CN107765510B - 9-phenylacridine macromolecular photosensitizer and preparation method and application thereof - Google Patents
9-phenylacridine macromolecular photosensitizer and preparation method and application thereof Download PDFInfo
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- CN107765510B CN107765510B CN201610673715.2A CN201610673715A CN107765510B CN 107765510 B CN107765510 B CN 107765510B CN 201610673715 A CN201610673715 A CN 201610673715A CN 107765510 B CN107765510 B CN 107765510B
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- photosensitizer
- phenylacridine
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 47
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 14
- 229920002521 macromolecule Polymers 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Chemical group 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 206010034960 Photophobia Diseases 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 208000013469 light sensitivity Diseases 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- 239000000543 intermediate Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- -1 acridine compound Chemical class 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000012634 fragment Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 150000001251 acridines Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33379—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group
- C08G65/33393—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33317—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group heterocyclic
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a 9-phenylacridine macromolecule photosensitizer which is at least one of compounds with a structure shown as a formula (I). When the photosensitizer is applied to a photocuring system, the compatibility is good, the improvement effect on the light sensitivity is good, and the prepared film has excellent resolution and adhesive force and high water solubility.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a 9-phenylacridine macromolecular photosensitizer, a preparation method thereof, and application of the photosensitizer in the field of photocuring.
Background
The acridine compound is a macrocyclic conjugated system, has a rigid planar structure, has extremely strong fluorescence performance, is a good fluorescent reagent, can be used as a photoinitiator in a photopolymerization system, and can also be used as a sensitizer to initiate the photoinitiator for photopolymerization. The 9-phenylacridine is a derivative of acridine, belongs to a biphenyl structure, can initiate the crosslinking and curing of photocuring materials (photocuring coating, printing ink, photoresist and the like) mainly composed of unsaturated resin and monomer materials thereof under ultraviolet light, X rays or illumination, has stable properties, and has good photosensitivity in the photocuring materials composed of the unsaturated resin and the monomer materials thereof, thereby being widely applied to the photocuring field.
The use of acridine compounds as photosensitizers is known, and for example, chinese patent applications CN101525392A, CN102675203A, etc. disclose the use of different acridine compounds in photosensitive resins. However, these acridine compounds have disadvantages such as unsatisfactory solubility and poor sensitivity-enhancing effect when used as photosensitizers. The 9-phenylacridine is one of the most widely used products in the existing acridine photosensitizer, and as a micromolecule photosensitizer, the micromolecule photosensitizer often has the problems of difficult separation from reactants, difficult recovery or poor intersolubility with a system, easy agglomeration and precipitation and the like in the using process, so that the reaction efficiency is reduced, and the material performance is influenced. In particular, the extremely low water solubility of 9-phenylacridine seriously affects the popularization and application of the 9-phenylacridine as a photosensitizer in the field of photocuring, particularly dry film photoresist. In the dry film development stage, unexposed parts are usually washed away by using an alkaline aqueous solution, and 9-phenylacridine is precipitated and adsorbed on the surface of the circuit board at the moment due to the extremely low water solubility, so that the use of the dry film is influenced, the precision of a product is reduced, and a subsequent circuit board surface cleaning procedure needs to be added, so that the process is complicated, and the cost is greatly increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a 9-phenylacridine macromolecular photosensitizer. Compared with the traditional photosensitizer, the photosensitizer has good compatibility when applied to a photocuring system, and has good effect of improving the light sensitivity, and the prepared film has excellent resolution and adhesive force and high water solubility (is easy to clean and remove).
Specifically, the 9-phenylacridine macromolecule photosensitizer is at least one of compounds with the structure shown in the formula (I):
wherein,
R1is represented by C1-C60Is a straight or branched alkyl group having a valence of m + n, wherein-CH2-optionally (optinally) substituted by oxygen, sulphur or 1, 4-phenylene;
a independently of one another denotes- [ (CHR)4)x-O]y-, wherein R4Each independently represents hydrogen, methyl or ethyl, x is an integer from 1 to 10, and y is an integer from 1 to 20;
R2is represented by C1-C20Straight or branched alkylene of (a), wherein-CH2-optionally substituted by oxygen, sulphur or phenylene;
R3represents hydrogen or a substituent group;
m represents an integer of 0 to 20, and n represents an integer of 1 to 20.
Preferably, R is1Is represented by C1-C20Is a straight or branched alkyl group having a valence of m + n, wherein-CH2-optionally substituted by oxygen or 1, 4-phenylene, provided that there is no direct linkage between the two oxygens.
More preferably, in the structure represented by the formula (I), R is1Selected from the following groups:
preferably, A represents- [ (CHR)4)x-O]y-, wherein R4Each independently represents hydrogen, methyl or ethyl, x is an integer of 1 to 10, and y is an integer of 1 to 20. - [ (CHR)4)x-O]y-the terminal oxygen atom of the group withR1Are connected.
Further preferably, a is selected from the group consisting of:
-[CH2O]y-、-[CH2CH2O]y-、-[CH2CH2CH2O]y-、-[CH2CH2CH2CH2O]y-、-[CH(CH3)-CH2O]y-、-[CH2-CH(CH3)-CH2O]y-, wherein y represents an integer of 1 to 20.
Preferably, R is2Is represented by C1-C8Straight or branched alkylene of (a), wherein-CH2-optionally substituted by oxygen or 1, 4-phenylene, provided that there is no direct linkage between the two oxygens.
Further preferably, R2Selected from the group consisting of:
*CH2*、*CH2-CH2*、*CH2-CH2-CH2*、*CH(CH3)-CH2*、*CH2CH2CH2CH2*、*CH2-O-CH2*、*CH2-CH2-O-CH2*、*CH2-CH2-O-CH2-CH2*。
preferably, R3Selected from H, CH3、NO2Or halogen (e.g., F, Cl, Br).
Preferably, m represents an integer of 0 to 7, n represents an integer of 1 to 8, and the sum of m and n is an integer of 2 to 8.
Correspondingly, the invention also relates to a preparation method of the 9-phenylacridine macromolecular photosensitizer, which comprises the following steps:
(1) reacting the raw material a and the raw material b under the action of a catalyst to obtain an intermediate a;
(2) reacting the intermediate a and the raw material c in a solvent containing an acid-binding agent to obtain an intermediate b;
(3) the intermediate b and the raw material d are subjected to ester exchange reaction under the action of a catalyst to obtain a product;
the reaction equation is as follows:
wherein R is5Is represented by C1-C8Linear or branched alkyl.
The photosensitizer of the invention is an improvement and optimization of the structure of the existing compound. As shown in the above reaction equation, the synthesis involved in the preparation method involves acridine structure construction, esterification, ester exchange, etc., which are conventional processes in the field of organic chemistry. Specific process parameters are readily determined by those skilled in the art, given the specifics of the synthesis process and its principles. See, for example, the disclosure in chinese patent CN101525392A, which is incorporated herein by reference in its entirety.
Preferably, in step (1), the catalyst is a composite catalyst of zinc chloride and 85% phosphoric acid. The reaction temperature is slightly different according to the types of raw materials, and is usually 150 ℃ to 220 ℃, and the reaction time is 4-8 h.
Preferably, in step (2), R in the structure of the raw material c5Is represented by C1-C4Straight or branched alkyl of, especially CH3、CH2CH3、CH2CH2CH3. The type of solvent used is not particularly limited as long as it can dissolve the reaction raw materials and does not adversely affect the reaction, and examples thereof include acetone, acetonitrile, methanol, ethanol, and N, N-dimethylformamide. The acid-binding agent can be sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine, triethylamine and the like. The reaction temperature is 40-100 ℃ and the reaction time is usually 4-18 h.
Preferably, in step (3), the transesterification reaction is carried out in a solvent. The solvent is not particularly limited as long as it can dissolve the reaction raw material and does not adversely affect the reaction, and examples thereof include toluene, xylene, benzene, cyclohexane, and the like. The catalyst can be one or the combination of more than two of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid and hypophosphorous acid. The amount of the catalyst used is preferably 5 to 15 parts per thousand of the total mass of the reaction raw materials. The reaction temperature is generally from 70 to 130 ℃. The reaction time is generally from 1 to 8 h.
As can be seen by those skilled in the art from the transesterification reaction of step (3), m + n hydroxyl groups capable of undergoing transesterification with intermediate b are present in starting material d. This leads to the formation of a single R when m + n is greater than 1 and the intermediate b is deficient with respect to the hydroxyl group1(AOH)m+nThere are instances where there is inconsistency in the number of intermediates b in the molecular reaction, resulting in the resulting product not being a single structural compound, but rather a mixture of structural compounds of formula (I). Such mixtures fall within the definition of the above-mentioned 9-phenylacridine macromolecule-based photosensitizer.
The 9-phenylacridine macromolecular photosensitizer has excellent water solubility, is particularly suitable for being used as a photosensitizer in a photocuring system, has a good light sensitivity improvement effect, and the prepared film has good resolution and adhesion. Therefore, the invention also relates to the application of the 9-phenylacridine macromolecular photosensitizer in a photocuring composition, wherein the photoinitiator used in the photocuring composition is preferably selected from a photoacid generator, a photobase generator and a free radical photoinitiator.
The beneficial effects of the invention also include:
1. energy transfer and intermolecular reaction in a macromolecular chain become easier, so that the macromolecular photosensitizer has higher photosensitive activity;
2. the distance between photosensitive groups is adjusted and designed through copolymerization with inactive groups, or the distance between the photoactive groups and the main chain is changed, so that products with different reactivity are obtained;
3. the high molecular of the photosensitive group limits the migration of the photosensitive group, thereby preventing the yellowing and aging of the coating;
4. since most of the photolytic fragments remain attached to the polymeric matrix, the odor and toxicity of the system can be reduced.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Preparation examples
Example 1
(1) Preparation of intermediate 1a
165.6g (1.2mol) of p-hydroxybenzoic acid, 169.0g (1.0mol) of diphenylamine, 244.8g (1.8mol) of zinc chloride and 115.3g (1.0mol) of 85% phosphoric acid were added to a 1000ml four-necked flask, and the mixture was stirred and heated to 200 ℃ and 210 ℃ for reaction for 6 hours. Then cooling to 130-;
the structure of intermediate 1a was confirmed by LCMS.
Mass spectrometry analysis was performed with the aid of software attached to the instrument to obtain 272 and 273 molecular fragment peaks, the molecular weight of the product was 271, consistent with T +1 and T + 2.
(2) Preparation of intermediate 1b
Adding 27.1g (0.1mol) of intermediate 1a, 16.6g (0.12mol) of potassium carbonate and 167g of acetonitrile into a 500mL four-neck flask, heating and refluxing at 80 ℃, dropwise adding 12.0g (0.11mol) of methyl chloroacetate, finishing dropwise adding for about 1h, continuing to react for 8h after dropwise adding is finished, filtering to remove unreacted potassium carbonate when the solution is hot, evaporating most of solvent under reduced pressure, precipitating solid, performing suction filtration, rinsing with methanol, and drying to obtain 32.5g of light yellow solid, namely intermediate 1b with the purity of 98%;
intermediate 1b is structurally characterized by LCMS and1H-NMR was confirmed.
Mass spectrometry analysis was performed with the aid of the instrument attached software to obtain 344 and 345 molecular fragment peaks, with the product having a molecular weight of 343, consistent with T +1 and T + 2.
1H-NMR(CDCl3，500MHz)：3.6721(3H，s)，4.9034(2H，s)，6.7254-6.8351(2H，d)，7.2812-7.3708(2H，d)，7.3424-7.4765(2H，d),7.5432-7.6278(4H，d),7.9234-8.0509(2H，d)。
(3) Preparation of product 1
154.3g (0.45mol) of the intermediate 1b, 166.2g (0.3mol) of the raw material 1d, 1.3g of lithium hydroxide and 540g of toluene are added into a 1000mL four-neck flask, the internal temperature is controlled to be 90-100 ℃, heating and stirring are carried out, methanol generated by the reaction is evaporated while heating is carried out, the toluene is supplemented timely until no methanol is evaporated, the mixture is filtered when the mixture is hot, the obtained filtrate is subjected to reduced pressure distillation until the toluene residue is less than 5000ppm, and 304.4g of light yellow viscous substance, namely the product 1, is obtained.
It will be understood that starting material 1d has 3 hydroxyl groups of the same or similar reactivity, and that products 1-1, 1-2 and 1-3 are included in product 1 due to the difference in the degree of molecular reaction of the individual starting material 1 d.
Example 2
(1) Preparation of intermediate 2a
219.6g (1.2mol) of 4-hydroxy-3-nitrobenzoic acid benzoic acid, 169.0g (1.0mol) of diphenylamine, 244.8g (1.8mol) of zinc chloride and 115.3g (1.0mol) of 85% phosphoric acid are added into a 1000ml four-port bottle, the temperature is raised to 200 ℃ and 210 ℃ by stirring, the reaction is carried out for 6h, and the liquid phase tracking reaction is carried out until the reaction is finished. Cooling to 130-;
the structure of intermediate 2a was confirmed by LCMS.
Mass spectrometry analysis with the aid of instrument attached software gave 317 and 318 molecular fragment peaks, with a product molecular weight of 316, consistent with T +1 and T + 2.
(2) Preparation of intermediate 2b
Adding 31.6g (0.1mol) of the intermediate 2a, 16.6g (0.12mol) of potassium carbonate and 156g of acetonitrile into a 500mL four-neck flask, heating and refluxing at 80 ℃, dropwise adding 13.4g (0.11mol) of ethyl chloroacetate, finishing dropwise adding for about 1h, continuing to react for 8h after dropwise adding is finished, filtering to remove unreacted potassium carbonate when the solution is hot, evaporating most of solvent under reduced pressure, precipitating solid, performing suction filtration, rinsing with methanol, and drying to obtain 36.8g of light yellow solid, namely the intermediate 2b with the purity of 98% and the yield of 91.5;
the structure of intermediate 2b was confirmed by LCMS.
Mass spectrometry was performed using the instrument with software to obtain 403 and 404 molecular fragment peaks, with the product having a molecular weight of 402, consistent with T +1 and T + 2.
The structure of intermediate 2b was confirmed by 1H-NMR.
1H-NMR(CDCl3，500MHz)：3.6721-3.7232(3H，t)，4.9034-4.9985(2H，q)，7.0942(2H，s)，7.3424-7.4765(2H，d),7.5432-7.6278(2H，q),7.6082-7.6191(2H，d)，7.7634-7.7705(2H，d)，7.9234-8.0509(2H，d)，8.3233(1H，s)。
(3) Preparation of product 2:
adding 180.4g (0.45mol) of the intermediate 2b, 79.8g (0.3mol) of the raw material 2d, 1.3g of lithium hydroxide and 540g of toluene into a 1000mL four-neck flask, controlling the temperature to be 90-100 ℃, heating and stirring, evaporating methanol generated by the reaction while heating, replenishing toluene timely until no methanol is evaporated, filtering while the solution is hot, and distilling the obtained filtrate under reduced pressure until the toluene residue is less than 5000ppm to obtain 221g of light yellow sticky matter, wherein the yield is 92.4%, and the mixture is the product 2.
Examples 3 to 9
Referring to the method of example 1 or 2, products 3 to 9 having the following structures were synthesized.
And (3) a product:
and (3) a product 4:
and (3) a product 5:
and (3) a product 6:
and (3) a product 7:
and (3) a product 8:
and (3) a product:
evaluation of Performance
The application properties of the photosensitizer of the present invention were evaluated by formulating an exemplary photocurable composition (i.e., a photosensitive resin composition).
1. Preparation of Performance evaluation object
< preparation of photosensitive resin laminate >
A photosensitive resin composition having a composition shown in Table 1 and propylene glycol monoethyl ether acetate were sufficiently stirred, mixed, coated on the surface of a 19 μm-thick polyethylene terephthalate film as a support using a bar, uniformly coated, and then dried in a dryer at 95 ℃ for 4min to form a photosensitive resin layer having a thickness of 40 μm. Subsequently, a polyethylene film having a thickness of 23 μm was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, to obtain a photosensitive resin laminate.
< leveling of substrate surface >
As a substrate for sensitivity and resolution evaluation, a ketone-coated laminate treated with a jet-cleaning grinder under a spray pressure of 0.20MPa was prepared.
< lamination >
While the polyethylene film of the photosensitive resin laminate was peeled off, the surface was flattened, and the laminate was laminated on a ketone-laminated sheet preheated to 60 ℃ by a hot roll laminator at a roll temperature of 105 ℃ under a gas pressure of 0.35MPa and a lamination speed of 1.5 m/min.
< Exposure >
Exposure was performed by an h-ray type direct writing exposure apparatus (Digital Light Processing) with an exposure amount of 8 in a stepwise exposure table evaluated in terms of sensitivity as described below.
< development >
After peeling off the polyethylene terephthalate film, the film was developed with 2.38 mass% aqueous tetramethylammonium hydroxide at 23 ℃ for 2min to dissolve and remove the unexposed portion of the photosensitive resin layer, and then washed with ultrapure water for one minute. At this time, the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved is set as the minimum development time.
TABLE 1
Note: the names/compositions of the components denoted by the symbols in table 1 are shown in table 2.
TABLE 2
2. Performance evaluation method
(1) Compatibility test
The photosensitive resin compositions having the compositions shown in Table 1 were sufficiently stirred and mixed, and uniformly applied to the surface of a 19 μm-thick polyethylene terephthalate film as a support by using a bar coater. Drying at 95 deg.C for 4min to form photosensitive resin layer. Thereafter, the coated surface was visually inspected and classified as follows:
◇, coating the surface evenly;
◆ undissolved substances are precipitated on the coated surface.
(2) Evaluation of sensitivity
The laminated substrate was exposed for 15min using a 21-step exposure table manufactured by Stouffer having a 21-step brightness change from transparent to black to evaluate its sensitivity. After exposure, development was performed for 2 times the minimum development time, and the following steps were performed according to the exposure amount of 8 in the step exposure table in which the resist film was completely left:
○ Exposure is 20mJ/cm2The following;
◎ Exposure is 20mJ/cm2-50mJ/cm2(not inclusive);
●: the exposure amount was 50mJ/cm2The above.
(3) Resolution evaluation
The laminated substrate was exposed for 15min through a line pattern mask in which the widths of the exposed and unexposed portions were in a ratio of 1: 1, and then developed with a time 2 times the minimum development time, to normally form the minimum mask line width of the cured resist line as a resolution value. The following classification was performed:
○, resolution value is below 30 μm;
◎ resolution values of 30 μm to 50 μm (not inclusive);
●: the resolution value is 50 μm or more.
(4) Evaluation of adhesion
The laminated substrate was exposed for 15min through a line pattern mask in which the widths of the exposed and unexposed portions were in a ratio of 1: 100, and then developed with a time 2 times the minimum development time to normally form the minimum mask line width of the cured resist line as an adhesion value. The following classification was performed:
○, the adhesion value is below 30 μm;
◎, the adhesion value is 30-50 μm (not including the end value);
●: the adhesion value is 50 μm or more.
(5) Evaluation of Water solubility
After peeling off the polyethylene terephthalate film, the film was developed with 2.38 mass% aqueous tetramethylammonium hydroxide at 23 ℃ for 2min to dissolve and remove the unexposed portion of the photosensitive resin layer, and then washed with ultrapure water for one minute. The following classification was performed:
◇, completely dissolving without solid residue;
◆ solid precipitated on the coated side.
3. Results of Performance evaluation
The results of the property evaluations are shown in Table 3.
TABLE 3
Note: 1-no resist lines formed, not fully cured, and not used for resolution and adhesion evaluation.
As can be seen from the evaluation results in table 3, the compositions using the 9-phenylacridine-based photosensitizer of the present invention (schemes 1 to 5) have good compatibility, high sensitivity, and good resolution and adhesion, and have good water solubility, which is significantly better than those of comparative examples 1 to 2 using the conventional photosensitizer, under the same other components. In contrast, in comparative example 3, in the case of only TPS photoacid generator, the composition was much lower in compatibility, sensitivity, resolution, adhesion and water solubility than the composition using the 9-phenylacridine-based photosensitizer of the present invention (schemes 1 to 5). Comparative example 4 shows that the composition did not cure at all in the absence of TPS and photosensitizer.
4. Further characterization
Photosensitive resin compositions having the formulations shown in Table 4 were prepared.
TABLE 4
Note: the names/compositions of the components denoted by the symbols in table 4 are shown in table 5.
TABLE 5
The sensitivity was evaluated by referring to the above evaluation methods, and the evaluation results are shown in table 6.
TABLE 6
Note: 1 — not fully cured.
Experiments show that when the photosensitizer is used alone, the photosensitive effect is poor, and the composition cannot be fully cured. When the photoinitiator is used in combination with a radical photoinitiator, a photobase generator, or the like, the sensitivity is higher than that when the photoinitiator is used alone, without changing the total amount.
In conclusion, the photosensitizer disclosed by the invention has very excellent application performance in the field of photocuring and has a wide application prospect. In addition, the photosensitizer of the present invention is not limited to the application fields shown in the above formula, and all systems such as photo-curing coating, ink and photoresist, etc., as long as the photosensitizer of the present invention is used, are within the protection scope of the present patent.
Claims (8)
1. A9-phenylacridine macromolecule photosensitizer is at least one of compounds with the structure shown as a formula (I):
wherein,
R1is represented by C1-C60Is a straight or branched alkyl group having a valence of m + n, wherein-CH2-optionally substituted by oxygen, sulphur or 1, 4-phenylene;
a independently of one another denotes- [ (CHR)4)x-O]y-, wherein R4Each independently represents hydrogen, methyl or ethyl, x is an integer from 1 to 10, and y is an integer from 1 to 20;
R2is represented by C1-C20Straight or branched alkylene of (a), wherein-CH2-optionally substituted by oxygen, sulphur or phenylene;
R3selected from H, CH3、NO2Or halogen;
m represents an integer of 0 to 20, and n represents an integer of 1 to 20.
2. The photosensitizer of claim 1, wherein the photosensitizer is a 9-phenylacridine macromolecule photosensitizer: r1Is represented by C1-C20Is a straight or branched alkyl group having a valence of m + n, wherein-CH2-optionally substituted by oxygen or 1, 4-phenylene, provided that there is no direct linkage between the two oxygens.
3. The photosensitizer of claim 1, wherein the photosensitizer is a 9-phenylacridine macromolecule photosensitizer: - [ (CHR)4)x-O]y-terminal oxygen atom of group with R1Are connected.
4. The photosensitizer of claim 1, wherein the photosensitizer is a 9-phenylacridine macromolecule photosensitizer: r2Is represented by C1-C8Straight or branched alkylene of (a), wherein-CH2-optionally substituted by oxygen or 1, 4-phenylene, provided that there is no direct linkage between the two oxygens.
5. The photosensitizer of claim 1, wherein the photosensitizer is a 9-phenylacridine macromolecule photosensitizer: m represents an integer of 0 to 7, n represents an integer of 1 to 8, and the sum of m and n is an integer of 2 to 8.
6. The method for producing a 9-phenylacridine macromolecular photosensitizer according to any one of claims 1 to 5, comprising the steps of:
(1) reacting the raw material a and the raw material b under the action of a catalyst to obtain an intermediate a;
(2) reacting the intermediate a and the raw material c in a solvent containing an acid-binding agent to obtain an intermediate b;
(3) the intermediate b and the raw material d are subjected to ester exchange reaction under the action of a catalyst to obtain a product;
the reaction equation is as follows:
wherein R is5Is represented by C1-C8Linear or branched alkyl.
7. Use of the 9-phenylacridine macromolecular photosensitizer according to any one of claims 1 to 5 in a photocurable composition.
8. Use according to claim 7, characterized in that: the photoinitiator used in the photocurable composition is selected from the group consisting of photoacid generators, photobase generators, and radical type photoinitiators.
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| JP2019503540A JP6697125B2 (en) | 2016-08-16 | 2017-08-01 | 9-phenylacridine large molecule photosensitizer, method for producing the same and use thereof |
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| CN102952071A (en) * | 2011-08-30 | 2013-03-06 | 比亚迪股份有限公司 | Ultraviolet curing monomer and preparation method thereof, polymerizable composition and backlight module |
| CN103819583A (en) * | 2014-03-18 | 2014-05-28 | 常州强力电子新材料股份有限公司 | Photoinitiator containing nitro dioxime ester and preparation method and application thereof |
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| JP2846132B2 (en) * | 1991-03-29 | 1999-01-13 | 日立化成工業株式会社 | Photoinitiator and photopolymerizable composition |
| DE19548623A1 (en) * | 1995-12-23 | 1997-06-26 | Hoechst Ag | 2-Acylamino-9-aryl-acridines, process for their preparation and light-sensitive mixtures containing them |
| JP5344034B2 (en) * | 2009-03-13 | 2013-11-20 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method |
| CN101525392B (en) * | 2009-03-31 | 2011-03-16 | 江苏工业学院 | 9-phenylacridine photoinitiator and preparation method thereof |
| EP2246330A1 (en) * | 2009-04-30 | 2010-11-03 | Siegwerk Benelux SA | New photoinitiators |
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| JP6221560B2 (en) * | 2012-09-27 | 2017-11-01 | Jnc株式会社 | Organic electroluminescence device |
| CN104151243B (en) * | 2014-07-22 | 2016-05-11 | 清华大学 | Prepare the method for polysubstituted Acridine derivatives |
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| CN102952071A (en) * | 2011-08-30 | 2013-03-06 | 比亚迪股份有限公司 | Ultraviolet curing monomer and preparation method thereof, polymerizable composition and backlight module |
| CN103819583A (en) * | 2014-03-18 | 2014-05-28 | 常州强力电子新材料股份有限公司 | Photoinitiator containing nitro dioxime ester and preparation method and application thereof |
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