CN1655932A - 稳定化红外敏感可聚合体系 - Google Patents
稳定化红外敏感可聚合体系 Download PDFInfo
- Publication number
- CN1655932A CN1655932A CN03811797.5A CN03811797A CN1655932A CN 1655932 A CN1655932 A CN 1655932A CN 03811797 A CN03811797 A CN 03811797A CN 1655932 A CN1655932 A CN 1655932A
- Authority
- CN
- China
- Prior art keywords
- compound
- composition
- group
- alkyl
- precursor
- 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
- 239000002243 precursor Substances 0.000 claims abstract description 77
- -1 mercapto compounds Chemical class 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 238000007639 printing Methods 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 92
- 239000000463 material Substances 0.000 claims description 38
- 239000000975 dye Substances 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 150000003254 radicals Chemical class 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 11
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical class ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000002955 isolation Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 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 7
- 150000001721 carbon Chemical group 0.000 claims description 7
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 6
- SYDGXXBZTSDRFV-UHFFFAOYSA-N 2-anilinooxy-2-oxoacetic acid Chemical compound OC(=O)C(=O)ONC1=CC=CC=C1 SYDGXXBZTSDRFV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 3
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 claims description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 239000001017 thiazole dye Substances 0.000 claims description 3
- 125000005259 triarylamine group Chemical group 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 2
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001072 heteroaryl group Chemical group 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 37
- 230000032683 aging Effects 0.000 description 19
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 16
- 230000006866 deterioration Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 15
- 238000000576 coating method Methods 0.000 description 13
- 238000003384 imaging method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 239000003086 colorant Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 150000002168 ethanoic acid esters Chemical class 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229920005692 JONCRYL® Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical class OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- XHQZJYCNDZAGLW-UHFFFAOYSA-N 3-methoxybenzoic acid Chemical compound COC1=CC=CC(C(O)=O)=C1 XHQZJYCNDZAGLW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YZGQDNOIGFBYKF-UHFFFAOYSA-N Ethoxyacetic acid Chemical compound CCOCC(O)=O YZGQDNOIGFBYKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000004455 (C1-C3) alkylthio group Chemical group 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- ASLICXGLMBICCD-UHFFFAOYSA-N 1-ethyl-4,5-dihydroimidazole Chemical compound CCN1CCN=C1 ASLICXGLMBICCD-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-M 2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-M 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
- CWQZLVPKEVXEOB-UHFFFAOYSA-N 2-(tribromomethyl)-1,3,5-triazine Chemical class BrC(Br)(Br)C1=NC=NC=N1 CWQZLVPKEVXEOB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- HWURWIWEIFEWDZ-UHFFFAOYSA-N 2-[carboxymethyl(ethyl)amino]benzoic acid Chemical compound OC(=O)CN(CC)C1=CC=CC=C1C(O)=O HWURWIWEIFEWDZ-UHFFFAOYSA-N 0.000 description 1
- SSERUHHPRWEKSG-UHFFFAOYSA-N 2-[n-(carboxymethyl)anilino]benzoic acid Chemical compound C=1C=CC=C(C(O)=O)C=1N(CC(=O)O)C1=CC=CC=C1 SSERUHHPRWEKSG-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- LABJFIBQJFPXHZ-UHFFFAOYSA-N 4-(carboxymethoxy)benzoic acid Chemical compound OC(=O)COC1=CC=C(C(O)=O)C=C1 LABJFIBQJFPXHZ-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- NGTZRRAYYJFRDA-UHFFFAOYSA-N 5-bromo-2-(carboxymethylamino)benzoic acid Chemical compound OC(=O)CNC1=CC=C(Br)C=C1C(O)=O NGTZRRAYYJFRDA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HJIYHOVBJRVELV-UHFFFAOYSA-N C(C)OCC(=S)OCCO Chemical compound C(C)OCC(=S)OCCO HJIYHOVBJRVELV-UHFFFAOYSA-N 0.000 description 1
- CIQFXAVBMIRPJD-UHFFFAOYSA-N CC(N=C1S)=N[S+]1S([O-])(=O)=O Chemical class CC(N=C1S)=N[S+]1S([O-])(=O)=O CIQFXAVBMIRPJD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LVJOFJVCBFMGPW-UHFFFAOYSA-N SC1=C(C(=O)O)C=C(C=C1C(=O)O)C Chemical compound SC1=C(C(=O)O)C=C(C=C1C(=O)O)C LVJOFJVCBFMGPW-UHFFFAOYSA-N 0.000 description 1
- UCVPMQYQGQJLTN-UHFFFAOYSA-N SC1=CC(CC(C(=O)O)=C1)(C(=O)O)C Chemical compound SC1=CC(CC(C(=O)O)=C1)(C(=O)O)C UCVPMQYQGQJLTN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000003331 infrared imaging Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- FOVRCVYQPBQVTL-UHFFFAOYSA-N isocyanatomethyl prop-2-enoate Chemical compound C=CC(=O)OCN=C=O FOVRCVYQPBQVTL-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 210000001138 tear Anatomy 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/107—Polyamide or polyurethane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/109—Polyester
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/145—Infrared
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Printing Plates And Materials Therefor (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明公开了某些巯基化合物作为储存寿命改进剂用于红外敏感平版印刷板前体的用途。这些化合物是包含氮原子和至少一个可以是氧,硫,或另一氮原子的其它杂原子的五元杂芳族环,使得两个环杂原子被键接至带有硫醇基团的环碳。
Description
发明领域
本发明涉及平版印刷板。更特别地,本发明涉及具有良好储存寿命的红外敏感平版印刷板前体。
发明背景
在平版印刷中,称作图像区域的油墨接受区域在亲水表面上产生。如果该表面被水润湿并施用油墨,亲水区域保留水和排斥油墨,而油墨接受区域接受油墨和排斥水。油墨被转移至其上要产生图像的材料的表面上。通常,油墨首先被转移至中间覆盖层上,然后又将油墨转移至其上要产生图像的材料的表面上。
可用于制造平版印刷板的一类称作印刷板前体的可成像元件包括在基材的亲水表面上的光敏层。光敏层包含一种或多种可分散在合适粘结剂中的辐射敏感组分。另外,辐射敏感组分可以是粘结剂材料自身。
如果在暴露于辐射之后,光敏层的曝光区域在显影工艺中被去除,露出基材的下方亲水表面,该元件称作正性工作的。相反,如果未曝光区域通过显影工艺被去除,该元件是负性工作的。在每种情况下,留下的辐射敏感层的区域(即,图像区域)是油墨接受性的,且通过显影工艺露出的亲水表面的区域接受水,通常自流溶液,并排斥油墨。
无需通过负片进行曝光的胶印印刷板的直接数字成像在印刷工业中正日益变得重要。通常用于使这些板成像的高性能激光器或激光二极管发出在800和1100nm之间的射线。
因此,通过这些辐射源要成像的印刷板前体必须对该波长区域内的射线敏感。这些印刷板前体可在环境光中处理,这明显有利于其生产,使用和处理。
可以用红外激光成像曝光的负性工作平版印刷板前体例如描述于EP-A-0 672 544;EP-A-0 672 954;DeBoer,U.S.Pat.No.5,491,046;和EP-A-0 819 985。但如果在热和/或潮湿气氛中储存,这些印刷板前体的可用性受限于其储存寿命。该储存寿命问题使得板在某些情况下仅可使用一个月或更短。因此,需要具有较长储存寿命的负性工作印刷板前体。
发明综述
本发明是一种红外敏感组合物,包含:
(i)引发剂体系,包含:
(a)至少一种能够吸收红外线的化合物,该化合物选自三芳基胺染料,噻唑鎓染料,吲哚鎓染料,噁唑鎓染料,菁染料,聚苯胺染料,聚吡咯染料,聚噻吩染料,和酞菁颜料,
(b)至少一种能够产生自由基的化合物,该化合物选自多卤代烷基取代的化合物,和
(c)至少一种表示为结构式(I)的羧酸:
R4-(CR5R6)n-Y-CH2COOH (I)
其中:
Y选自O,S和NR7;
R7选自氢,C1-C6烷基,-CH2CH2OH,和被-COOH取代的C1-C5烷基;
R4,R5和R6分别独立地选自氢,C1-C4烷基,取代的或未取代的芳基,-COOH和-NR8CH2COOH;
R8选自CH2COOH,-CH2OH,和-(CH2)2N(CH2COOH)2;和
n是0,1,2或3;
(ii)至少一种组分,选自不饱和自由基可聚合单体,自由基可聚合的不饱和低聚物,在主链和侧链之一或两者中包含自由基可聚合碳-碳双键的聚合物,和其混合物;
(iii)至少一种聚合物粘结剂;和
(iv)包含其上具有硫醇基团取代的芳族5-元杂环的杂环巯基化合物,所述环包含氮原子和至少一个选自氮,氧和硫的杂原子,其中杂原子在环中与氮原子被一个碳原子分开,和其中硫醇基团键合至碳原子上;
其中:
oxa<redb+1.6 eV,
其中oxa是组分(a)的氧化电势,以eV计,和redb是组分(b)的还原电势,以eV计。
在另一方面,本发明是一种包括基材和在该基材上的红外敏感组合物层的印刷板前体。
在另一方面,本发明是一种用于形成可用作平版印刷板的图像的方法,包括使前体成像方式曝光于红外线以形成在红外敏感组合物层中包含曝光和未曝光区域的成像方式曝光前体,和用显影剂显影该成像方式曝光前体以去除未曝光区域。
视需要,曝光前体可简短地在显影之前加热以增加在曝光区域中的固化。
在另一方面,本发明是一种通过成像方式曝光并随后显影该前体而形成的印刷板。
在本发明一个优选实施方案中,印刷板前体另外包括在红外敏感组合物层的外表面上的基本上氧不可渗透隔绝层。
不愿局限于任何特殊理论,而且认为该稳定化作用的确切机理尚未明确知晓,目前相信,为了同时实现高度辐射敏感度和高储存稳定性,所有的组分的存在是必要的。如果红外吸收化合物(a),多卤代烷基-取代的化合物(b),或羧酸(c)的任一种缺少的话,只能得到非常辐射不敏感的板前体。排除杂环巯基化合物(iv)导致储存不太稳定的组合物,但当存在引发剂体系的所有的组分(a),(b),和(c)时,辐射敏感度不受(iv)存在与否的明显影响。
发明的详细描述
杂环巯基化合物明显有利地增加红外敏感组合物和由其制成的印刷板前体在干和潮湿两种储存条件下在较高温度下的储存稳定性。不同于不含这些化合物的组合物,这些组合物保留良好的红外曝光敏感度和分辨细图像特征的能力。
本文所用的″烷基″包括直链,支化链,和环状烷基基团,除非另有定义。″芳基″是指碳环芳族基团和杂环芳族基团,其中一个或多个独立地选自N,O和S的杂原子存在于芳族环中。
碳环芳族基团的例子是苯基和萘基。杂环芳族基团的例子是2-吡啶基和4-吡啶基。″取代的或未取代的芳基″是指定义如上的芳基基团,视需要包含一个或多个独立地选自COOH,-OH,C1-C6烷基,-NH2,卤素(即氟,氯,溴和碘),C1-C4烷氧基,乙酰氨基,-OCH2COOH,-NHCH2COOH和芳基的取代基。
″总固体″是指存在于组合物中的非挥发性材料的量,即使存在于组合物中的一些材料在室温可以是液体。除非另有所指,″杂环巯基化合物,″″引发剂体系,″″羧酸,″″聚合物粘结剂″和类似术语还表示这些化合物或组分的混合物。
红外敏感组合物包含杂环巯基化合物,红外敏感引发剂体系,自由基可聚合组分,和聚合物粘结剂。
该组合物包含杂环巯基化合物或杂环巯基化合物的混合物。有用的杂环巯基化合物包括包含带有硫醇取代基的芳族5-元杂环的化合物,其中所述环包含氮原子和至少一个其它的氮原子,或氧原子或硫原子,其中硫,氧或第二个氮与第一个氮被一个带有硫醇基团的碳原子分开。合适的杂环巯基化合物包括,例如,3-巯基-1,2,4-三唑;3-巯基-4-甲基-4H-1,2,4-三唑;3-巯基-5-(4-吡啶基)-1H-1,2,4-三唑;2-巯基苯并咪唑;2-巯基苯并噁唑;2-巯基苯并噻唑;6-乙氧基-2-巯基苯并噻唑;2-巯基-5-甲基-1,3,4-噻二唑;2-巯基-5-苯基-1,3,4-噁二唑;2-巯基-5-(4-吡啶基)-1,3,4-噁二唑;5-巯基-3-甲基硫代-1,2,4-噻二唑;2-巯基-5-甲基硫代-1,3,4-噻二唑;2-巯基咪唑;2-巯基-1-甲基咪唑;5-巯基-1-甲基-1H-四唑;和5-巯基-1-苯基-1H-四唑。优选的杂环巯基化合物包括3-巯基-1,2,4-三唑;2-巯基苯并咪唑;2-巯基苯并噁唑;5-巯基-3-甲基硫代-1,2,4-噻二唑;和2-巯基-1-甲基咪唑。
红外敏感组合物优选包含约0.5至约10wt%,优选约2至约5wt%的杂环巯基化合物或杂环巯基化合物的混合物,基于红外敏感组合物的总固体。
红外敏感引发剂体系包含红外吸收化合物,产生自由基的化合物,和羧酸。
有用的红外吸收化合物通常具有在约750nm和约1200nm之间;更通常在约800nm和约1100nm之间的最大吸收。红外吸收化合物(a)选自三芳基胺染料,噻唑鎓染料,吲哚鎓染料,噁唑鎓染料,菁染料,聚苯胺染料,聚吡咯染料,聚噻吩染料和酞菁颜料。
优选的一组染料是菁染料。更优选的是具有结构式(A)的菁染料:
其中:
X1和X2分别独立地是S,O,NR或C(烷基)2;
R1a和R1b分别独立地是烷基基团,烷基磺酸盐基团,烷基羧酸盐基团或烷基铵基团;
R2是氢,卤素,SR,SO2R,OR或NR2;
R3a和R3b分别为独立地氢原子,烷基基团,COOR,OR,SR,NR2,卤素原子,或取代的或未取代的苯并稠合环;
R是烷基基团或芳基基团;
C是以足够实现菁染料(A)的电荷中性的量存在的抗衡离子;
---是两个氢原子或两碳或三碳链;和
n1和n2分别独立地是0,1,2或3。
这些菁染料吸收范围是750nm至1100nm。在甲醇溶液中吸收范围为790nm至850nm的具有结构式(A)的染料是优选的。
X1和X2分别优选为C(烷基)2基团。R1a和R1b分别优选为具有1至4个碳原子的烷基基团。R2优选为SR。R3a和R3b分别优选为氢原子。R优选为苯基基团。
破折线表示可有可无的环的剩余部分,优选具有5或6个碳原子。
抗衡离子C在一些情况下是负离子,在一些情况下是正离子,和在一些情况下根本不需要,这取决于R1a和R1b所贡献的总电荷。例如,如果R1a和R1b都带有单个负电荷,抗衡离子C必须带正电荷和以1当量抗衡离子C/摩尔菁染料(A)的含量存在。相反,如果R1a和R1b都是中性烷基基团,抗衡离子C必须带负电荷和以1当量抗衡离子C/摩尔菁染料(A)的含量存在。R1a和R1b的带正电荷的、带负电荷的、和中性实施方案的其它组合当然是可能的,且抗衡离子C的所需当量数可容易由本领域熟练技术人员确定。
如果需要负抗衡离子,C是强酸的共轭碱,如三氟甲烷磺酸盐,全氟丁酸盐,六氟磷酸盐,过氯酸盐,或任何这些的混合物。优选地,C是氯化物或甲苯磺酸盐。如果需要正抗衡离子,C是Na+,K+,Li+,NH4 +,烷基铵,或任何这些的混合物。
尤其优选的是具有对称的结构式(A)的红外吸收染料。这些尤其优选的染料的例子包括:2-[2-[2-苯基磺酰基-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚氯化鎓;2-[2-[2-硫代苯基-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚氯化鎓;2-[2-[2-硫代苯基-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环戊烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚甲苯磺酸鎓盐;2-[2-[2-氯-3-[2-乙基-(3H-苯并噻唑-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-3-乙基-苯并噻唑甲苯磺酸鎓盐;和2-[2-[2-氯-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚甲苯磺酸鎓盐。
以下也是有用的红外吸收剂:
红外敏感组合物优选包含约0.5至约8wt%,更优选约1至约3wt%红外吸收剂,基于红外敏感组合物的总固体。
引发剂体系包含能够产生自由基的化合物或化合物的混合物。体系包含多卤代烷基取代的化合物或多卤代烷基取代的化合物的混合物。这些化合物包含至少一个多卤化或几个单卤化或二卤化烷基取代基。卤化烷基基团优选具有1至3个碳原子。优选的卤化烷基基团是卤化甲基基团。
尤其合适的多卤代烷基取代的化合物包括,例如:2-(4-甲氧基苯基)-4,6-二(三氯甲基)-1,3,5-三嗪;2-(4-氯苯基)-4,6-二(三氯甲基)-1,3,5-三嗪;2-苯基-4,6-二(三氯甲基)-1,3,5-三嗪;2,4,6-三(三氯甲基)-1,3,5-三嗪;2,4,6-三(三溴甲基)-1,3,5-三嗪;和三溴甲基苯基砜。
红外敏感组合物优选包含基于红外敏感组合物总固体的约2至约15wt%,更优选约4至约7wt%的多卤代烷基取代的化合物或多卤代烷基取代的化合物的混合物。
多卤代烷基取代的化合物的吸收性能决定红外敏感组合物的日光稳定性。紫外/可见光最大吸收>330nm的化合物所产生的组合物在印刷板前体已在日光中保持6至8分钟并随后加热然后显影之后也不能完全显影。如果需要高度的日光稳定性,在>330nm处不具有明显紫外/可见光吸收的多卤代烷基取代的化合物是优选的。
能够吸收红外线的化合物(a)的氧化电势应该低于多卤代烷基取代的化合物(b)的还原电势加上1.6eV。
羧酸(c)表示为以下结构式(I)
R4-(CR5R6)n-Y-CH2COOH (I)
其中:
Y选自O,S和NR7,其中R7选自氢,C1-C6烷基,-CH2CH2OH,和被-COOH取代的C1-C5烷基;
R4,R5和R6分别独立地选自氢,C1-C4烷基,取代的或未取代的芳基,-COOH和-NR8CH2COOH;
R8是选自CH2COOH,-CH2OH和-(CH2)2N(CH2COOH)2;和
n是0,1,2或3。
有用的羧酸是,例如:(p-乙酰氨基苯基亚氨基)-二乙酸;3-(二(羧基甲基)氨基)苯甲酸;4-(二(羧基甲基)氨基)苯甲酸;2-[(羧基甲基)苯基氨基]-苯甲酸;2-[(羧基甲基)苯基氨基]-5-甲氧基苯甲酸;3-[二(羧基甲基)氨基]-2-萘羧酸;N-(4-氨基苯基)-N-(羧基甲基)甘氨酸;N,N′-1,3-亚苯基二甘氨酸;N,N′-1,3-亚苯基二[N-(羧基甲基)]甘氨酸;N,N′-1,2-亚苯基二[N-(羧基甲基)]甘氨酸;N-(羧基甲基)-N-(4-甲氧基苯基)甘氨酸;N-(羧基甲基)-N-(3-甲氧基苯基)甘氨酸;N-(羧基甲基)-N-(3-羟基苯基)甘氨酸;N-(羧基甲基)-N-(3-氯苯基)甘氨酸;N-(羧基甲基)-N-(4-溴苯基)甘氨酸;N-(羧基甲基)-N-(4-氯苯基)甘氨酸;N-(羧基甲基)-N-(2-氯苯基)甘氨酸;N-(羧基甲基)-N-(4-乙基苯基)甘氨酸;N-(羧基甲基)-N-(2,3-二甲基苯基)甘氨酸;N-(羧基甲基)-N-(3,4-二甲基苯基)甘氨酸;N-(羧基甲基)-N-(3,5-二甲基苯基)甘氨酸;N-(羧基甲基)-N-(2,4-二甲基苯基)甘氨酸;N-(羧基甲基)-N-(2,6-二甲基苯基)甘氨酸;N-(羧基甲基)-N-(4-甲酰基苯基)甘氨酸;N-(羧基甲基)-N-乙基邻氨基苯甲酸;N-(羧基甲基)-N-丙基邻氨基苯甲酸;N-(羧基甲基)-N-苄基甘氨酸;5-溴-N-(羧基甲基)邻氨基苯甲酸;N-(2-羧基苯基)甘氨酸;o-联茴香胺-N,N,N′,N′-四乙酸;4-羧基苯氧基乙酸;儿茶酚-O,O′-二乙酸;4-甲基儿茶酚-O,O′-二乙酸;间苯二酚-O,O′-二乙酸;对苯二酚-O,O′-二乙酸;α-羧基-o-茴香酸;4,4-亚异丙基二苯氧基乙酸;2,2′-(二苯并呋喃-2,8-二基二氧基)二乙酸;2-(羧基甲基硫代)苯甲酸;5-氨基-2-(羧基甲基硫代)苯甲酸;3-[(羧基甲基)硫代]-2-萘羧酸;亚乙基二胺四乙酸;次氨基三乙酸;二亚乙基三胺五乙酸;N-羟基乙基亚乙基二胺三乙酸;苯氧基乙酸;2,3-甲氧基苯氧基乙酸;(苯基硫代)乙酸;和(3,4-二甲氧基苯基硫代)乙酸。
优选的羧酸是N-芳基多羧酸,尤其是具有结构式(B)的那些
其中Ar是单-,多-或未取代的芳基基团,p是整数1至5,R9和R10独立地选自氢和C1-C4烷基,和q是0或整数1至3,
和具有结构式(C)的那些
其中R11是氢或C1-C6烷基基团,k和m分别独立地是整数1至5,和R9,R10和q定义如上。
结构式(B)中的芳基基团可被一个或多个C1-C3烷基基团,C1-C3烷氧基基团,C1-C3硫代烷基基团和/或卤素取代。芳基基团可具有1至3个相同或不同的取代基。p优选为1;Ar优选是苯基基团。
在结构式(B)和(C)中,基团R9和R10优选独立地选自氢和甲基;更优选R9和R10都是氢。q优选为0或1。k和m分别优选为1或2;R11优选为氢,甲基或乙基。
最优选的芳族羧酸是苯氨基二乙酸,N-(羧基甲基)-N-苄基甘氨酸和(3,4-二甲氧基苯基硫代)乙酸。
红外敏感组合物优选包含约1至约10wt%,更优选约1.5至约3wt%的羧酸,基于红外敏感组合物的总固体。
组分(ii)是具有至少一个烯属不饱和碳-碳双键的自由基可聚合化合物。它选自具有至少一个,和优选两个或多个端烯属不饱和键的那些化合物。这些化合物是熟知的和广泛用于本领域,且可没有任何特殊限制地用于本发明。作为不饱和自由基可聚合单体或低聚物,可使用例如丙烯酸,甲基丙烯酸,衣康酸,巴豆酸,异巴豆酸,马来酸,和富马酸的衍生物。优选的是单体,低聚物或预聚物形式的丙烯酸或甲基丙烯酸的酯。它们可以固体或液体形式存在,其中固体和高度粘稠形式是优选的。适用作单体的化合物包括例如三羟甲基丙烷三丙烯酸酯和三甲基丙烯酸酯,季戊四醇三丙烯酸酯和三甲基丙烯酸酯,二季戊四醇单羟基五丙烯酸酯和五甲基丙烯酸酯,二季戊四醇六丙烯酸酯和六甲基丙烯酸酯,季戊四醇四丙烯酸酯和四甲基丙烯酸酯,二(三羟甲基丙烷)四丙烯酸酯和四甲基丙烯酸酯,二甘醇二丙烯酸酯和二甲基丙烯酸酯,三甘醇二丙烯酸酯和二甲基丙烯酸酯,或四甘醇二丙烯酸酯和二甲基丙烯酸酯。合适的低聚物和/或预聚物是氨基甲酸乙酯丙烯酸酯和甲基丙烯酸酯,环氧化物丙烯酸酯和甲基丙烯酸酯,聚酯丙烯酸酯和甲基丙烯酸酯,聚醚丙烯酸酯和甲基丙烯酸酯,和不饱和聚酯树脂。
除了单体和低聚物,可使用在主链和/或在侧链中具有自由基可聚合碳-碳双键的聚合物。例子包括马来酸酐-烯烃共聚物与(甲基)丙烯酸羟基烷基酯的反应产物;包含烯丙基醇酯基团的聚酯;聚合物聚醇与异氰酸根合(甲基)丙烯酸酯的反应产物;不饱和聚酯;(甲基)丙烯酸酯封端的聚苯乙烯,(甲基)丙烯酸酯封端的聚(甲基)丙烯酸,(甲基)丙烯酸酯封端的聚(甲基)丙烯酸酯,(甲基)丙烯酸酯封端的聚(甲基)丙烯酸酰胺和(甲基)丙烯酸酯封端的聚醚。本文所用的″丙烯酸″或″丙烯酸酯″之前的前缀″(甲基)″表示可使用丙烯酸或甲基丙烯酸官能度。
优选的自由基可聚合组分是季戊四醇四丙烯酸酯,二季戊四醇五丙烯酸酯,二(三羟甲基丙烷)四丙烯酸酯,二甘醇二丙烯酸酯,包含烯丙基醇酯基团的预聚物,和低聚物氨基甲酸乙酯(甲基)丙烯酸酯。
红外敏感组合物优选包含约35至约60wt%,更优选约45至约55wt%的自由基可聚合组分,基于红外敏感组合物的总固体。
可用于本发明的粘结剂优选为线性有机聚合物。优选的粘结剂在常用作平版印刷板显影剂的水或弱碱性水溶液中是可溶或可膨胀的。本领域已知的各种各样的聚合物或聚合物混合物可用作聚合物粘结剂,例如丙烯酸共聚物,甲基丙烯酸共聚物,衣康酸共聚物,巴豆酸共聚物,马来酸共聚物,部分酯化马来酸共聚物,和酸性纤维素衍生物。优选,聚合物具有重均分子量10,000至1,000,000(通过凝胶渗透色谱测定)。
对于在印刷工艺过程中的良好的油墨接受性,优选的是,聚合物或聚合物混合物具有酸值>70mg KOH/g。酸值>110mg KOH/g的聚合物或聚合物混合物是更优选的。最优选的是酸值在140和160mg KOH/g之间的聚合物或聚合物混合物。
红外敏感组合物优选包含约30至约60wt%,更优选约35至约45wt%的聚合物粘结剂,基于红外敏感组合物的总固体。
红外敏感组合物可另外包含作为光可聚合组合物常规组分的组分,如增塑剂,脂肪敏化剂和着色剂。
红外敏感组合物可另外包含增塑剂。合适的增塑剂包括,例如,邻苯二甲酸二丁酯,三乙酰基甘油,磷酸三芳基酯,和邻苯二甲酸二辛酯。如果存在增塑剂,组合物优选包含约0.25至约2wt%增塑剂,基于组合物中的总固体。
红外敏感组合物可另外包含着色剂以帮助视觉检查曝光和显影的板前体。这有助于视觉检测图像缺陷,排字错误,等,和图像光密度计的使用。合适的着色剂是在用于涂覆的溶剂或溶剂混合物中溶解良好或容易以颜料分散形式被引入的那些。典型例子包括若丹明染料,三芳基甲烷染料,蒽醌颜料,偶氮型颜料和酞菁染料和/或颜料。如果存在着色剂,组合物通常包含约0.5wt%至约3wt%的着色剂。
为了提高成品板的油墨接受性,组合物也可包含脂肪敏化剂如聚甲基丙烯酸甲酯或聚乙酸乙烯酯。如果存在脂肪敏化剂或脂肪敏化剂的混合物,组合物通常包含约2.0wt%至约8.0wt%的脂肪敏化剂或脂肪敏化剂的混合物。
红外敏感组合物可包含非离子和/或两性表面活性剂或这些表面活性剂的混合物。这些表面活性剂提高涂覆性能(如板前体的化妆品)和增加在显影条件下的处理稳定性。合适的表面活性剂的例子是脱水山梨醇三硬脂酸酯,甘油单硬脂酸酯,聚氧基亚乙基壬基醚,烷基二(氨基乙基)甘氨酸,2-烷基-N-羧基乙基咪唑啉鎓甜菜碱,和全氟化合物。如果存在表面活性剂或表面活性剂的混合物,组合物优选包含约0.01至约1wt%,更优选约0.05至约0.5wt%的表面活性剂或表面活性剂的混合物。
印刷板前体包含在合适基材上的红外敏感组合物层和视需要在红外敏感组合物层上的基本上氧不可渗透隔绝层。
红外敏感组合物可应用于各种各样的基材。基材包括天然或合成载体,优选已被表面处理以提高红外敏感组合物粘附性和/或显影平版印刷板的非图像区域的亲水性。
基材优选是强健的,稳定的和柔性的片材。它应该耐受在使用条件下的尺寸改变,这样颜色记录会出现在全色图像中。通常,它可以是任何自承载材料,包括,例如,聚合物膜如聚对苯二甲酸乙二醇酯膜,陶瓷片材,金属片材,或硬纸,或任何这些材料的层压品。金属基材包括铝,锌,钛,铜和其合金,其中铝是优选的。
特殊基材一般根据预期用途决定。本发明的红外敏感组合物尤其适用于生产平版印刷板。
对于平版印刷,印刷板基材包括具有至少一个亲水表面的载体,后者可以是常用于制备平版印刷板前体的任何材料。铝箔和聚合物膜是常用的印刷板基材材料。通常,红外敏感材料在印刷板基材的亲水表面上形成一层。
基材的背面(即,与红外敏感材料层相对的面)可涂有抗静电剂和/或滑动层或无光粗糙层以提高红外敏感前体的使用和″感觉″。
如果印刷板基材是铝,表面可通过包括物理粒化,电化学粒化,化学粒化,和阳极化的本领域已知的技术进行处理。基材应该足够厚,通常约100至约600μm,以承受印刷磨损,而且要足够薄以在印刷形式周围缠绕。通常,基材包含在铝载体和红外敏感层之间的中间层。中间层可通过利用本领域熟知的手段和材料将载体例如涂以糊精,六氟硅酸,磷酸盐/氟化物混合物,聚乙烯基膦酸,聚乙烯基膦酸共聚物,或硅酸盐而形成。
前体可通过使用常规涂布或层压方法将红外敏感组合物层施用到基材的亲水表面之上而制成。通常将这些成分分散或溶解在合适的涂覆溶剂中,并将所得混合物通过常规方法,如旋涂,杆涂,凹版涂布,辊涂,浸涂,空气刮涂,料斗涂布,叶片涂布,和喷涂进行涂覆。术语″涂覆溶剂″包括溶剂混合物,尤其有机溶剂混合物。
对用于施用红外敏感层的溶剂的选择取决于存在于红外敏感组合物中的引发剂体系,可聚合组分,粘结剂,巯基化合物,和其它成分(如果有的话)的准确特性和量。可使用各种常规有机溶剂。但考虑到在干燥工艺过程中的便利,通常使用具有沸点约40℃至约160℃,优选约60℃至约130℃的溶剂。涂覆溶液的固体含量通常是约2至约25wt%,基于溶剂重量。
合适的有机溶剂包括,例如,醇如甲基醇,乙基醇,正-和异-丙基醇,正-和异-丁基醇和二丙酮醇;酮如丙酮,甲基乙基酮,甲基丙基酮,甲基丁基酮,甲基戊基酮,甲基己基酮,二乙基酮,二异丁基酮,环己酮,甲基环己酮,和乙酰基丙酮;多元醇和其衍生物如乙二醇,乙二醇单甲基醚或其乙酸酯,乙二醇单乙基醚或其乙酸酯,乙二醇二乙基醚,乙二醇单丁基醚或其乙酸酯,丙二醇单甲基醚或其乙酸酯,丙二醇单乙基醚或其乙酸酯,丙二醇单丁基醚,3-甲基-3-甲氧基丁醇;和特殊溶剂如二甲基亚砜,N,N-二甲基甲酰胺,乳酸甲酯,和乳酸乙酯。这些溶剂可单独或两种或多种溶剂混合使用。在涂覆工艺过程中施用的红外敏感组合物溶液或分散体的量优选在范围约10mL/m2至约100mL/m2内。
红外敏感前体的干燥通常使用热空气进行。空气温度优选为约30℃至约200℃,更优选约40℃至约120℃.空气温度可在干燥工艺过程中保持恒定,或可逐渐梯度升高。在一些情况下可有利地使用空气气流用于水分吸收。热空气可优选以速率约0.1m/s至约30m/s吹过该层之上,其中值约0.5m/s至约20m/s是尤其理想的。在干燥之后,红外敏感层的涂覆重量通常是约0.5至约4g/m2,优选约1至约3g/m2。
将常规氧不可渗透隔绝层优选施用到红外敏感层上。适用于此的材料包括,但不限于,聚乙烯基醇,聚乙烯基醇/聚乙酸乙烯酯共聚物,聚乙烯基吡咯烷酮,聚乙烯基吡咯烷酮/聚乙酸乙烯酯共聚物,聚乙烯基甲基醚,聚丙烯酸,聚乙烯基咪唑和明胶。这些聚合物可以是单独或结合使用。氧不可渗透隔绝层的干层重量优选为约0.1至约4g/m2,更优选约0.7至约2g/m2。该层不仅可用作氧隔绝层而且保护板前体在暴露于红外线过程中不受烧蚀。另外,隔绝层提高板前体的耐擦性,这对于易处理性非常重要。隔绝层也可包含在波长区域800至1100nm内不吸收,但能够在可见光区域中有效地吸收的着色剂(水可溶染料),这样提高前体在偶尔暴露于环境光时的稳定性。
将如此得到的印刷板前体使用市售设备用在800至1100nm范围内发光的半导体激光器或激光二极管曝光。这种激光束可通过计算机进行数字控制;即它可被开关使得板前体的成像方式曝光通过计算机中储存的数字化信息而进行。因此,本发明红外敏感组合物适用于制备也称作数字板前体的所谓计算机-至-板(ctp)印刷板前体。
通过成像方式曝光,红外敏感组合物的曝光区域变得不可通过显影剂被去除,而未曝光区域保持可被去除。在印刷板前体已被成像方式曝光之后,它视需要被简短地加热至温度约85至约135℃以固化曝光区域。根据所用的温度,这需要约20至约100秒。
随后板前体通过现有技术中常用的方法,通常使用市售含水碱性显影剂进行显影,去除红外敏感组合物的未曝光区域和留下曝光区域。显影板通常用防腐剂处理(″涂胶″)。防腐剂通常是一种或多种亲水聚合物,润湿剂和其它添加剂的水溶液。
工业实用性
红外敏感组合物可用于许多场合,包括,但不限于,用于在合适的载体和接受片材上产生图像的记录材料,产生可用作印刷板,筛网和类似物的浮雕,用作光刻胶,用作用于表面保护的辐射可固化清漆,和用于配制辐射可固化印刷油墨。尽管本发明组合物可用于许多场合,它们尤其可用于制备可通过红外线成像的负性工作平版印刷板前体。
本发明的有利的性能可通过参考用于说明而非限定本发明的以下实施例看出。
实施例
术语集
AC 50 | 甲基丙烯酸共聚物,酸值48mg KOH/g,在乙二醇单甲基醚中的70wt%溶液(PCAS,Longjumeau,France) |
AIRVOL203 | 聚乙烯基醇;12wt%残余乙酰基基团(AirProducts,Allentown,PA,USA) |
DESMODURN100 | 无溶剂的,包含缩二脲官能度的脂族三异氰酸酯树脂(Bayer,Leverkusen,德国)。 |
JONCRYL683 | 丙烯酸共聚物,酸值175mg KOH/g(S.C.Johnson,Racine,Wl,USA)。 |
MOWIOL4/88 | 聚乙烯基醇Clariant;12wt%残余乙酰基基团(ClariantInternational,Muttenz,Switzerl′and) |
PVI | 聚乙烯基咪唑(Panchim,Lisses,France) |
RENOLBlue B2GHW | 使用聚乙烯基缩丁醛制备的铜酞菁颜料(ClariantInternational,Muttenz,Switzerland) |
SCRIPSET540 | 马来酸酐丁基半酯/苯乙烯共聚物(Solutia,St.Louis,MO,USA) |
三元聚合物 | 45mol%苯乙烯,22mol%甲基丙烯酸,和33mol%甲基丙烯酸甲酯的三元聚合物,酸值130mg KOH/g |
氨基甲酸乙酯丙烯酸酯 | 通过DESMODURN100与丙烯酸羟乙基酯和季戊四醇三丙烯酸酯反应而得到的氨基甲酸乙酯丙烯酸酯的80%甲基乙基酮溶液,在异氰酸酯基团完全反应之后具有双键含量0.5摩尔双键/100g(在非挥发份基础上) |
实施例1
由以下组分制备涂覆溶液:6.4g JONCRYL683;8.0g AC 50;2.6g二季戊四醇五丙烯酸酯;16.8g氨基甲酸乙酯丙烯酸酯;0.8g苯氨基二乙酸;0.3g 2-[2-[2-硫代苯基-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚氯化鎓;1.5g 2-(4-甲氧基苯基)-4,6-二(三氯甲基)-1,3,5-三嗪;0.65g 3-巯基-1,2,4-三唑;和0.6g RENOLBlue B2G HW。组分在搅拌下溶解在由90体积份1-甲氧基-2-丙醇和10体积份丙酮组成的200mL混合物中。
在溶液过滤之后,将它施用到已用聚乙烯基膦酸水溶液通过标准方法预处理的电化学粒化和阳极化的铝箔,并将涂层在90℃下干燥4min。所得红外敏感层的干重达到约2g/m2。
然后,将具有干重2g/m2的氧不可渗透隔绝层通过使用具有以下组成的溶液涂覆而施用:42.5g AIRVOL203;7.5g PVI;和170g水。干燥在90℃下进行5min。如此制成的板前体称作″新鲜″板前体。
如此制成的前体使用具有830nm激光二极管的来自Creo/Scitex的Trendsetter 3244曝光。包含用于评估复制件质量的不同图像元件的UGRA/FOGRA Postscript Strip version 2.0 EPS(得自UGRA)用于成像。
曝光前体在配有预热部分,预洗部分,浸渍型显影浴,用于水漂洗的部分,和涂胶和干燥部分的MercuryNews处理器(Kodak PolychromeGraphics LLC)中处理。处理器用显影剂980(Kodak PolychromeGraphics LLC)填充。以下设定用于处理板前体:速度120cm/min,预热630,预洗速率0.5L/m2板,显影浴温度(23±1)℃。在该处理之后,曝光部分留在板上,而未曝光部分通过显影剂被完全去除。
为了评估在预加热和显影之后得到的复制件,检查以下标准:1-像素元件的复制质量,像素元件的检查板点的光学密度,和原色元件的光学密度。为了确定颜色对比度和实心和网孔点的密度,使用D19/D196装置(Gretag/Macbeth颜色数据体系,The Wirral,UK)。
能量需求的结果表明,为了原色的良好复制,需要曝光能量75mJ/cm2,而对于1-像素元件,需要105mJ/cm2。
将以105mJ/cm2曝光的板安装在片材加料式胶印平版印刷机中并检验。图像区域没有任何问题地接受油墨和纸复制件在非图像区域中没有表现出任何调色。在200,000次良好印刷之后,停止印刷,但板可用于更多的印刷品。
为了试验板前体的储存寿命,将它们进行快速模拟老化。为此,前体在一种情况下在保温箱中在温度60℃下加热15小时(以下称作″干老化″板前体),和在另一情况下在具有温度40℃和相对湿度80%的气候腔中储存7天(以下称作″湿老化″前体)。随后如上所述测定这些前体的红外敏感度和复制件结果。前体的未曝光区域可通过显影剂完全去除。能量需求的结果表明,对于原色的良好复制,需要曝光能85mJ/cm2(对于干老化前体)和85mJ/cm2(对于湿老化前体)。为了1-像素元件的良好复制,需要曝光118mJ/cm2(干老化)和115mJ/cm2(湿老化)。
将用良好复制1-像素元件所需的能量曝光的由湿老化和干老化前体制成的板安装在片材加料式胶印平版印刷机中并检测。图像区域没有任何问题地接受油墨和纸复制件在非图像区域中没有表现出任何调色。在200,000次良好印刷之后,停止印刷,但板可用于更多印刷品。
实施例2
实施例1使用以下涂覆溶液重复:2.5g SCRIPSET540;0.55g二季戊四醇五丙烯酸酯;3.4g氨基甲酸乙酯丙烯酸酯;0.18g苯氨基二乙酸;0.32g 2-[2-[2-氯-3-[2-乙基-(3H-苯并噻唑)-2-叉基]-1-环己烯-1-基]-乙烯基]-3-乙基-苯并噻唑甲苯磺酸鎓;0.32g三溴甲基苯基砜;和0.15g 2-巯基苯并咪唑。
能量需求的结果表明,对于新鲜前体的原色的良好复制,需要曝光能量85mJ/cm2,而对于1-像素元件,需要120mJ/cm2。对于原色的良好复制,需要曝光能量95mJ/cm2(对于干老化前体),和100mJ/cm2(对于湿老化前体)。对于1-像素元件的良好复制,需要曝光133mJ/cm2(干老化)和140mJ/cm2(湿老化)。这些结果表明,通过改变巯基化合物,红外染料,多卤代烷基化合物和聚合物粘结剂,新鲜和老化前体的敏感度参数几乎都保持恒定。
实施例3
重复实施例1,只是2-巯基苯并噁唑用于替代红外敏感层中的3-巯基-1,2,4-三唑。然后,氧不可渗透隔绝层2g/m2干层由50g MOWIOL4/88在170g水中的溶液涂覆。该层在90℃下干燥5min。
能量需求的结果表明,对于新鲜前体的原色的良好复制,需要曝光能量80mJ/cm2,而对于1-像素元件,需要110mJ/cm2。对于原色的良好复制,需要曝光能量90mJ/cm2(对于干老化前体),和90mJ/cm2(对于湿老化前体)。对于1-像素元件的良好复制,需要曝光125mJ/cm2(干老化)和120mJ/cm2(湿老化)。这些数据表明,通过改变巯基化合物和层组成,新鲜和老化前体的敏感度参数几乎都保持恒定。
将用良好复制1-像素元件所需的能量曝光的老化板前体安装在片材加料式胶印平版印刷机中并检测。图像区域没有任何问题地接受油墨和纸复制件在非图像区域中没有表现出任何调色。在150,000次良好印刷之后,停止印刷,但板可用于更多印刷品。
实施例4
涂覆溶液由以下组分制成:1.6g JONCRYL683;1.6g三元聚合物;0.72g二季戊四醇五丙烯酸酯;3.6g氨基甲酸乙酯丙烯酸酯;0.2g(3,4-二甲氧基苯基硫代)乙酸;0.15g 2-[2-[2-硫代苯基-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚氯化鎓;0.35g 2-苯基-4,6-二(三氯甲基)-1,3,5-三嗪;0.1g结晶紫;和0.2g 5-巯基-3-甲基硫代-1,2,4-噻二唑(Synthec GmbH,Wolfen,德国)。板前体的制备和随后处理按照实施例1所述进行。
能量需求的结果表明,对于新鲜前体的原色的良好复制,需要曝光能量100mJ/cm2,而对于1-像素元件,需要120mJ/cm2。对于原色的良好复制,需要曝光能量115mJ/cm2(对于干老化前体),和120mJ/cm2(对于湿老化前体)。对于1-像素元件的良好复制,需要曝光135mJ/cm2(干老化)和135mJ/cm2(湿老化)。通过与实施例1比较显然看出,巯基化合物,聚合物粘结剂混合物,羧酸和多卤代烷基化合物的交换仅引起老化前体与新鲜前体相比在红外敏感度方面的无关紧要的变化。
实施例5
实施例1的涂覆溶液通过将2-[2-[2-硫代苯基-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚氯化鎓替换为0.30g染料IRT(Showa DenkoK.K.,日本),它是一种聚次甲基染料,和将3-巯基-1,2,4-三唑替换为2-巯基-1-甲基咪唑而改变。所得组合物按照实施例1进行涂覆,成像和处理。可确定,新鲜前体时85mJ/cm2(对于原色),110mJ/cm2(对于1像素元件),干老化前体时90mJ/cm2(对于原色),120mJ/cm2(对于1-像素元件),和湿老化前体时90mJ/cm2(对于原色)和120mJ/cm2(对于1-像素元件)足以用于良好复制。
对比例1(类似于US 6,309,792)
涂覆溶液由以下组分制成:3.0g JONCRYL683;4.4g AC 50;1.4g二季戊四醇五丙烯酸酯;8.4g氨基甲酸乙酯丙烯酸酯;0.4g苯氨基二乙酸;0.25g 2-[2-[2-硫代苯基-3-[2-(1,3-二氢-1,3,3-三甲基-2H-吲哚-2-叉基)-乙叉基]-1-环己烯-1-基]-乙烯基]-1,3,3-三甲基-3H-吲哚氯化鎓;和0.75g 2-(4-甲氧基苯基)-4,6-二(三氯甲基)-1,3,5-三嗪;和0.3g RENOLBlue B2G HW。这些组分在搅拌下溶解在由30体积份乙二醇单甲基醚,45体积份甲醇,和25体积份甲基乙基酮组成的100mL混合物中。
在溶液过滤之后,将它施用到实施例1的基材上并将所得元件在90℃下干燥4min。所得红外敏感层的干重是约2g/m2。如实施例1所述施用2.0g/m2的氧不可渗透隔绝层并将前体在90℃下干燥5min。前体如实施例1所述进行老化。
前体的红外敏感度和复制件结果随后如实施例1所述进行测定。前体的未曝光区域可通过显影剂被完全去除。能量需求的结果表明,对于原色的良好复制,需要曝光能量78mJ/cm2(对于新鲜前体),125mJ/cm2(对于干老化前体),和130mJ/cm2(对于湿老化前体)。对于1-像素元件的良好复制,需要曝光107mJ/cm2(新鲜前体),155mJ/cm2(干老化前体),和160mJ/cm2(湿老化前体)。
这些发现表明,3-巯基-1,2,4-三唑在组合物中的不存在导致配方具有与新鲜前体相同的敏感度,但在较高温度和/或更高湿度条件下储存时不太稳定。
对比例2
重复实施例1,只是苯氨基二乙酸没有被加入配方中,并将所得组合物如实施例1进行涂覆,成像和处理。
能量需求的结果表明,对于原色图像区域的良好复制,需要曝光能量125mJ/cm2(对于新鲜前体),140mJ/cm2(对于干老化前体),和140mJ/cm2(对于湿老化前体)。对于1-像素元件的良好复制,需要曝光160mJ/cm2(对于新鲜前体),175mJ/cm2(对于干老化前体)和180mJ/cm2(对于湿老化前体)。
这些发现表明,羧酸的不存在导致配方不太红外敏感。红外敏感印刷前体的储存寿命要求却得到满足,表明即使在该不太敏感的配方中,巯基化合物用作稳定化剂。
Claims (10)
1.一种红外敏感组合物,包含:
(i)引发剂体系,包含:
(a)至少一种能够吸收红外线的化合物,选自三芳基胺染料,噻唑鎓染料,吲哚鎓染料,噁唑鎓染料,菁染料,聚苯胺染料,聚吡咯染料,聚噻吩染料,和酞菁颜料,
(b)至少一种能够产生自由基的化合物,该化合物选自多卤代烷基取代的化合物,和
(c)至少一种表示为结构式(I)的羧酸:
R4-(CR5R6)n-Y-CH2COOH (I)
其中:
Y选自O,S和NR7;
R7选自氢,C1-C6烷基,-CH2CH2OH,和被-COOH取代的C1-C5烷基;
R4,R5和R6分别独立地选自氢,C1-C4烷基,取代的或未取代的芳基,-COOH和-NR8CH2COOH;
R8选自-CH2COOH,-CH2OH,和-(CH2)2N(CH2COOH)2;和
n是0,1,2或3;
(ii)至少一种组分,选自不饱和自由基可聚合单体,自由基可聚合的不饱和低聚物,在主链和侧链之一或两者中包含自由基可聚合碳-碳双键的聚合物,和其混合物;
(iii)至少一种聚合物粘结剂;和
(iv)包含其上具有硫醇基团取代的芳族5-元杂环的杂环巯基化合物,所述环包含氮原子和至少一个选自氮,氧和硫的杂原子,其中杂原子在环中与氮原子被一个碳原子分开,和其中硫醇基团键至碳原子上;
其中:
oxa<redb+1.6eV,
其中oxa是组分(a)的氧化电势,以eV计,和redb是组分(b)的还原电势,以eV计。
3.权利要求1或权利要求2的组合物,其中能够产生自由基的化合物是2-苯基-4,6-二(三氯甲基)-1,3,5-三嗪;2-(4-甲氧基苯基)-4,6-二(三氯甲基)-1,3,5-三嗪;三溴甲基苯基砜;2,4,6-三(三氯甲基)-1,3,5-三嗪;或1,2,3,4-四溴-正-丁烷。
5.权利要求1至3任一项的组合物,其中羧酸是(3,4-二甲氧基苯基硫代)乙酸,苯胺基二乙酸,或N-(羧基甲基)-N-苄基甘氨酸。
6.任何前述权利要求的组合物,其中巯基化合物是3-巯基-1,2,4-三唑;2-巯基苯并咪唑;2-巯基苯并噁唑;5-巯基-3-甲基硫代-1,2,4-噻二唑;或2-巯基-1-甲基咪唑。
7.任何前述权利要求的组合物,其中组分(ii)是季戊四醇四丙烯酸酯,二季戊四醇五丙烯酸酯,二(三羟甲基丙烷)四丙烯酸酯,二甘醇二丙烯酸酯,包含烯丙基醇酯基团的预聚物,低聚的氨基甲酸乙酯(甲基)丙烯酸酯,或其混合物。
8.一种印刷板前体,包括基材和在基材之上的根据权利要求1-7任一项的组合物的层。
9.权利要求8的印刷板前体,它另外包括在红外敏感组合物层之上的基本上氧不可渗透的隔绝层。
10.一种用于生产平版印刷板前体的方法,包括将根据任何权利要求1-7的组合物的层施用到基材上。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/131,866 | 2002-04-25 | ||
US10/131,866 US6884568B2 (en) | 2000-10-17 | 2002-04-25 | Stabilized infrared-sensitive polymerizable systems |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1655932A true CN1655932A (zh) | 2005-08-17 |
CN1329190C CN1329190C (zh) | 2007-08-01 |
Family
ID=29268746
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB038117975A Expired - Fee Related CN1329190C (zh) | 2002-04-25 | 2003-04-24 | 红外敏感组合物,包括它的印刷版前体和其生产方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US6884568B2 (zh) |
EP (1) | EP1497122B1 (zh) |
JP (1) | JP2005523484A (zh) |
CN (1) | CN1329190C (zh) |
AT (1) | ATE327888T1 (zh) |
AU (1) | AU2003233055A1 (zh) |
BR (1) | BR0309663A (zh) |
DE (1) | DE60305683T2 (zh) |
WO (1) | WO2003091022A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104788987A (zh) * | 2015-02-02 | 2015-07-22 | 北京印刷学院 | 链转移近红外染料及其高分子聚合乳液制备方法及应用 |
CN105218806A (zh) * | 2015-11-02 | 2016-01-06 | 国网吉林省电力有限公司电力科学研究院 | 一种侧链含三唑基团的聚芳醚类聚合物及其制备方法 |
Families Citing this family (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6824879B2 (en) | 1999-06-10 | 2004-11-30 | Honeywell International Inc. | Spin-on-glass anti-reflective coatings for photolithography |
AU5600200A (en) | 1999-06-10 | 2001-01-02 | Allied-Signal Inc. | Spin-on-glass anti-reflective coatings for photolithography |
JP4156784B2 (ja) * | 2000-07-25 | 2008-09-24 | 富士フイルム株式会社 | ネガ型画像記録材料及び画像形成方法 |
JP2002082429A (ja) * | 2000-09-08 | 2002-03-22 | Fuji Photo Film Co Ltd | ネガ型画像記録材料 |
US7261998B2 (en) | 2001-04-04 | 2007-08-28 | Eastman Kodak Company | Imageable element with solvent-resistant polymeric binder |
US6846614B2 (en) * | 2002-02-04 | 2005-01-25 | Kodak Polychrome Graphics Llc | On-press developable IR sensitive printing plates |
US20040091811A1 (en) * | 2002-10-30 | 2004-05-13 | Munnelly Heidi M. | Hetero-substituted aryl acetic acid co-initiators for IR-sensitive compositions |
US7056639B2 (en) * | 2001-08-21 | 2006-06-06 | Eastman Kodak Company | Imageable composition containing an infrared absorber with counter anion derived from a non-volatile acid |
JP4381143B2 (ja) | 2001-11-15 | 2009-12-09 | ハネウェル・インターナショナル・インコーポレーテッド | フォトリソグラフィー用スピンオン反射防止膜 |
US7172850B2 (en) * | 2002-04-10 | 2007-02-06 | Eastman Kodak Company | Preparation of solvent-resistant binder for an imageable element |
US7659046B2 (en) * | 2002-04-10 | 2010-02-09 | Eastman Kodak Company | Water-developable infrared-sensitive printing plate |
US7338748B2 (en) * | 2002-09-30 | 2008-03-04 | Fujifilm Corporation | Polymerizable composition and planographic printing plate precursor |
JP2004126050A (ja) * | 2002-09-30 | 2004-04-22 | Fuji Photo Film Co Ltd | 平版印刷版原版 |
JP4137577B2 (ja) * | 2002-09-30 | 2008-08-20 | 富士フイルム株式会社 | 感光性組成物 |
EP1431032B1 (en) * | 2002-12-18 | 2015-12-09 | FUJIFILM Corporation | Polymerizable composition and lithographic printing plate precursor |
JP4150261B2 (ja) * | 2003-01-14 | 2008-09-17 | 富士フイルム株式会社 | 平版印刷版原版の製版方法 |
JP4458778B2 (ja) * | 2003-02-20 | 2010-04-28 | 富士フイルム株式会社 | 重合性組成物及びそれを用いた平版印刷版原版 |
JP2004252201A (ja) * | 2003-02-20 | 2004-09-09 | Fuji Photo Film Co Ltd | 平版印刷版原版 |
JP4048134B2 (ja) * | 2003-02-21 | 2008-02-13 | 富士フイルム株式会社 | 平版印刷版原版 |
JP4048133B2 (ja) * | 2003-02-21 | 2008-02-13 | 富士フイルム株式会社 | 感光性組成物及びそれを用いた平版印刷版原版 |
JP2004252285A (ja) * | 2003-02-21 | 2004-09-09 | Fuji Photo Film Co Ltd | 感光性組成物及びそれを用いた平版印刷版原版 |
JP4299639B2 (ja) * | 2003-07-29 | 2009-07-22 | 富士フイルム株式会社 | 重合性組成物及びそれを用いた画像記録材料 |
JP2005099284A (ja) * | 2003-09-24 | 2005-04-14 | Fuji Photo Film Co Ltd | 感光性組成物及び平版印刷版原版 |
US8053159B2 (en) | 2003-11-18 | 2011-11-08 | Honeywell International Inc. | Antireflective coatings for via fill and photolithography applications and methods of preparation thereof |
US6902866B1 (en) * | 2003-11-24 | 2005-06-07 | Gary Ganghui Teng | Thermosensitive lithographic printing plate comprising specific acrylate monomers |
DE102004003143A1 (de) * | 2004-01-21 | 2005-08-18 | Kodak Polychrome Graphics Gmbh | Strahlungsempfindliche Zusammensetzungen mit mercapto-funktionalisierten, radikalisch polymerisierbaren Monomeren |
JP4411226B2 (ja) * | 2005-02-22 | 2010-02-10 | 富士フイルム株式会社 | 感光性平版印刷版 |
JP4524235B2 (ja) * | 2005-03-29 | 2010-08-11 | 富士フイルム株式会社 | 平版印刷版原版 |
EP1862301B1 (en) * | 2006-06-02 | 2011-09-28 | FUJIFILM Corporation | Image recording material, planographic printing plate precursor, and planographic printing method using the same |
US8642246B2 (en) | 2007-02-26 | 2014-02-04 | Honeywell International Inc. | Compositions, coatings and films for tri-layer patterning applications and methods of preparation thereof |
JP5166016B2 (ja) * | 2007-12-28 | 2013-03-21 | 株式会社シンク・ラボラトリー | ネガ型感光性組成物 |
JP5155677B2 (ja) * | 2008-01-22 | 2013-03-06 | 富士フイルム株式会社 | 平版印刷版原版、およびその製版方法 |
US8084182B2 (en) | 2008-04-29 | 2011-12-27 | Eastman Kodak Company | On-press developable elements and methods of use |
US20100151385A1 (en) | 2008-12-17 | 2010-06-17 | Ray Kevin B | Stack of negative-working imageable elements |
US8034538B2 (en) | 2009-02-13 | 2011-10-11 | Eastman Kodak Company | Negative-working imageable elements |
US20100215919A1 (en) | 2009-02-20 | 2010-08-26 | Ting Tao | On-press developable imageable elements |
US20100227269A1 (en) | 2009-03-04 | 2010-09-09 | Simpson Christopher D | Imageable elements with colorants |
US8318405B2 (en) | 2009-03-13 | 2012-11-27 | Eastman Kodak Company | Negative-working imageable elements with overcoat |
US8557877B2 (en) | 2009-06-10 | 2013-10-15 | Honeywell International Inc. | Anti-reflective coatings for optically transparent substrates |
US8247163B2 (en) | 2009-06-12 | 2012-08-21 | Eastman Kodak Company | Preparing lithographic printing plates with enhanced contrast |
US8257907B2 (en) | 2009-06-12 | 2012-09-04 | Eastman Kodak Company | Negative-working imageable elements |
US8383319B2 (en) | 2009-08-25 | 2013-02-26 | Eastman Kodak Company | Lithographic printing plate precursors and stacks |
IN2012DN00777A (zh) | 2009-09-15 | 2015-06-26 | Mylan Group | |
US8329383B2 (en) * | 2009-11-05 | 2012-12-11 | Eastman Kodak Company | Negative-working lithographic printing plate precursors |
EP2566900B1 (en) | 2010-09-14 | 2016-02-17 | Mylan Group | Copolymers for near-infrared radiation-sensitive coating compositions for positive-working thermal lithographic printing plates |
US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
EP2916171B1 (en) * | 2014-03-03 | 2017-05-31 | Agfa Graphics Nv | A method for making a lithographic printing plate precursor |
EP3067216B1 (en) * | 2015-03-10 | 2019-01-16 | Basf Se | Chromophoric compositions |
US10544329B2 (en) | 2015-04-13 | 2020-01-28 | Honeywell International Inc. | Polysiloxane formulations and coatings for optoelectronic applications |
US20170021656A1 (en) | 2015-07-24 | 2017-01-26 | Kevin Ray | Lithographic imaging and printing with negative-working photoresponsive printing members |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4410621A (en) | 1981-04-03 | 1983-10-18 | Toyo Boseki Kabushiki Kaisha | Photosensitive resin containing a combination of diphenyl-imiazolyl dimer and a heterocyclic mercaptan |
US4937159A (en) | 1985-11-20 | 1990-06-26 | The Mead Corporation | Photosensitive materials and compositions containing ionic dye compounds as initiators and thiols as autooxidizers |
DE68917099T2 (de) | 1988-12-07 | 1995-01-05 | Kao Corp | Produktion von sekundären aliphatischen Aminen. |
EP0672954B1 (en) | 1994-03-14 | 1999-09-15 | Kodak Polychrome Graphics LLC | Radiation-sensitive composition containing a resole resin, a novolac resin, an infrared absorber and a triazine and use thereof in lithographic printing plates |
US5491046A (en) | 1995-02-10 | 1996-02-13 | Eastman Kodak Company | Method of imaging a lithographic printing plate |
EP0819985B1 (en) | 1996-07-19 | 2002-06-05 | Agfa-Gevaert | A radiation sensitive imaging element and a method for producing lithographic plates therewith |
US6060222A (en) | 1996-11-19 | 2000-05-09 | Kodak Polcyhrome Graphics Llc | 1Postitve-working imaging composition and element and method of forming positive image with a laser |
EP0889363B1 (en) | 1997-07-03 | 2005-10-05 | E.I. Du Pont De Nemours And Company | Near IR sensitive photoimageable/photopolymerizable compositions, media, and associated processes |
JP3844853B2 (ja) | 1997-07-22 | 2006-11-15 | 富士写真フイルム株式会社 | ネガ型画像記録材料 |
JP2000086670A (ja) | 1997-08-26 | 2000-03-28 | Showa Denko Kk | 有機ホウ素酸塩の安定化剤および感光性組成物 |
US6352811B1 (en) | 1998-06-23 | 2002-03-05 | Kodak Polychrome Graphics Llc | Thermal digital lithographic printing plate |
DE19906823C2 (de) * | 1999-02-18 | 2002-03-14 | Kodak Polychrome Graphics Gmbh | IR-Empfindliche Zusammensetzung und deren Verwendung zur Herstellung von Druckplatten |
US6391524B2 (en) | 1999-11-19 | 2002-05-21 | Kodak Polychrome Graphics Llc | Article having imagable coatings |
US6309792B1 (en) | 2000-02-18 | 2001-10-30 | Kodak Polychrome Graphics Llc | IR-sensitive composition and use thereof for the preparation of printing plate precursors |
US6660446B2 (en) | 2000-05-30 | 2003-12-09 | Fuji Photo Film Co., Ltd. | Heat-sensitive composition and planographic printing plate |
US6864040B2 (en) * | 2001-04-11 | 2005-03-08 | Kodak Polychrome Graphics Llc | Thermal initiator system using leuco dyes and polyhalogene compounds |
US6846614B2 (en) * | 2002-02-04 | 2005-01-25 | Kodak Polychrome Graphics Llc | On-press developable IR sensitive printing plates |
JP2003114520A (ja) * | 2001-10-05 | 2003-04-18 | Fuji Photo Film Co Ltd | 光重合性組成物及びそれを用いた記録材料 |
-
2002
- 2002-04-25 US US10/131,866 patent/US6884568B2/en not_active Expired - Fee Related
-
2003
- 2003-04-24 AU AU2003233055A patent/AU2003233055A1/en not_active Abandoned
- 2003-04-24 EP EP03727351A patent/EP1497122B1/en not_active Expired - Lifetime
- 2003-04-24 WO PCT/EP2003/004271 patent/WO2003091022A1/en active IP Right Grant
- 2003-04-24 AT AT03727351T patent/ATE327888T1/de not_active IP Right Cessation
- 2003-04-24 JP JP2003587621A patent/JP2005523484A/ja active Pending
- 2003-04-24 DE DE60305683T patent/DE60305683T2/de not_active Expired - Lifetime
- 2003-04-24 CN CNB038117975A patent/CN1329190C/zh not_active Expired - Fee Related
- 2003-04-24 BR BR0309663-7A patent/BR0309663A/pt not_active Application Discontinuation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104788987A (zh) * | 2015-02-02 | 2015-07-22 | 北京印刷学院 | 链转移近红外染料及其高分子聚合乳液制备方法及应用 |
CN105218806A (zh) * | 2015-11-02 | 2016-01-06 | 国网吉林省电力有限公司电力科学研究院 | 一种侧链含三唑基团的聚芳醚类聚合物及其制备方法 |
CN105218806B (zh) * | 2015-11-02 | 2018-01-16 | 国网吉林省电力有限公司电力科学研究院 | 一种侧链含三唑基团的聚芳醚类聚合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1329190C (zh) | 2007-08-01 |
DE60305683D1 (de) | 2006-07-06 |
BR0309663A (pt) | 2005-02-22 |
AU2003233055A1 (en) | 2003-11-10 |
JP2005523484A (ja) | 2005-08-04 |
EP1497122A1 (en) | 2005-01-19 |
ATE327888T1 (de) | 2006-06-15 |
US6884568B2 (en) | 2005-04-26 |
WO2003091022A1 (en) | 2003-11-06 |
US20020197564A1 (en) | 2002-12-26 |
EP1497122B1 (en) | 2006-05-31 |
DE60305683T2 (de) | 2006-12-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1655932A (zh) | 稳定化红外敏感可聚合体系 | |
JP4037676B2 (ja) | ロイコ染料およびポリハロゲン化合物を使用した熱開始剤システム | |
JP4598755B2 (ja) | オキサゾール誘導体を含む輻射線感受性組成物、及び該組成物に基づく画像形成性要素 | |
JP4800972B2 (ja) | メルカプト官能化ラジカル重合可能モノマーを有する平版印刷版前駆体 | |
JP4060411B2 (ja) | 感光性組成物及びそれを含む感光性要素並びにネガ像形成方法 | |
CN1675064A (zh) | 高速负像热感印刷版 | |
CN1334490A (zh) | 负像记录材料和图像形成方法 | |
JP2000131837A (ja) | 光重合性組成物、光重合性平版印刷版及び画像形成方法 | |
JP2002023360A (ja) | ネガ型画像記録材料 | |
JP2004012706A (ja) | 平版印刷版原版 | |
CN1708409A (zh) | 用于红外敏感组合物的杂取代的芳基乙酸共引发剂 | |
CN101142531B (zh) | 具有强的印刷运转稳定性的平版印刷印版 | |
JP4226759B2 (ja) | 平版印刷版原版 | |
JP4861678B2 (ja) | 平版印刷版原版および平版印刷版原版の製造方法 | |
JP4395276B2 (ja) | 感光性組成物 | |
JP2002341519A (ja) | 感熱性組成物及びそれを用いた平版印刷版原版 | |
US20060154172A1 (en) | 1-4-Dihydropyridine-containing ir-sensitive composition and use thereof for the production of imageable elements | |
JP2001166461A (ja) | ネガ型平版印刷版原版 | |
WO2008007539A1 (fr) | Cliché matrice pour l'impression lithographique et procédé d'impression lithographique | |
JP2001242621A (ja) | 平版印刷版原版 | |
JP2003107751A (ja) | 平版印刷版原版及び平版印刷版の製版方法 | |
JP2003098688A (ja) | 平版印刷版原版及び平版印刷版の製版方法 | |
JP4425041B2 (ja) | 感光性組成物 | |
JP2001272787A (ja) | 画像形成材料 | |
JP2003251954A (ja) | 平版印刷版製版用フィニッシングガム液及び平版印刷版の製版方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070801 Termination date: 20180424 |
|
CF01 | Termination of patent right due to non-payment of annual fee |