoxy radicals replaces, wherein R
21, R
22and R
23represent hydrogen, C independently of one another
1-C
20alkyl, C
6-C
30aryl, C
7-C
30aralkyl or C
2-C
20heterocyclic radical; Optionally, R
11, R
12, R
21, R
22and R
23in methylene can by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond interrupt 1-5 time; Above-mentioned substituent moieties can have branched building block, also can be naphthenic base, and above-mentioned substituent alkyl end also can be unsaturated link, and R
11, R
12, and R
21, R
22, R
23also can be connected to form ring arbitrarily each other;
R
4and R
5represent C independently of one another
1-C
20straight or branched alkyl, C
3-C
20naphthenic base, C
4-C
20cycloalkyl-alkyl, C
4-C
20alkyl-cycloalkyl, C
3-C
20heteroaryl, C
6-C
20aryl; Optionally, the group that the hydrogen in these groups can be selected from halogen, phenyl, nitro, hydroxyl, carboxyl, sulfonic group, amino, cyano group and alkoxy replaces;
R
6and R
7represent hydrogen or nitro independently of one another.
(D) colorant of 0-50 mass parts.
2. photosensitive polymer combination according to claim 1, is characterized in that: component (A) ultraviolet photosensitive resin resin is selected from one or more the potpourri in epoxy acrylic ester prepolymer, acrylic ester prepolymer, polyurethane acrylate prepolymer, aliphatic urethane acrylate prepolymer, aromatic urethane acrylate prepolymer, polyester acrylic ester prepolymer.
3. photosensitive polymer combination according to claim 1 and 2, is characterized in that: component (A) ultraviolet photosensitive resin resin is one or more homopolymer in methacrylic acid, (methyl) methyl acrylate, (methyl) benzyl acrylate, (methyl) ethyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) i-butyl base ester or multipolymer.
4. photosensitive polymer combination according to claim 1, it is characterized in that, component (B) activity diluting monomer is one or more acrylic ester monomer, and described acrylic ester monomer is selected from: (methyl) acrylate of the aklylene glycol such as ethylene glycol, propylene glycol; (methyl) acrylate of the poly alkylene glycol such as polyglycol, polypropylene glycol; Poly-(methyl) acrylate of the above polyvalent alcohols of ternary such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol or its dicarboxylic acid modifier; Oligomeric (methyl) acrylate such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin; (methyl) acrylate etc. of the two terminal hydroxyl fluidized polymers such as two terminal hydroxyl polyisoprene, two terminal hydroxyl polycaprolactones, the poly-1,3-butadiene of two terminal hydroxyls.
5. the photosensitive polymer combination according to claim 1 or 4, is characterized in that: component (B) activity diluting monomer is one or more the mixing in trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three ((methyl) acryloyloxyethyl) phosphate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.
6. photosensitive polymer combination according to claim 1, is characterized in that, component (C) light trigger is selected from one or more the combination in oxime ester lightlike initiating agent shown in formula (II),
Wherein,
R
1represent hydrogen, C
1-C
10straight or branched alkyl, C
3-C
10naphthenic base, C
4-C
15cycloalkyl-alkyl or C
4-C
15alkyl-cycloalkyl;
R
2and R
3represent hydrogen, C independently of one another
1-C
10straight or branched alkyl, C
3-C
15naphthenic base, C
4-C
15cycloalkyl-alkyl, C
4-C
15alkyl-cycloalkyl, C
7-C
15aralkyl or C
2-C
15heterocyclic radical ,-OR
11,-COR
11,-COOR
11,-SR
11,-SO
2r
11,-CONR
11r
12, wherein R
11and R
12represent hydrogen, C independently of one another
1-C
10straight or branched alkyl, C
3-C
15naphthenic base, C
4-C
15cycloalkyl-alkyl, C
4-C
15alkyl-cycloalkyl, C
7-C
15aralkyl or C
2-C
15heterocyclic radical; Optionally, R
2and R
3in hydrogen can be selected from-OR
21,-COR
21,-SR
21,-NR
22r
23,-CONR
22r
23,-NR
22-OR
23,-NCOR
22-OCOR
23,-C (=N-OR
21)-R
22,-C (-N-OCOR
21)-R
22,-CN, halogen atom ,-CR
21=CR
22r
23,-CO-CR
21=CR
22r
23, carboxyl and epoxy radicals group replace, wherein R
21, R
22and R
23represent hydrogen atom, C independently of one another
1-C
20alkyl, C
6-C
15aryl, C
7-C
15aralkyl or C
2-C
15heterocyclic radical; Optionally, R
11, R
12, R
21, R
22and R
23in methylene can by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond interrupt 1-5 time; Above-mentioned substituent moieties can have branched building block, also can be naphthenic base, and above-mentioned substituent alkyl end also can be unsaturated link, and R
11, R
12and R
21, R
22, R
23also can be connected to form ring arbitrarily each other;
R
4and R
5represent C independently of one another
1-C
10straight or branched alkyl, C
3-C
15naphthenic base, C
4-C
15cycloalkyl-alkyl, C
4-C
15alkyl-cycloalkyl, C
3-C
15heteroaryl or C
6-C
15aryl;
R
6and R
7represent hydrogen or nitro independently of one another.
7. photosensitive polymer combination according to claim 6, is characterized in that, in oxime ester lightlike initiating agent shown in formula (II):
R
1represent C
1-C
8straight or branched alkyl, particularly methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 6-methylheptyl;
R
2and R
3represent C independently of one another
3-C
5straight or branched alkyl ,-O-CH
2-R
31,-CH
2-O-R
31,-CH
2-S-R
31,-CH
2-OCO-CH
2-R
31,-CO-CH
2-R
31,-CH
2-CH
2-R
31, or-OCO-R
31, wherein R
31represent C
4-C
6naphthenic base or heterocyclic radical; Particularly preferably, described straight or branched alkyl is selected from n-pro-pyl, normal-butyl, isobutyl, R
31representative ring amyl group, cyclohexyl, 2-furyl, 2-tetrahydrofuran base or 1-nafoxidine base; Further, R
2and R
3in at least one be above-mentioned containing R
31group;
R
4and R
5represent C independently of one another
1-C
5straight or branched alkyl, particularly methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl;
R
6and R
7represent hydrogen or nitro independently of one another.
8. the photosensitive polymer combination according to any one of claim 1-7, is characterized in that, component (C) light trigger is selected from one or more the combination in compound shown in having structure:
9. the photosensitive polymer combination according to any one of claim 1-8 is preparing the application in colored filter film, black matrix", light spacer and rib grid.
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| CN201510061684.0A CN104614940B (en) | 2015-02-05 | 2015-02-05 | A kind of photosensitive polymer combination and its application |
| PCT/CN2016/073119 WO2016124127A1 (en) | 2015-02-05 | 2016-02-01 | Photosensitive resin composition and application thereof |
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|---|---|---|---|
| CN201510061684.0A CN104614940B (en) | 2015-02-05 | 2015-02-05 | A kind of photosensitive polymer combination and its application |
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| CN104614940B CN104614940B (en) | 2019-04-09 |
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| WO (1) | WO2016124127A1 (en) |
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| WO2016124127A1 (en) * | 2015-02-05 | 2016-08-11 | 常州强力先端电子材料有限公司 | Photosensitive resin composition and application thereof |
| CN106444282A (en) * | 2015-08-13 | 2017-02-22 | 常州强力先端电子材料有限公司 | Photosensitive resin composition containing oxime ester photoinitiator and application of photosensitive resin composition |
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| CN110066225A (en) * | 2018-01-23 | 2019-07-30 | 常州强力先端电子材料有限公司 | Double oxime ester lightlike initiating agents, preparation method, photosensitive polymer combination and application |
| JP7370425B1 (en) | 2022-06-23 | 2023-10-27 | 東洋インキＳｃホールディングス株式会社 | Photosensitive composition for organic EL display device and organic EL display device |
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| WO2016124127A1 (en) * | 2015-02-05 | 2016-08-11 | 常州强力先端电子材料有限公司 | Photosensitive resin composition and application thereof |
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| JP2017167399A (en) * | 2016-03-17 | 2017-09-21 | 株式会社Ｄｎｐファインケミカル | Photosensitive coloring resin composition for color filter, color filter, and display |
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| CN107325206B (en) * | 2016-04-12 | 2018-12-18 | 常州强力先端电子材料有限公司 | One kind oxime ester lightlike initiating agent containing nitrocarbazole and its preparation method and application |
| CN107300828A (en) * | 2016-04-15 | 2017-10-27 | 常州强力电子新材料股份有限公司 | A kind of photosensitive resin for 3D printing |
| CN109459914A (en) * | 2017-09-06 | 2019-03-12 | 常州强力先端电子材料有限公司 | Light curing resin composition and its application |
| CN110066225A (en) * | 2018-01-23 | 2019-07-30 | 常州强力先端电子材料有限公司 | Double oxime ester lightlike initiating agents, preparation method, photosensitive polymer combination and application |
| CN110066225B (en) * | 2018-01-23 | 2022-06-03 | 常州强力先端电子材料有限公司 | Dioxime ester photoinitiator, preparation method, photosensitive resin composition and application |
| JP7370425B1 (en) | 2022-06-23 | 2023-10-27 | 東洋インキＳｃホールディングス株式会社 | Photosensitive composition for organic EL display device and organic EL display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104614940B (en) | 2019-04-09 |
| WO2016124127A1 (en) | 2016-08-11 |
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