JP3949882B2 - Positive photosensitive composition and positive photosensitive lithographic printing plate - Google Patents
Positive photosensitive composition and positive photosensitive lithographic printing plate Download PDFInfo
- Publication number
- JP3949882B2 JP3949882B2 JP2000250762A JP2000250762A JP3949882B2 JP 3949882 B2 JP3949882 B2 JP 3949882B2 JP 2000250762 A JP2000250762 A JP 2000250762A JP 2000250762 A JP2000250762 A JP 2000250762A JP 3949882 B2 JP3949882 B2 JP 3949882B2
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- JP
- Japan
- Prior art keywords
- substituent
- group
- positive photosensitive
- photosensitive composition
- dye
- 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.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims description 62
- 238000007639 printing Methods 0.000 title claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 115
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000000623 heterocyclic group Chemical group 0.000 claims description 25
- -1 oxonium cation Chemical class 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229920003986 novolac Polymers 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims 2
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 1
- 230000036211 photosensitivity Effects 0.000 claims 1
- 239000000975 dye Substances 0.000 description 88
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 17
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 14
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 13
- 238000000576 coating method Methods 0.000 description 12
- 125000005843 halogen group Chemical group 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 10
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 8
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 5
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 5
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920003987 resole Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 0 *Cc1c(*)*cc*1* Chemical compound *Cc1c(*)*cc*1* 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000002596 lactones Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229910052913 potassium silicate Inorganic materials 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000866 electrolytic etching Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 239000010979 ruby Substances 0.000 description 2
- 229910001750 ruby Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-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
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- KGWYICAEPBCRBL-UHFFFAOYSA-N 1h-indene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C=CC2=C1 KGWYICAEPBCRBL-UHFFFAOYSA-N 0.000 description 1
- SOFCWHXDGRMUMF-UHFFFAOYSA-N 2-(2-hydroxyphenyl)ethene-1,1,2-triol Chemical compound OC(O)=C(O)C1=CC=CC=C1O SOFCWHXDGRMUMF-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- MBGHHXWAKSEHMA-UHFFFAOYSA-N 2-phenylethene-1,1,2-triol Chemical compound OC(O)=C(O)C1=CC=CC=C1 MBGHHXWAKSEHMA-UHFFFAOYSA-N 0.000 description 1
- BKUZZZJNRDDTRP-UHFFFAOYSA-N 2-phenylethene-1,1-diol Chemical compound OC(O)=CC1=CC=CC=C1 BKUZZZJNRDDTRP-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical group CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 206010057040 Temperature intolerance Diseases 0.000 description 1
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- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
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- 239000002280 amphoteric surfactant Substances 0.000 description 1
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- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 238000005530 etching Methods 0.000 description 1
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- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
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- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000004043 oxo group Chemical group O=* 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- FTUYQIPAPWPHNC-UHFFFAOYSA-M sodium;4-[[4-[benzyl(ethyl)amino]phenyl]-[4-[benzyl(ethyl)azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]benzene-1,3-disulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=CC=CC=2)C=2C(=CC(=CC=2)S([O-])(=O)=O)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC=C1 FTUYQIPAPWPHNC-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000464 thioxo group Chemical group S=* 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 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
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/02—Positive working, i.e. the exposed (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
- B41C2210/26—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 not involving carbon-to-carbon unsaturated bonds
- B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
Landscapes
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Description
【０００１】
【発明の属する技術分野】
本発明は、平版印刷版、印刷校正用カラープルーフ、液晶ディスプレイやプラズマディスプレイ用カラーフィルターレジスト、半導体素子の集積回路用フォトレジスト、配線板やグラビア製版用銅エッチングレジスト等に使用される、近赤外線領域の光に対して高感度なポジ型感光性組成物及びポジ型感光性平版印刷版に関し、特に、半導体レーザーやＹＡＧレーザー等による直接製版に好適なポジ型感光性組成物及びポジ型感光性平版印刷版に関する。
【０００２】
【従来の技術】
従来より、ポジ型感光性組成物としては、例えば、光照射によりインデンカルボン酸を生じアルカリ可溶性となるｏ−キノンジアジド基含有化合物、ｏ−ニトロカルビノールエステル基を有する有機高分子物質、或いは、光により酸を発生する化合物（光酸発生剤）と酸により加水分解を生じアルカリ可溶性となる化合物との組成物等が知られている。
【０００３】
一方、コンピュータ画像処理技術の進歩に伴い、デジタル画像情報から、銀塩マスクフィルムへの出力を行わずに、レーザー光或いはサーマルヘッド等により、直接レジスト画像を形成する感光又は感熱ダイレクト製版システムが注目されている。特に、高出力の半導体レーザーやＹＡＧレーザー等を用いる、高解像度のレーザー感光ダイレクト製版システムは、小型化、製版作業時の環境光、及び版材コスト等の面から、その実現が強く望まれている。
【０００４】
これに対し、従来より、レーザー感光又は感熱を利用した画像形成方法としては、昇華転写色素を利用し色材画像を形成する方法並びに平版印刷版を作製する方法等が知られており、後者においては、具体的に、例えば、ジアゾ化合物の架橋反応を利用し平版印刷版を作製する方法、ニトロセルロースの分解反応を利用し平版印刷版を作製する方法等が知られている。
【０００５】
近年、化学増幅型のフォトレジストに長波長光線吸収色素を組み合わせた技術が散見されるようになった。例えば、特開平６−４３６３３号公報には、特定のスクアリリウム系色素に光酸発生剤及びバインダーを組み合わせた感光性材料が開示されており、又、これに類する技術として、特開平７−２０６２９号公報には、赤外線吸収色素、潜伏性ブレンステッド酸、レゾール樹脂及びノボラック樹脂を含む感光性組成物層を半導体レーザー等により像状に露光し平版印刷版を作製する方法が、特開平７−２７１０２９号公報には、前記潜伏性ブレンステッド酸に代えｓ−トリアジン系化合物を用いる方法が、更に、特開平９−４３８４７号公報には、赤外線の照射により加熱して感光材の結晶性を変化させるレジスト材及びそれを利用したパターン形成方法が、それぞれ開示されている。
【０００６】
しかしながら、本発明者の検討によれば、これら従来の技術は、近赤外線領域の光に対して感度が低く、現像液に対する露光部と非露光部の溶解性の差が小さく、その結果、非画像部が十分に除去されなかったり、画像部の残膜率が十分に保持されず、又、そのため、現像条件の幅が狭い等の、実用上の欠点を有していた。
【０００７】
これに対して、本願出願人は、ポリメチン鎖を介して複素原子が結合された構造の近赤外線吸収色素からなる光熱変換物質とアルカリ可溶性樹脂という光化学的変化を期待し得ない単純な系で、前述の欠点を解消したポジ画像を形成できる感光性組成物が得られることを見い出し、先に特許出願（特開平１０−２６８５１２号公報参照）し、引き続いて、更なる改良を検討中であった。
【０００８】
【発明が解決しようとする課題】
本発明は、前述の従来技術に鑑みてなされたものであって、従って、本発明は、近赤外線領域の光に対して高感度であって、画像部と非画像部とのコントラストに優れ、よって、現像条件の幅の広いポジ型感光性組成物及びポジ型感光性平版印刷版を提供することを目的とする。
【０００９】
【課題を解決するための手段】
本発明者は、前記課題を解決すべく鋭意検討した結果、ポリメチン鎖を介して複素環の複素原子が結合された構造を基本構造とする色素であって、該ポリメチン鎖上に特定の置換基を有する色素を光熱変換物質としてアルカリ可溶性樹脂と共に用いた組成物が前記目的を達成できることを見い出し本発明を完成したもので、即ち、本発明は、画像露光光源の光を吸収して熱に変換する光熱変換物質とアルカリ可溶性樹脂とを含有するポジ型感光性組成物であって、該光熱変換物質として、ポリメチン鎖を介して複素原子が結合された構造を基本構造とする色素であって、該ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を有する色素を含有してなるポジ型感光性組成物、及び、支持体表面に該感光性組成物の層が形成されてなるポジ型感光性平版印刷版、を要旨とする。
【００１０】
【発明の実施の形態】
本発明のポジ型感光性組成物において、画像露光光源の光を吸収して熱に変換する光熱変換物質とは、吸収した光を熱に変換し得る化合物であって、本発明においては、その光熱変換物質として、ポリメチン鎖を介して複素環の複素原子が結合された構造を基本構造とする色素であって、該ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を有する色素を含有する。ここで、「色素分子中で共鳴する」とは、換言すれば、「色素の発色団と共鳴する」ことを意味し、色素が前記置換基を有することによって色素分子中の発色団のπ電子系が広がり、吸収ピークを通常２０ｎｍ以上長波長側へシフトさせ、特に波長域７００〜１３００ｎｍの近赤外線領域の吸収効率を向上させ得るものである。これらの近赤外線吸収色素は、前記波長域の光を効率よく吸収する一方、紫外線領域の光は殆ど吸収しないか、吸収しても実質的に感応せず、白色灯に含まれるような弱い紫外線によっては感光性組成物を変成させる作用のない化合物である。
【００１１】
本発明において、これらの色素は、ポリメチン（−ＣＨ＝）n 鎖を介して、窒素原子、酸素原子、又は硫黄原子等の複素原子が結合された構造を基本構造とし、その基本構造としては、代表的には、それらの複素原子が複素環を形成し、ポリメチン鎖を介して複素環が結合された構造の広義の所謂シアニン系色素、具体的には、例えば、キノリン系（所謂、狭義のシアニン系）、インドール系（所謂、インドシアニン系）、ベンゾチアゾール系（所謂、チオシアニン系）、ピリリウム系、チアピリリウム系、スクアリリウム系、クロコニウム系、アズレニウム系等、及び、ポリメチン鎖を介して非環式複素原子が結合された構造の所謂ポリメチン系色素等が挙げられ、中で、キノリン系、インドール系、ベンゾチアゾール系、ピリリウム系、チアピリリウム系等のシアニン系色素、及びポリメチン系色素が好ましい。
【００１２】
本発明における色素の基本構造として、前記シアニン系色素の中で、キノリン系色素としては、特に、下記一般式（Ia) 、(Ib)、又は(Ic)で表されるものが好ましい。
【００１３】
【化７】
〔式(Ia)、(Ib)、及び(Ic)中、Ｒ1 及びＲ2 は各々独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、又は置換基を有していてもよいフェニル基を示し、Ｌ1 は置換基として、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を少なくとも有するトリ、ペンタ、ヘプタ、ノナ、又はウンデカメチン基を示し、該ペンタ、ヘプタ、ノナ、又はウンデカメチン基上の２つの置換基が互いに連結して炭素数５〜７のシクロアルケン環、シクロアルケノン環、又はシクロアルケンジオン環を形成していてもよく、キノリン環は置換基を有していてもよく、その場合、隣接する２つの置換基が互いに連結して縮合ベンゼン環を形成していてもよい。Ｘa - は対アニオンを示す。〕
【００１５】
ここで、式(Ia)、(Ib)、及び(Ic)中のＲ1 及びＲ2 がアルキル基であるときの炭素数は、通常１〜１５、好ましくは１〜１０、アルケニル基、アルキニル基であるときの炭素数は、通常２〜１５、好ましくは２〜１０であり、フェニル基も含めたそれらの置換基としては、炭素数が通常１〜１５、好ましくは１〜１０のアルコキシ基、フェノキシ基、ヒドロキシ基、又はフェニル基等が挙げられ、Ｌ1 における前記エーテル結合を含む置換基以外の置換基としては、同上炭素数のアルキル基、アミノ基、又はハロゲン原子等が挙げられ、キノリン環における置換基としては、同上炭素数のアルキル基、同上炭素数のアルコキシ基、ニトロ基、又はハロゲン原子等が挙げられる。
【００１６】
又、本発明における色素の基本構造として、前記シアニン系色素の中で、インドール系、及びベンゾチアゾール系色素としては、特に、下記一般式(II)で表されるものが好ましい。
【００１７】
【化８】
〔式(II)中、Ｙ1 及びＹ2 は各々独立して、ジアルキルメチレン基又は硫黄原子を示し、Ｒ3 及びＲ4 は各々独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、又は置換基を有していてもよいフェニル基を示し、Ｌ2 は置換基として、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を少なくとも有するトリ、ペンタ、ヘプタ、ノナ、又はウンデカメチン基を示し、該ペンタ、ヘプタ、ノナ、又はウンデカメチン基上の２つの置換基が互いに連結して炭素数５〜７のシクロアルケン環、シクロアルケノン環、又はシクロアルケンジオン環を形成していてもよく、縮合ベンゼン環は置換基を有していてもよく、その場合、隣接する２つの置換基が互いに連結して縮合ベンゼン環を形成していてもよい。Ｘa - は対アニオンを示す。〕
【００１９】
ここで、式(II)中のＲ3 及びＲ4 がアルキル基であるときの炭素数は、通常１〜１５、好ましくは１〜１０、アルケニル基、アルキニル基であるときの炭素数は、通常２〜１５、好ましくは２〜１０であり、フェニル基も含めたそれらの置換基としては、炭素数が通常１〜１５、好ましくは１〜１０のアルコキシ基、フェノキシ基、ヒドロキシ基、又はフェニル基等が挙げられ、Ｌ2 における前記エーテル結合を含む置換基以外の置換基としては、同上炭素数のアルキル基、アミノ基、又はハロゲン原子等が挙げられ、縮合ベンゼン環における置換基としては、同上炭素数のアルキル基、同上炭素数のアルコキシ基、ニトロ基、又はハロゲン原子等が挙げられる。
【００２０】
又、本発明における色素の基本構造として、前記シアニン系色素の中で、ピリリウム系、及びチアピリリウム系色素としては、特に、下記一般式(IIIa)、(IIIb)、又は(IIIc)で表されるものが好ましい。
【００２１】
【化９】
〔式(IIIa)、(IIIb)、及び(IIIc)中、Ｚ1 及びＺ2 は各々独立して、酸素原子又は硫黄原子を示し、Ｒ5 、Ｒ6 、Ｒ7 、及びＲ8 は各々独立して、水素原子又はアルキル基、又は、Ｒ5 とＲ7 、及びＲ6 とＲ8 が互いに連結して炭素数５又は６のシクロアルケン環を形成していてもよく、Ｌ3 は置換基として、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を少なくとも有するモノ、トリ、ペンタ、又はヘプタメチン基を示し、該トリ、ペンタ、又はヘプタメチン基上の２つの置換基が互いに連結して炭素数５〜７のシクロアルケン環、シクロアルケノン環、又はシクロアルケンジオン環を形成していてもよく、ピリリウム環及びチアピリリウム環は置換基を有していてもよく、その場合、隣接する２つの置換基が互いに連結して縮合ベンゼン環を形成していてもよい。Ｘa - は対アニオンを示す。〕
【００２３】
ここで、式(IIIa)、(IIIb)、及び(IIIc)中のＲ5 、Ｒ6 、Ｒ7 、及びＲ8 がアルキル基であるときの炭素数は、通常１〜１５、好ましくは１〜１０であり、Ｌ3 における前記エーテル結合を含む置換基以外の置換基としては、同上炭素数のアルキル基、アミノ基、又はハロゲン原子等が挙げられ、ピリリウム環及びチアピリリウム環における置換基としては、フェニル基等のアリール基等が挙げられる。
【００２４】
又、本発明における色素の基本構造として、ポリメチン系色素としては、特に、下記一般式(IV)で表されるものが好ましい。
【００２５】
【化１０】
〔式(IV)中、Ｒ9 、Ｒ10、Ｒ11、及びＲ12は各々独立して、アルキル基を示し、Ｒ13及びＲ14は各々独立して、置換基を有していてもよいアリール基、フリル基、又はチエニル基を示し、Ｌ4 は置換基として、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を少なくとも有するモノ、トリ、ペンタ、又はヘプタメチン基を示し、該トリ、ペンタ、又はヘプタメチン基上の２つの置換基が互いに連結して炭素数５〜７のシクロアルケン環、シクロアルケノン環、又はシクロアルケンジオン環を形成していてもよく、キノン環及びベンゼン環は置換基を有していてもよい。Ｘa - は対アニオンを示す。〕
【００２７】
ここで、式(IV)中のＲ9 、Ｒ10、Ｒ11、及びＲ12のアルキル基の炭素数は、通常１〜１５、好ましくは１〜１０、Ｒ13及びＲ14がアリール基であるときの炭素数は、通常６〜２０、好ましくは６〜１５であり、Ｒ13及びＲ14として具体的には、フェニル基、１−ナフチル基、２−ナフチル基、２−フリル基、３−フリル基、２−チエニル基、３−チエニル基等が挙げられ、それらの置換基としては、同上炭素数のアルキル基、同上炭素数のアルコキシ基、ジアルキルアミノ基、ヒドロキシ基、又はハロゲン原子等が挙げられ、Ｌ4 における前記エーテル結合を含む置換基以外の置換基としては、同上炭素数のアルキル基、アミノ基、又はハロゲン原子等が挙げられ、キノン環及びベンゼン環における置換基としては、同上炭素数のアルキル基、同上炭素数のアルコキシ基、ニトロ基、又はハロゲン原子等が挙げられる。
【００２８】
尚、前記一般式(Ia 〜c)、(II)、(IIIa 〜c)、及び(IV)における対アニオンＸa - としては、具体的には、例えば、Ｃｌ- 、Ｂｒ- 、Ｉ- 、ＣｌＯ4 - 、ＰＦ6 - 、ＳｂＦ6 - 、ＡｓＦ6 - 、及び、ＢＦ4 - 、ＢＣｌ4 - 等の無機硼素酸等の無機酸アニオン、並びに、ベンゼンスルホン酸、トルエンスルホン酸、ナフタレンスルホン酸、酢酸、及び、メチル、エチル、プロピル、ブチル、フェニル、メトキシフェニル、ナフチル、フルオロフェニル、ジフルオロフェニル、ペンタフルオロフェニル、チエニル、ピロリル等の有機基を有する有機硼素酸等の有機酸アニオンを挙げることができる。
【００２９】
本発明における色素の基本構造として、以上の前記一般式(Ia 〜c)で表されるキノリン系、前記一般式(II)で表されるインドール系又はベンゾチアゾール系、前記一般式(IIIa 〜c)で表されるピリリウム系又はチアピリリウム系等のシアニン系色素、及び前記一般式(IV)で表されるポリメチン系色素の中で、本発明においては、前記一般式(II)で表されるインドール系又はベンゾチアゾール系色素が特に好ましい。
【００３０】
又、前記各式におけるＬ1 、Ｌ2 、Ｌ3 、及びＬ4 を含めたポリメチン鎖として、波長域７００〜８５０ｎｍに対してはヘプタメチン鎖であるものが、波長域８５０〜９５０ｎｍに対してはノナメチン鎖であるものが、波長域９５０〜１３００ｎｍに対してはウンデカメチン鎖であるものが、それぞれ好ましい。
【００３１】
本発明における色素は、前記基本構造のポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を有する構造のものであることが必須であり、そのエーテル結合を含む置換基としては、鎖状エーテル結合で結合しているものが挙げられ、これらは、別のポリメチン鎖を介して色素のポリメチン鎖に結合していてもよい。
【００３２】
ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じる鎖状エーテル結合で結合している置換基を有する色素の共鳴機構は、例えば、ノナメチン鎖を介して窒素原子が結合している構造の色素を例にとると、下式の如くなる。
【００３３】
【化７】
本発明において、その鎖状エーテル結合を含む置換基としては、具体的には、下記一般式(Va)で表されるものが挙げられる。
【００３５】
【化１２】
〔式(Va)中、Ｗ1 は、酸素原子を示し、Ｒa は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよい複素環基を示す。〕
【００３７】
ここで、式(Va)中のＲa がアルキル基であるときの炭素数は、通常１〜１５、好ましくは１〜１０、アリール基であるときの炭素数は、通常６〜２０、好ましくは６〜１５、複素環であるときの炭素数は、通常２〜１５、好ましくは２〜１０であり、それらの置換基としては、炭素数が１〜５のアルキル基、炭素数が１〜５のアルコキシ基或いはチオアルコキシ基、炭素数が２〜５のアシル基、炭素数が２〜５のアシルオキシ基、炭素数が２〜５のアルコキシカルボニル基、フェニル基、ナフチル基、イソシアナート基或いはイソチオシアナート基、オキソ基或いはチオキソ基、炭素数が２〜５の複素環基、水酸基、又はハロゲン原子等が挙げられる。
【００３８】
前記一般式(Va)で表されるものの中で、Ｒa がフェニル基であるもの、又は、Ｒa が複素環基である下記一般式(Vb)で表されるものが好ましい。
【００３９】
【化１３】
〔式(Vb)中、Ｗ1 は、酸素原子を示し、Ｗ2 は、酸素原子、硫黄原子、窒素原子、又はジアルキルメチレン基を示し、Ｗ1 とＷ2 とは同一であっても異なっていてもよく、複素環は４〜６員環であり、置換基を有していてもよく、その場合、隣接する２つの置換基が互いに連結して縮合環を形成していてもよい。〕
【００４１】
更に、前記一般式(Vb)で表されるものの中で下記一般式(Vc)、(Vd)、又は(Ve)で表されるものが好ましく、下記一般式(Vc)で表されるものが特に好ましい。
【００４２】
【化８】
〔式(Vc)中、Ｗ1 は、酸素原子を示し、Ｗ 1 とＷ 2 は同一であっても異なっていてもよく、Ｒb は、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基或いはチオアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、又は水素原子を示す。〕
【００４４】
【化９】
〔式(Vd)中、Ｗ1 は、酸素原子を示し、Ｗ 1 とＷ 2 は同一であっても異なっていてもよく、Ｒc は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、又は水素原子を示す。〕
【００４６】
【化１６】
〔式(Ve)中、Ｗ1 は、酸素原子を示し、Ｗ2 は、酸素原子、硫黄原子、窒素原子、又はジアルキルメチレン基を示し、Ｗ1 とＷ2 とは同一であっても異なっていてもよく、縮合環は芳香族炭化水素環を示す。〕
【００４８】
ここで、式(Vc)中のＲb 、及び(Vd)中のＲc がアルキル基であるときの炭素数は通常１〜５、アルコキシ基或いはチオアルコキシ基であるときの炭素数は通常１〜５、アリール基であるときの炭素数は通常６〜１０、複素環基であるときの炭素数は通常２〜５であり、式(Ve)中のＷ2 がジアルキルメチレン基であるときの炭素数は通常３〜１５である。
【００４９】
以上の、ポリメチン鎖上の鎖状エーテル結合を含む置換基としての好適な例を以下に示す。
【００５０】
【化１０】
尚、本発明におけるこれらの色素としては、ポリメチン鎖上の鎖状エーテル結合を含む置換基が、別の鎖状エーテル結合を介して、直接に又は更に２価の結合基を介する等して、同種又は異種の色素のポリメチン鎖と結合した架橋構造を採るものであってもよい。
【００５２】
本発明における光熱変換物質として、以上の、ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じる鎖状エーテル結合を含む置換基を有する構造のシアニン系色素、及びポリメチン系色素の具体例を以下に示す。尚、以下の具体例中、Ａは、鎖状エーテル結合を含む置換基であり、Ｘa - は、Ｃｌ- 、Ｂｒ- 、Ｉ- 、ＣｌＯ4 - 、ＰＦ6 - 、ＢＦ4 - 、ｐ−トルエンスルホン酸、又は１−ナフタレンスルホン酸等の対アニオンである。
【００５３】
【化１８】
【化１９】
【化２０】
【化２１】
【化２２】
【化２３】
【化２４】
【化２５】
【化２６】
更に、本発明において、前記基本構造のポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基としては、２つの置換基によって環状エーテル結合を形成しているものが挙げられる。
【００６３】
ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じる環状エーテル結合を形成している置換基を有する色素の共鳴機構は、例えば、ノナメチン鎖を介して窒素原子が結合している構造の色素を例にとると、下式の如くなる。
【００６４】
【化１１】
本発明において、その環状エーテル結合を含む置換基としては、具体的には、トリメチン基を取り込んだ下記一般式(VIa) で表されるものが挙げられる。
【００６６】
【化２８】
〔式(VIa) 中、Ｗ3 は、酸素原子を示し、Ｗ3 を含む複素環は置換基を有していてもよい５又は６員環である。〕
【００６８】
ここで、式(VIa) 中の複素環における置換基としては、炭素数が１〜５のアルキル基、炭素数が２〜５のアシルオキシ基、炭素数が２〜５のアルコキシカルボニル基、フェニル基、ナフチル基、アミノ基、炭素数が２〜５の複素環基、水酸基、又はハロゲン原子等が挙げられる。
【００６９】
前記一般式(VIa) で表されるものの中で、トリメチン基を取り込んだ下記一般式(VIb) で表されるものが好ましい。
【００７０】
【化２９】
〔式(VIb) 中、Ｗ3 は、酸素原子を示し、Ｗ3 を含む複素環は置換基を有していてもよい。〕
【００７２】
ここで、式(VIb) 中の複素環における置換基としては、炭素数が１〜５のアルキル基、フェニル基、ナフチル基、アミノ基、又はハロゲン原子等が挙げられる。
【００７３】
以上の、ポリメチン鎖上の環状エーテル結合を含む置換基としての好適な例を以下に示す。
【００７４】
【化１２】
本発明における光熱変換物質として、以上の、ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じる環状エーテル結合を含む置換基を有する構造のシアニン系色素、及びポリメチン系色素の具体例としては、前記鎖状エーテル結合を含む置換基を有する色素として挙げた具体例中の、(I-1)〜(I-3) 、(II-1)〜(II-3)、(II-10) 〜(II-12) 、(III-2) 、(III-11)、(III-13)〜(III-14)、(III-20)、(IV-1)〜(IV-6)において、置換基としてＡを有する炭素原子とそれに結合する２個の炭素原子を含んだトリメチン基を前記一般式(VIa) に代えたものが挙げられる。
【００７６】
尚、ポリメチン鎖を介して複素原子が結合された構造を基本構造とし、該ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を有するこれらの色素は、例えば、N.Narayanan et al. "Near-Infrared Dyes for High Technology Applications" S.Daehne,U.R.Genger,O.S.Wolfbeis 編（Kluwer Academic Publishers出版）に記載されている方法、具体的には、例えば、塩素原子を置換基として有するポリメチン鎖を介して複素環が結合された構造の色素と、相当するアルコールのナトリウム塩化合物との反応等により、合成することができる。
【００７７】
本発明のポジ型感光性組成物において、光熱変換物質としての前記色素の含有割合は、０．５〜５０重量％であるのが好ましく、１〜４０重量％であるのが更に好ましく、２〜３０重量％であるのが特に好ましい。
【００７８】
尚、本発明のポジ型感光性組成物において、光熱変換物質として、ポリメチン鎖上に、色素分子中で共鳴して、オキソニウムカチオンを生じるエーテル結合を含む置換基を有する構造の前記色素の外に、ポリメチン鎖上にそれらのエーテル結合及びチオエーテル結合を含む置換基を有さない構造の色素を含有してもよく、それらの色素としては、前記一般式(Ia 〜c)、(II)、(IIIa 〜c)、及び(IV)におけるＬ1 、Ｌ2 、Ｌ3、及びＬ4 がそれらのエーテル結合及びチオエーテル結合を含む置換基を有さないポリメチン鎖であって、且つ、対アニオンとして、前記一般式(Ia 〜c)、(II)、(IIIa 〜c)、及び(IV)において挙げたと同様の無機酸アニオンや有機酸アニオンを有するものを挙げることができる。
【００７９】
本発明のポジ型感光性組成物において、光熱変換物質として、ポリメチン鎖上にそれらのエーテル結合及びチオエーテル結合を含む置換基を有さない構造の色素の含有割合は、０〜２０重量％であるのが好ましく、０．１〜１５重量％であるのが更に好ましく、１〜１０重量％であるのが特に好ましい。
【００８０】
本発明のポジ型感光性組成物において、アルカリ可溶性樹脂としては、フェノール性水酸基を有する樹脂、具体的には、例えば、ノボラック樹脂、レゾール樹脂、ポリビニルフェノール樹脂、フェノール性水酸基を有するアクリル酸誘導体の共重合体等が挙げられ、中で、ノボラック樹脂、レゾール樹脂、又はポリビニルフェノール樹脂が好ましく、特に、ノボラック樹脂が好ましい。
【００８１】
ノボラック樹脂は、例えば、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、２，５−キシレノール、３，５−キシレノール、ｏ−エチルフェノール、ｍ−エチルフェノール、ｐ−エチルフェノール、プロピルフェノール、ｎ−ブチルフェノール、ｔｅｒｔ−ブチルフェノール、１−ナフトール、２−ナフトール、４，４’−ビフェニルジオール、ビスフェノール−Ａ、ピロカテコール、レゾルシノール、ハイドロキノン、ピロガロール、１，２，４−ベンゼントリオール、フロログリシノール等のフェノール類の少なくとも１種を、酸触媒下、例えば、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、フルフラール等のアルデヒド類（尚、ホルムアルデヒドに代えてパラホルムアルデヒドを、アセトアルデヒドに代えてパラアルデヒドを、用いてもよい。）、又は、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、の少なくとも１種と重縮合させた樹脂であって、中で、本発明においては、フェノール類としてのフェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、２，５−キシレノール、３，５−キシレノール、レゾルシノール、ピロガロールと、アルデヒド類又はケトン類としてのホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒドとの重縮合体が好ましく、特に、ｍ−クレゾール：ｐ−クレゾール：２，５−キシレノール：３，５−キシレノール：レゾルシノールの混合割合がモル比で４０〜１００：０〜５０：０〜２０：０〜２０：０〜２０の混合フェノール類、又は、フェノール：ｍ−クレゾール：ｐ−クレゾールの混合割合がモル比で１〜１００：０〜７０：０〜６０の混合フェノール類と、ホルムアルデヒドとの重縮合体が好ましい。尚、本発明のポジ型感光性組成物は後述する溶剤抑止剤を含有していてもよく、その場合は、ｍ−クレゾール：ｐ−クレゾール：２，５−キシレノール：３，５−キシレノール：レゾルシノールの混合割合がモル比で７０〜１００：０〜３０：０〜２０：０〜２０：０〜２０の混合フェノール類、又は、フェノール：ｍ−クレゾール：ｐ−クレゾールの混合割合がモル比で１０〜１００：０〜６０：０〜４０の混合フェノール類と、ホルムアルデヒドとの重縮合体が好ましい。
【００８２】
前記ノボラック樹脂は、ゲルパーミエーションクロマトグラフィー測定によるポリスチレン換算の重量平均分子量（ＭW ）が、好ましくは１，０００〜１５，０００、更に好ましくは１，５００〜１０，０００のものが用いられる。
【００８３】
又、レゾール樹脂は、ノボラック樹脂の重縮合における酸触媒に代えてアルカリ触媒を用いる以外は同様にして重縮合させた樹脂であって、本発明においては、前記ノボラック樹脂におけると同様の、フェノール類及びその混合組成、及び、アルデヒド類又はケトン類が好ましく、又、同様の重量平均分子量（ＭW ）のものが好ましい。
【００８４】
又、ポリビニルフェノール樹脂は、例えば、ｏ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシスチレン、ジヒドロキシスチレン、トリヒドロキシスチレン、テトラヒドロキシスチレン、ペンタヒドロキシスチレン、２−（ｏ−ヒドロキシフェニル）プロピレン、２−（ｍ−ヒドロキシフェニル）プロピレン、２−（ｐ−ヒドロキシフェニル）プロピレン等のヒドロキシスチレン類（尚、これらは、ベンゼン環に塩素、臭素、沃素、弗素等のハロゲン原子、あるいは炭素数１〜４のアルキル基を置換基として有していてもよい。）の単独または２種以上を、ラジカル重合開始剤又はカチオン重合開始剤の存在下で重合させた樹脂であって、中で、本発明においては、ベンゼン環に炭素数１〜４のアルキル基を置換基として有していてもよいヒドロキシスチレン類の重合体が好ましく、特に、無置換のベンゼン環のヒドロキシスチレン類の重合体が好ましい。
【００８５】
前記ポリビニルフェノール樹脂は、又、一部水素添加を行ったものでもよく、ｔｅｒｔ−ブトキシカルボニル基、ピラニル基、フリル基等で一部の水酸基を保護したものでもよい。又、重量平均分子量（ＭW ）が、好ましくは１，０００〜１００，０００、特に好ましくは１，５００〜５０，０００のものが用いられる。
【００８６】
ノボラック樹脂、レゾール樹脂、及びポリビニルフェノール樹脂の分子量が、前記範囲よりよりも小さいとレジストとしての十分な塗膜が得られず、前記範囲よりも大きいとアルカリ現像液に対する溶解性が小さくなり、非画像部の抜けが不十分となってレジストのパターンが得られにくくなる傾向となる。
【００８７】
本発明のポジ型感光性組成物において、前記アルカリ可溶性樹脂の含有割合は、１〜９８重量％であるのが好ましく、５〜９５重量％であるのが更に好ましく、２０〜９０重量％であるのが特に好ましい。
【００８８】
尚、本発明のポジ型感光性組成物には、前記光熱変換物質と前記アルカリ可溶性樹脂の他に、露光部と非露光部のアルカリ現像液に対する溶解性の差を増大させる目的で、前記アルカリ可溶性樹脂と水素結合を形成して該樹脂の溶解性を低下させる機能を有し、かつ、近赤外線領域の光を殆ど吸収せず、近赤外線領域の光で分解されない溶解抑止剤が含有されていてもよい。
【００８９】
その溶解抑止剤としては、例えば、本願出願人による特開平１０−２６８５１２号公報に詳細に記載されているスルホン酸エステル、燐酸エステル、芳香族カルボン酸エステル、芳香族ジスルホン、カルボン酸無水物、芳香族ケトン、芳香族アルデヒド、芳香族アミン、芳香族エーテル等、同じく特開平１１−１９０９０３号公報に詳細に記載されている、ラクトン骨格、Ｎ，Ｎ−ジアリールアミド骨格、ジアリールメチルイミノ骨格を有する酸発色性色素、同じく特開平１１−１４３０７６号公報に詳細に記載されている、ラクトン骨格、チオラクトン骨格、スルホラクトン骨格を有する塩基発色性色素、同じく特開平１０−３４１４００号公報に詳細に記載されている非イオン性界面活性剤等を挙げることができる。中で、ラクトン骨格を有する酸発色性色素が好ましい。
【００９０】
本発明のポジ型感光性組成物にける前記溶解抑止剤の含有割合は、０〜５０重量％であるのが好ましく、０〜３０重量％であるのが更に好ましく、０〜２０重量％であるのが特に好ましい。
【００９１】
又、本発明のポジ型感光性組成物には、必要に応じて、例えば、ビクトリアピュアブルー（４２５９５）、クリスタルバイオレット（４２５５５）、クリスタルバイオレットラクトン、オーラミンＯ（４１０００）、カチロンブリリアントフラビン（ベーシック１３）、ローダミン６ＧＣＰ（４５１６０）、ローダミンＢ（４５１７０）、サフラニンＯＫ７０：１００（５０２４０）、エリオグラウシンＸ（４２０８０）、ファーストブラックＨＢ（２６１５０）、Ｎｏ．１２０／リオノールイエロー（２１０９０）、リオノールイエローＧＲＯ（２１０９０）、シムラーファーストイエロー８ＧＦ（２１１０５）、ベンジジンイエロー４Ｔ−５６４Ｄ（２１０９５）、シムラーファーストレッド４０１５（１２３５５）、リオノールレッドＢ４４０１（１５８５０）、ファーストゲンブルーＴＧＲ−Ｌ（７４１６０）、リオノールブルーＳＭ（２６１５０）等の顔料又は染料等の着色剤が含有されていてもよい。尚、ここで、前記の括弧内の数字はカラーインデックス（Ｃ．Ｉ．）を意味する。
【００９２】
本発明のポジ型感光性組成物における前記着色剤の含有割合は、０〜５０重量％であるのが好ましく、１〜３０重量％であるのが更に好ましく、２〜２０重量％であるのが特に好ましい。
【００９３】
本発明のポジ型感光性組成物には、前記成分以外に、例えば、塗布性改良剤、現像性改良剤、密着性改良剤、感度改良剤、感脂化剤等の通常用いられる各種の添加剤が更に１０重量％以下、好ましくは０．１〜５重量％の範囲で含有されていてもよい。
【００９４】
本発明の前記ポジ型感光性組成物は、通常、前記各成分を適当な溶媒に溶解した溶液として支持体表面に塗布した後、加熱、乾燥することにより、支持体表面に感光性組成物層が形成されたポジ型感光性平版印刷版とされる。
【００９５】
ここで、その溶媒としては、使用成分に対して十分な溶解度を持ち、良好な塗膜性を与えるものであれば特に制限はないが、例えば、メチルセロソルブ、エチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート等のセロソルブ系溶媒、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールジメチルエーテル等のプロピレングリコール系溶媒、酢酸ブチル、酢酸アミル、酪酸エチル、酪酸ブチル、ジエチルオキサレート、ピルビン酸エチル、エチル−２−ヒドロキシブチレート、エチルアセトアセテート、乳酸メチル、乳酸エチル、３−メトキシプロピオン酸メチル等のエステル系溶媒、ヘプタノール、ヘキサノール、ジアセトンアルコール、フルフリルアルコール等のアルコール系溶媒、シクロヘキサノン、メチルアミルケトン等のケトン系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の高極性溶媒、酢酸、あるいはこれらの混合溶媒、更にはこれらに芳香族炭化水素を添加したもの等が挙げられる。溶媒の使用割合は、感光性組成物の総量に対して、通常、重量比で１〜２０倍程度の範囲である。
【００９６】
又、その塗布方法としては、従来公知の方法、例えば、回転塗布、ワイヤーバー塗布、ディップ塗布、エアーナイフ塗布、ロール塗布、ブレード塗布、及びカーテン塗布等を用いることができる。塗布量は用途により異なるが、乾燥膜厚として、通常、０．３〜７μｍ、好ましくは０．５〜５μｍ、特に好ましくは１〜３μｍの範囲とする。尚、その際の乾燥温度としては、例えば、６０〜１７０℃程度、好ましくは７０〜１５０℃程度、乾燥時間としては、例えば、５秒〜１０分間程度、好ましくは１０秒〜５分間程度が採られる。
【００９７】
又、その支持体としては、アルミニウム、亜鉛、銅、鋼等の金属板、アルミニウム、亜鉛、銅、鉄、クロム、ニッケル等をメッキ又は蒸着した金属板、紙、樹脂を塗布した紙、アルミニウム等の金属箔を貼着した紙、プラスチックフィルム、親水化処理したプラスチックフィルム、及びガラス板等が挙げられる。中で、好ましいのはアルミニウム板であり、塩酸又は硝酸溶液中での電解エッチング又はブラシ研磨による砂目立て処理、硫酸溶液中での陽極酸化処理、及び必要に応じて封孔処理等の表面処理が施されたアルミニウム板がより好ましい。又、支持体表面の粗さとしては、ＪＩＳ Ｂ０６０１に規定される平均粗さＲa で、通常、０．３〜１．０μｍ、好ましくは０．４〜０．８μｍ程度とする。
【００９８】
本発明でのポジ型感光性組成物層を画像露光する光源としては、主として、ＨｅＮｅレーザー、アルゴンイオンレーザー、ＹＡＧレーザー、ＨｅＣｄレーザー、半導体レーザー、ルビーレーザー等のレーザー光源が挙げられるが、特に、光を吸収して発生した熱により画像形成させる場合には、７００〜１３００ｎｍの近赤外レーザー光線を発生する光源が好ましく、例えば、ルビーレーザー、ＹＡＧレーザー、半導体レーザー、ＬＥＤ等の固体レーザーを挙げることができ、特に、小型で長寿命な半導体レーザーやＹＡＧレーザーが好ましい。これらの光源により、通常、走査露光した後、現像液にて現像し画像が形成される。
【００９９】
尚、レーザー光源は、通常、レンズにより集光された高強度の光線（ビーム）として感光性組成物層表面を走査するが、それに感応する本発明での感光性組成物層の感度特性（ｍＪ／ｃｍ2 ）は受光するレーザービームの光強度（ｍＪ／ｓ・ｃｍ2 ）に依存することがある。ここで、レーザービームの光強度は、光パワーメーターにより測定したレーザービームの単位時間当たりのエネルギー量（ｍＪ／ｓ）を感光性組成物層表面におけるレーザービームの照射面積（ｃｍ2 ）で除することにより求めることができる。レーザービームの照射面積は、通常、レーザーピーク強度の１／ｅ2 強度を越える部分の面積で定義されるが、簡易的には相反則を示す感光性組成物を感光させて測定することもできる。
【０１００】
本発明において、光源の光強度としては、２．０×１０6 ｍＪ／ｓ・ｃｍ2 以上とすることが好ましく、１．０×１０7 ｍＪ／ｓ・ｃｍ2 以上とすることが更に好ましい。光強度が前記範囲であれば、本発明でのポジ型感光性組成物層の感度特性を向上させ得て、走査露光時間を短くすることができ実用的に大きな利点となる。
【０１０１】
本発明の前記ポジ型感光性平版印刷版を画像露光したポジ型感光体の現像に用いる現像液としては、例えば、珪酸ナトリウム、珪酸カリウム、珪酸リチウム、珪酸アンモニウム、メタ珪酸ナトリウム、メタ珪酸カリウム、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、重炭酸ナトリウム、炭酸カリウム、第二燐酸ナトリウム、第三燐酸ナトリウム、第二燐酸アンモニウム、第三燐酸アンモニウム、硼酸ナトリウム、硼酸カリウム、硼酸アンモニウム等の無機アルカリ塩、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、モノブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン等の有機アミン化合物の０．１〜５重量％程度の水溶液からなるアルカリ現像液を用いる。中で、無機アルカリ塩である珪酸ナトリウム、珪酸カリウム等のアルカリ金属の珪酸塩が好ましい。尚、現像液には、必要に応じて、アニオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤等の界面活性剤や、アルコール等の有機溶媒を加えることができる。
【０１０２】
尚、現像は、浸漬現像、スプレー現像、ブラシ現像、超音波現像等により、通常、好ましくは１０〜５０℃程度、特に好ましくは１５〜４５℃程度の温度でなされる。
【０１０３】
【実施例】
以下、本発明を実施例により更に具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。
【０１０４】
参考例１
アルミニウム板（厚さ０．２４ｍｍ）を、５重量％の水酸化ナトリウム水溶液中で６０℃で１分間脱脂処理を行った後、０．５モル／リットルの濃度の塩酸水溶液中で、温度２８℃、電流密度６０Ａ／ｄｍ2 、処理時間４０秒の条件で電解エッチング処理を行った。次いで４重量％水酸化ナトリウム水溶液中で６０℃、１２秒間のデスマット処理を施した後、２０重量％硫酸溶液中で、温度２０℃、電流密度３．５Ａ／ｄｍ2 、処理時間１分の条件で陽極酸化処理を行った。更に、８０℃の熱水で２０秒間熱水封孔処理を行い、平版印刷版支持体用のアルミニウム板を作製した。表面粗度計（小坂研究所社製、「ＳＥ−３ＤＨ」）によるこの板の平均粗さＲａの値は０．６０μｍであった。
【０１０５】
得られたアルミニウム板支持体表面に、アルカリ可溶性樹脂として、フェノール：ｍ−クレゾール：ｐ−クレゾールの混合割合がモル比で２０：５０：３０の混合フェノール類と、ホルムアルデヒドとの重縮合体からなるノボラック樹脂（ＭW ７，０００）１００重量部、光熱変換物質として、鎖状チオエーテル結合を含む置換基を有する下記式のシアニン系色素３重量部、及びクリスタルバイオレットラクトン１０重量部を、メチルセロソルブ９００重量部に室温で１０分間攪拌して調液した塗布液をワイヤーバーを用いて塗布し、１００℃で１分間乾燥させた後、５５℃で１６時間、加熱処理することにより、塗膜量２．５ｇ／ｍ2 のポジ型感光性組成物層を有するポジ型感光性平版印刷版を作製した。用いた色素等は、１０分間の攪拌で完全に溶解し、均一なポジ型感光性組成物層を有するポジ型感光性平版印刷版が得られた。
【０１０６】
【化３１】
得られたポジ型感光性平版印刷版につき、８３０ｎｍの半導体レーザーを光源とする露光装置（クレオ社製、「Ｔｒｅｎｄ Ｓｅｔｔｅｒ ３２４４Ｔ」）を用いて各種の露光エネルギーで２００線、１〜９９％の網点画像を画像露光し、次いで、アルカリ現像液（富士写真フィルム社製「ＤＰ−４」の１０倍希釈液）を用いて２８℃で現像処理を行い、１〜９９％の網点画像を再現させた印刷版を作製した。そのときの感度を、３％の網点画像が再現する露光量として求めたところ、２００ｍＪ／ｃｍ2 であった。
【０１０８】
参考例２
感光性組成物層における光熱変換物質として、鎖状チオエーテル結合を含む置換基を有する下記式のシアニン系色素を用いた外は、参考例１と同様にして、ポジ型感光性平版印刷版を作製し現像した。そのときの感度を、３％の網点画像が再現する露光量として求めたところ、１４０ｍＪ／ｃｍ2 であった。
【０１０９】
【化３２】
実施例３
感光性組成物層における光熱変換物質として、環状エーテル結合を含む置換基を有する下記式のシアニン系色素を用いた外は、参考例１と同様にして、ポジ型感光性平版印刷版を作製し現像した。そのときの感度を、３％の網点画像が再現する露光量として求めたところ、１７０ｍＪ／ｃｍ2 であった。
【０１１１】
【化３３】
実施例４
感光性組成物層における光熱変換物質として、環状エーテル結合を含む置換基を有する下記式のシアニン系色素を用いた外は、参考例１と同様にして、ポジ型感光性平版印刷版を作製し現像した。そのときの感度を、３％の網点画像が再現する露光量として求めたところ、１５０ｍＪ／ｃｍ2 であった。
【０１１３】
【化３４】
比較例１
感光性組成物層における光熱変換物質として、参考例１で用いたシアニン系色素における鎖状チオエーテル結合を含む置換基を有さないシアニン系色素のみを用いた外は、参考例１と同様にして、ポジ型感光性平版印刷版を作製したが、感光性組成物層中に色素の結晶粒子による塗布欠陥が見られ、実用に耐える平版印刷版ではなかった。
【０１１５】
比較例２
感光性組成物層における光熱変換物質として、参考例２で用いたシアニン系色素における鎖状チオエーテル結合を含む置換基を有さないシアニン系色素のみを用いた外は、参考例１と同様にして、ポジ型感光性平版印刷版を作製したが、感光性組成物層中に色素の結晶粒子による塗布欠陥が見られ、実用に耐える平版印刷版ではなかった。
【０１１６】
【発明の効果】
本発明によれば、近赤外線領域の光に対して高感度であって、画像部と非画像部とのコントラストに優れ、よって、現像条件の幅の広いポジ型感光性組成物及びポジ型感光性平版印刷版を提供することができる。更に、本発明のポジ型感光性組成物は、溶媒に対する溶解性に優れるので、溶液としての支持体表面への塗布による感光性組成物層の形成を効率的に行うことができ、生産性の優れた平版印刷版を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is used for lithographic printing plates, color proofs for printing proofing, color filter resists for liquid crystal displays and plasma displays, photoresists for integrated circuits of semiconductor elements, copper etching resists for wiring boards and gravure plates, etc. The present invention relates to a positive photosensitive composition and a positive photosensitive lithographic printing plate that are highly sensitive to light in a region, and in particular, a positive photosensitive composition and a positive photosensitive composition that are suitable for direct plate making using a semiconductor laser, a YAG laser, or the like. Related to lithographic printing plates.
[0002]
[Prior art]
Conventionally, as the positive photosensitive composition, for example, an o-quinonediazide group-containing compound that becomes insoluble in alkali by generating indene carboxylic acid upon irradiation with light, an organic polymer substance having an o-nitrocarbinol ester group, or light There are known compositions of a compound that generates an acid by photoacid generator (photoacid generator) and a compound that is hydrolyzed by an acid and becomes alkali-soluble.
[0003]
On the other hand, with the advancement of computer image processing technology, a photosensitive or thermal direct plate making system that directly forms a resist image by laser light or a thermal head, etc., without outputting digital image information to a silver salt mask film is attracting attention. Has been. In particular, a high-resolution laser-sensitive direct plate-making system using a high-power semiconductor laser, a YAG laser, or the like is strongly desired to be realized from the viewpoints of downsizing, ambient light during plate-making work, and plate material cost. Yes.
[0004]
On the other hand, conventionally, as an image forming method using laser sensitivity or heat sensitivity, a method of forming a color material image using a sublimation transfer dye and a method of preparing a lithographic printing plate are known. Specifically, for example, a method of producing a lithographic printing plate using a crosslinking reaction of a diazo compound, a method of producing a lithographic printing plate using a decomposition reaction of nitrocellulose, and the like are known.
[0005]
In recent years, a technique in which a long-wavelength light-absorbing dye is combined with a chemically amplified photoresist has come to be seen. For example, JP-A-6-43633 discloses a photosensitive material in which a specific squarylium dye is combined with a photoacid generator and a binder, and as a similar technique, JP-A-7-20629 is disclosed. Japanese Laid-Open Patent Publication No. 7-271029 discloses a method for producing a lithographic printing plate by exposing a photosensitive composition layer containing an infrared absorbing dye, a latent Bronsted acid, a resole resin and a novolak resin to an image with a semiconductor laser or the like. JP-A-9-43847 discloses a method in which an s-triazine compound is used instead of the latent Bronsted acid, and JP-A-9-43847 changes the crystallinity of a photosensitive material by heating with infrared irradiation. A resist material and a pattern forming method using the resist material are disclosed.
[0006]
However, according to the study of the present inventors, these conventional techniques have low sensitivity to light in the near infrared region, and the difference in solubility between the exposed portion and the non-exposed portion with respect to the developer is small. The image portion is not sufficiently removed, the remaining film ratio of the image portion is not sufficiently maintained, and therefore, there are practical disadvantages such as a narrow range of development conditions.
[0007]
In contrast, the applicant of the present application is a simple system in which a photochemical change between a photothermal conversion substance and an alkali-soluble resin composed of a near-infrared absorbing dye having a structure in which a hetero atom is bonded via a polymethine chain cannot be expected, It was found that a photosensitive composition capable of forming a positive image with the above-mentioned drawbacks eliminated was obtained, and a patent application was first filed (see JP-A-10-268512), and further improvements were under consideration. .
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described prior art. Therefore, the present invention is highly sensitive to light in the near infrared region, and has excellent contrast between the image portion and the non-image portion. Accordingly, an object is to provide a positive photosensitive composition and a positive photosensitive lithographic printing plate having a wide range of development conditions.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor is a dye having a basic structure of a structure in which a hetero atom of a heterocyclic ring is bonded via a polymethine chain, and a specific substituent on the polymethine chain. The present invention has been completed by finding that a composition using an alkali-soluble resin as a photothermal conversion substance together with an alkali-soluble resin can achieve the above object, that is, the present invention absorbs light from an image exposure light source and converts it into heat. A positive-type photosensitive composition containing a photothermal conversion substance and an alkali-soluble resin, wherein the photothermal conversion substance is a dye having a structure in which a hetero atom is bonded via a polymethine chain, A positive photosensitive composition comprising a dye having a substituent having an ether bond that resonates in the dye molecule and generates an oxonium cation on the polymethine chain, and a support surface A layer of photosensitive composition The positive photosensitive lithographic printing plate comprising formed, and the gist to.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the positive photosensitive composition of the present invention, the photothermal conversion substance that absorbs the light from the image exposure light source and converts it into heat is a compound that can convert the absorbed light into heat. As a photothermal conversion substance, a dye having a basic structure in which a hetero atom of a heterocycle is bonded via a polymethine chain, and an ether that resonates in the dye molecule and generates an oxonium cation on the polymethine chain It contains a dye having a substituent containing a bond. Here, “resonate in the dye molecule” means, in other words, “resonate with the chromophore of the dye”, and the π electron of the chromophore in the dye molecule when the dye has the substituent. The system spreads, and the absorption peak is usually shifted to the longer wavelength side by 20 nm or more. In particular, the absorption efficiency in the near-infrared region of the wavelength region of 700 to 1300 nm can be improved. While these near-infrared absorbing dyes efficiently absorb light in the above-mentioned wavelength region, they absorb little light in the ultraviolet region or are substantially insensitive even when absorbed, and are weak ultraviolet rays contained in white lamps. Some compounds do not have the action of modifying the photosensitive composition.
[0011]
In the present invention, these dyes have, as a basic structure, a structure in which a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom is bonded via a polymethine (—CH═) n chain. Typically, those heteroatoms form a heterocyclic ring, and a so-called cyanine dye having a broad structure in which the heterocyclic ring is bonded via a polymethine chain, specifically, for example, a quinoline dye (so-called narrowly defined dye). Cyanine), indole (so-called indocyanine), benzothiazole (so-called thiocyanine), pyrylium, thiapyrylium, squarylium, croconium, azurenium, etc., and acyclic via a polymethine chain Examples include so-called polymethine dyes having a structure in which heteroatoms are bonded. Among them, quinoline, indole, benzothiazole, pyrylium, Cyanine dyes Apiririumu system, etc., and polymethine dye.
[0012]
As the basic structure of the dye in the present invention, among the cyanine dyes, those represented by the following general formula (Ia), (Ib), or (Ic) are particularly preferable as the quinoline dyes.
[0013]
[Chemical 7]
[In the formulas (Ia), (Ib), and (Ic), R 1 and R 2 are each independently an optionally substituted alkyl group or an optionally substituted alkenyl group. , An alkynyl group that may have a substituent, or a phenyl group that may have a substituent, and L 1 as an substituent, an ether bond that resonates in a dye molecule to generate an oxonium cation A tri-, penta-, hepta-, nona-, or undecametin group having at least a substituent containing, wherein two substituents on the penta-, hepta-, nona-, or undecametin group are linked together to form a cycloalkene having 5 to 7 carbon atoms May form a ring, a cycloalkenone ring, or a cycloalkenedione ring, and the quinoline ring may have a substituent, and in this case, two adjacent substituents are connected to each other to form a condensed benzene ring. Even if formed There. X a − represents a counter anion. ]
[0015]
Here, when R 1 and R 2 in the formulas (Ia), (Ib), and (Ic) are alkyl groups, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, alkenyl group, alkynyl group. Carbon number is usually 2 to 15, preferably 2 to 10, and the substituents including phenyl group are usually alkoxy groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, Examples include a phenoxy group, a hydroxy group, or a phenyl group, and examples of the substituent other than the substituent including the ether bond in L 1 include an alkyl group having the same number of carbon atoms, an amino group, or a halogen atom. Examples of the substituent in the ring include an alkyl group having the same carbon number, an alkoxy group having the same carbon number, a nitro group, and a halogen atom.
[0016]
As the basic structure of the dye in the present invention, among the cyanine dyes, the indole and benzothiazole dyes are particularly preferably those represented by the following general formula (II).
[0017]
[Chemical 8]
[In Formula (II), Y 1 and Y 2 each independently represent a dialkylmethylene group or a sulfur atom, and R 3 and R 4 each independently represent an alkyl group which may have a substituent, An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent, L 2 as a substituent in the dye molecule Represents a tri, penta, hepta, nona, or undecametine group having at least a substituent that includes an ether bond that produces an oxonium cation, wherein the two substituents on the penta, hepta, nona, or undecametin group linked to cycloalkene ring having 5 to 7 carbon atoms, cycloalkenone ring or cycloalkene dione ring may form a condensed benzene ring may have a substituent, in which case the adjacent One of the substituents may form a fused benzene ring linked to each other. X a − represents a counter anion. ]
[0019]
Here, the carbon number when R 3 and R 4 in the formula (II) is an alkyl group is usually 1 to 15, preferably 1 to 10, and the carbon number when an alkenyl group or an alkynyl group is usually These substituents including 2 to 15, preferably 2 to 10 and including phenyl group are usually alkoxy groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, phenoxy group, hydroxy group, or phenyl group. Examples of the substituent other than the substituent containing the ether bond in L 2 include an alkyl group having the same carbon number, an amino group, or a halogen atom, and the substituent in the condensed benzene ring is the same as above. Examples thereof include an alkyl group having a carbon number, an alkoxy group having the same carbon number, a nitro group, and a halogen atom.
[0020]
In addition, as the basic structure of the dye in the present invention, among the cyanine dyes, the pyrylium and thiapyrylium dyes are particularly represented by the following general formulas (IIIa), (IIIb), or (IIIc) Those are preferred.
[0021]
[Chemical 9]
[In formulas (IIIa), (IIIb), and (IIIc), Z 1 and Z 2 each independently represent an oxygen atom or a sulfur atom, and R 5 , R 6 , R 7 , and R 8 are each independently In addition, a hydrogen atom or an alkyl group, or R 5 and R 7 , and R 6 and R 8 may be connected to each other to form a cycloalkene ring having 5 or 6 carbon atoms, and L 3 is a substituent. As a mono, tri, penta, or heptamethine group having at least a substituent containing an ether bond that resonates in the dye molecule to produce an oxonium cation, and the two substituents on the tri, penta, or heptamethine group May be linked to each other to form a C5-C7 cycloalkene ring, cycloalkenone ring, or cycloalkenedione ring, and the pyrylium ring and the thiapyrylium ring may have a substituent. Two adjacent substituents are It may form a fused benzene ring linked to. X a − represents a counter anion. ]
[0023]
Here, when R 5 , R 6 , R 7 , and R 8 in formulas (IIIa), (IIIb), and (IIIc) are alkyl groups, the carbon number is usually 1 to 15, preferably 1 to Examples of the substituent other than the substituent including the ether bond in L 3 include an alkyl group having the same carbon number, an amino group, or a halogen atom, and the substituents in the pyrylium ring and the thiapyrylium ring are as follows. An aryl group such as a phenyl group can be mentioned.
[0024]
In addition, as the basic structure of the dye in the present invention, a polymethine dye is particularly preferably represented by the following general formula (IV).
[0025]
[Chemical Formula 10]
[In the formula (IV), R 9 , R 10 , R 11 and R 12 each independently represents an alkyl group, and R 13 and R 14 may each independently have a substituent. An aryl group, a furyl group, or a thienyl group, and L 4 is a mono-, tri-, penta-, or heptamethine group having at least a substituent containing an ether bond that resonates in a dye molecule to generate an oxonium cation. And the two substituents on the tri, penta, or heptamethine group may be linked to each other to form a cycloalkene ring, a cycloalkenone ring, or a cycloalkenedione ring having 5 to 7 carbon atoms. The ring and the benzene ring may have a substituent. X a − represents a counter anion. ]
[0027]
Here, the carbon number of the alkyl group of R 9 , R 10 , R 11 and R 12 in the formula (IV) is usually 1 to 15, preferably 1 to 10, and R 13 and R 14 are aryl groups. The number of carbon atoms is usually 6 to 20, preferably 6 to 15, and specifically as R 13 and R 14 , a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-furyl group, 3- A furyl group, a 2-thienyl group, a 3-thienyl group, and the like. Examples of the substituent include an alkyl group having the same carbon number, an alkoxy group having the same carbon number, a dialkylamino group, a hydroxy group, and a halogen atom. Examples of the substituent other than the substituent including the ether bond in L 4 include an alkyl group having the same number of carbon atoms, an amino group, or a halogen atom, and the substituents in the quinone ring and the benzene ring are the same as above. Alkyl group of carbon number Same as above alkoxy group carbon atoms include a nitro group, or a halogen atom and the like.
[0028]
The counter anions X a − in the general formulas (Ia to c), (II), (IIIa to c), and (IV) are specifically exemplified by Cl − , Br − , I − , Inorganic acid anions such as inorganic boronic acid such as ClO 4 − , PF 6 − , SbF 6 − , AsF 6 − and BF 4 − and BCl 4 − , and benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, Examples include acetic acid and organic acid anions such as organic boronic acid having an organic group such as methyl, ethyl, propyl, butyl, phenyl, methoxyphenyl, naphthyl, fluorophenyl, difluorophenyl, pentafluorophenyl, thienyl, and pyrrolyl. it can.
[0029]
As the basic structure of the dye in the present invention, the quinoline type represented by the above general formula (Ia to c), the indole type or benzothiazole type represented by the general formula (II), the general formula (IIIa to c) In the present invention, the indole represented by the general formula (II) is a cyanine dye such as a pyrylium-based or thiapyrylium-based dye represented by the formula (IV) and the polymethine-based dye represented by the general formula (IV). And benzothiazole dyes are particularly preferred.
[0030]
The polymethine chains including L 1 , L 2 , L 3 , and L 4 in the above formulas are heptamethine chains for the wavelength range of 700 to 850 nm, but for the wavelength range of 850 to 950 nm. Those that are nonametin chains are preferably undecametine chains for the wavelength range of 950 to 1300 nm.
[0031]
The dye in the present invention must have a structure having a substituent containing an ether bond that resonates in the dye molecule and generates an oxonium cation on the polymethine chain having the basic structure. Examples of the substituent containing include those bonded by a chain ether bond, and these may be bonded to the polymethine chain of the dye via another polymethine chain.
[0032]
The resonance mechanism of a dye having a substituent bonded to a polymethine chain by a chain ether bond that resonates in the dye molecule and generates an oxonium cation is, for example, that a nitrogen atom is bonded via a nonamethine chain. For example, the following formula is used.
[0033]
[Chemical 7]
In the present invention, specific examples of the substituent containing a chain ether bond include those represented by the following general formula (Va).
[0035]
Embedded image
[In formula (Va), W 1 represents an oxygen atom, and R a has an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An optionally substituted heterocyclic group is shown. ]
[0037]
Here, the carbon number when R a in the formula (Va) is an alkyl group is usually 1 to 15, preferably 1 to 10, and the carbon number when it is an aryl group is usually 6 to 20, preferably 6-15, the number of carbons in the case of a heterocyclic ring is usually 2-15, preferably 2-10, and the substituents thereof are alkyl groups having 1-5 carbon atoms, and carbon numbers 1-5. Alkoxy group or thioalkoxy group, an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, a phenyl group, a naphthyl group, an isocyanate group or an isothiocyanate group. Examples include an isocyanate group, an oxo group or a thioxo group, a heterocyclic group having 2 to 5 carbon atoms, a hydroxyl group, or a halogen atom.
[0038]
Among those represented by the general formula (Va), those in which R a is a phenyl group or those represented by the following general formula (Vb) in which R a is a heterocyclic group are preferable.
[0039]
Embedded image
[In Formula (Vb), W 1 represents an oxygen atom, W 2 represents an oxygen atom, a sulfur atom, a nitrogen atom, or a dialkylmethylene group, and W 1 and W 2 may be the same or different. Alternatively, the heterocyclic ring is a 4- to 6-membered ring and may have a substituent. In that case, two adjacent substituents may be connected to each other to form a condensed ring. ]
[0041]
Further, among those represented by the general formula (Vb), those represented by the following general formula (Vc), (Vd), or (Ve) are preferable, and those represented by the following general formula (Vc) Particularly preferred.
[0042]
[Chemical 8]
[In formula (Vc), W 1 represents an oxygen atom, W 1 and W 2 may be the same or different, and R b represents an alkyl group which may have a substituent, An alkoxy group or a thioalkoxy group which may have a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. ]
[0044]
[Chemical 9]
[In formula (Vd), W 1 represents an oxygen atom, W 1 and W 2 may be the same or different, and R c represents an alkyl group which may have a substituent, An aryl group which may have a group, a heterocyclic group which may have a substituent, or a hydrogen atom. ]
[0046]
Embedded image
[In Formula (Ve), W 1 represents an oxygen atom, W 2 represents an oxygen atom, a sulfur atom, a nitrogen atom, or a dialkylmethylene group, and W 1 and W 2 are the same or different. The condensed ring may be an aromatic hydrocarbon ring. ]
[0048]
Here, the carbon number when R b in the formula (Vc) and R c in (Vd) are alkyl groups is usually 1 to 5, and the carbon number when it is an alkoxy group or thioalkoxy group is usually 1 -5, the number of carbons in the case of an aryl group is usually from 6 to 10, the number of carbons in the case of a heterocyclic group is usually from 2 to 5, and when W 2 in the formula (Ve) is a dialkylmethylene group Carbon number is 3-15 normally.
[0049]
Suitable examples of the above substituents containing a chain ether bond on the polymethine chain are shown below.
[0050]
[Chemical Formula 10]
In addition, as these dyes in the present invention, a substituent containing a chain ether bond on the polymethine chain is directly or further via a divalent bond group via another chain ether bond, etc. A cross-linked structure bonded to the polymethine chain of the same or different dye may be used.
[0052]
As the photothermal conversion substance in the present invention, a cyanine dye having a structure having a substituent containing a chain ether bond that resonates in a dye molecule and generates an oxonium cation on the polymethine chain, and a polymethine dye. Specific examples are shown below. In the following specific examples, A is a substituent containing a chain ether bond, and X a − is Cl − , Br − , I − , ClO 4 − , PF 6 − , BF 4 − , p−. Counter anions such as toluenesulfonic acid or 1-naphthalenesulfonic acid.
[0053]
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Furthermore, in the present invention, on the polymethine chain having the above basic structure, as a substituent containing an ether bond that resonates in the dye molecule and generates an oxonium cation, a cyclic ether bond is formed by two substituents. Things.
[0063]
The resonance mechanism of a dye having a substituent that forms a cyclic ether bond that resonates in the dye molecule to form an oxonium cation on the polymethine chain is, for example, a nitrogen atom bonded via a nonametin chain Taking the structural dye as an example, the following formula is obtained.
[0064]
Embedded image
In the present invention, specific examples of the substituent containing a cyclic ether bond include those represented by the following general formula (VIa) incorporating a trimethine group.
[0066]
Embedded image
[In Formula (VIa), W 3 represents an oxygen atom, and the heterocyclic ring containing W 3 is a 5- or 6-membered ring optionally having a substituent. ]
[0068]
Here, the substituent in the heterocyclic ring in the formula (VIa) includes an alkyl group having 1 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, and a phenyl group. , A naphthyl group, an amino group, a heterocyclic group having 2 to 5 carbon atoms, a hydroxyl group, or a halogen atom.
[0069]
Of those represented by the general formula (VIa), those represented by the following general formula (VIb) incorporating a trimethine group are preferable.
[0070]
Embedded image
[In Formula (VIb), W 3 represents an oxygen atom, and the heterocyclic ring containing W 3 may have a substituent. ]
[0072]
Here, examples of the substituent in the heterocyclic ring in the formula (VIb) include an alkyl group having 1 to 5 carbon atoms, a phenyl group, a naphthyl group, an amino group, and a halogen atom.
[0073]
Suitable examples of the above substituents containing a cyclic ether bond on the polymethine chain are shown below.
[0074]
Embedded image
Specific examples of the above-described cyanine dyes and polymethine dyes having a structure having a substituent containing a cyclic ether bond that resonates in the dye molecule and generates an oxonium cation on the polymethine chain as the photothermal conversion substance in the present invention. Examples include (I-1) to (I-3), (II-1) to (II-3), (II) in the specific examples given as the dye having a substituent containing a chain ether bond. -10) to (II-12), (III-2), (III-11), (III-13) to (III-14), (III-20), (IV-1) to (IV-6) ), A trimethine group containing a carbon atom having A as a substituent and two carbon atoms bonded thereto is replaced by the general formula (VIa).
[0076]
These dyes having a structure in which a hetero atom is bonded via a polymethine chain as a basic structure and having a substituent containing an ether bond that resonates in the dye molecule and generates an oxonium cation on the polymethine chain are: For example, N.Narayanan et al. “Near-Infrared Dyes for High Technology Applications” S. Daehne, URGenger, edited by OSWolfbeis (published by Kluwer Academic Publishers), specifically, for example, chlorine atom It can be synthesized by a reaction of a dye having a structure in which a heterocyclic ring is bonded via a polymethine chain as a substituent and a sodium salt compound of the corresponding alcohol.
[0077]
In the positive photosensitive composition of the present invention, the content of the dye as the photothermal conversion substance is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, 30% by weight is particularly preferred.
[0078]
In the positive photosensitive composition of the present invention, as the photothermal conversion substance, the dye other than the dye having a structure having an ether bond that resonates in the dye molecule and generates an oxonium cation on the polymethine chain. In addition, a dye having a structure not having a substituent containing an ether bond and a thioether bond on the polymethine chain may be contained, and as the dye, the general formulas (Ia to c), (II), In (IIIa to c) and (IV), L 1 , L 2 , L 3 , and L 4 are polymethine chains having no substituents containing their ether bond and thioether bond, and as a counter anion Examples thereof include those having the same inorganic acid anions and organic acid anions as mentioned in the general formulas (Ia to c), (II), (IIIa to c) and (IV).
[0079]
In the positive photosensitive composition of the present invention, the content ratio of the dye having a structure not having a substituent containing an ether bond and a thioether bond on the polymethine chain is 0 to 20% by weight as the photothermal conversion substance. It is preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight.
[0080]
In the positive photosensitive composition of the present invention, the alkali-soluble resin may be a resin having a phenolic hydroxyl group, specifically, for example, a novolac resin, a resole resin, a polyvinylphenol resin, or an acrylic acid derivative having a phenolic hydroxyl group. Among them, a novolak resin, a resole resin, or a polyvinylphenol resin is preferable, and a novolak resin is particularly preferable.
[0081]
The novolak resin includes, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, tert-butylphenol, 1-naphthol, 2-naphthol, 4,4′-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglicinol, etc. At least one of the phenols in the form of an acid catalyst, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural (in addition to formaldehyde, paraformaldehyde , Or paraaldehyde instead of acetaldehyde), or a resin polycondensed with at least one of ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. In phenol, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, pyrogallol and formaldehyde, acetaldehyde, propion as aldehydes or ketones A polycondensate with an aldehyde is preferable, and the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcinol in a molar ratio of 40 to 100: 0 to 50: 0 to 20 : 0-20: 0-20 mixed phenols, or Phenol: m-cresol: a mixing ratio molar ratio of p- cresol 1-100: 0-70: 0-60 and mixed phenol, preferably polycondensate of formaldehyde. In addition, the positive photosensitive composition of this invention may contain the solvent inhibitor mentioned later, and in that case, m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcinol The mixing ratio of 70 to 100: 0 to 30: 0 to 20: 0 to 20: 0 to 20 in molar ratio, or the mixing ratio of phenol: m-cresol: p-cresol is 10 in molar ratio. A polycondensate of mixed phenols of ˜100: 0 to 60: 0 to 40 and formaldehyde is preferable.
[0082]
The novolak resin has a weight average molecular weight in terms of polystyrene by gel permeation chromatography measurement (M W) is preferably 1,000 to 15,000, more preferably those of 1,500 to 10,000 is used.
[0083]
The resol resin is a resin polycondensed in the same manner except that an alkali catalyst is used in place of the acid catalyst in the polycondensation of the novolak resin. In the present invention, the phenols are the same as those in the novolak resin. And mixed compositions thereof, and aldehydes or ketones are preferable, and those having the same weight average molecular weight (M W ) are preferable.
[0084]
Polyvinylphenol resins include, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2 Hydroxystyrenes such as-(m-hydroxyphenyl) propylene and 2- (p-hydroxyphenyl) propylene (note that these are halogen atoms such as chlorine, bromine, iodine and fluorine on the benzene ring, or carbon atoms of 1 to 4 In the presence of a radical polymerization initiator or a cationic polymerization initiator, and in the present invention, Has a C1-C4 alkyl group as a substituent on the benzene ring. Preferably the polymer of which may hydroxystyrenes have, in particular, polymers of hydroxystyrene unsubstituted benzene ring.
[0085]
The polyvinyl phenol resin may be partially hydrogenated, or may be partially protected with a tert-butoxycarbonyl group, pyranyl group, furyl group, or the like. The weight average molecular weight (M W ) is preferably 1,000 to 100,000, particularly preferably 1,500 to 50,000.
[0086]
When the molecular weight of the novolak resin, resol resin, and polyvinylphenol resin is smaller than the above range, a sufficient coating film as a resist cannot be obtained, and when the molecular weight is larger than the above range, the solubility in an alkaline developer is reduced. The omission of the image portion is insufficient, and the resist pattern tends to be difficult to obtain.
[0087]
In the positive photosensitive composition of the present invention, the content of the alkali-soluble resin is preferably 1 to 98% by weight, more preferably 5 to 95% by weight, and 20 to 90% by weight. Is particularly preferred.
[0088]
The positive photosensitive composition of the present invention contains, in addition to the photothermal conversion substance and the alkali-soluble resin, for the purpose of increasing the difference in solubility in an alkaline developer between an exposed area and an unexposed area. Contains a dissolution inhibitor that has a function of reducing the solubility of the resin by forming hydrogen bonds with the soluble resin, and hardly absorbs light in the near infrared region and is not decomposed by light in the near infrared region. May be.
[0089]
Examples of the dissolution inhibitor include sulfonic acid esters, phosphoric acid esters, aromatic carboxylic acid esters, aromatic disulfones, carboxylic acid anhydrides, aromatics described in detail in JP-A-10-268512 by the applicant of the present application. Acids having a lactone skeleton, an N, N-diarylamide skeleton, and a diarylmethylimino skeleton, which are also described in detail in JP-A-11-190903, such as aromatic ketones, aromatic aldehydes, aromatic amines, aromatic ethers, etc. Color-forming dyes, which are also described in detail in JP-A-11-143076, and base-coloring dyes having a lactone skeleton, thiolactone skeleton, and sulfolactone skeleton, which are also described in detail in JP-A-10-341400 And nonionic surfactants. Of these, acid-coloring dyes having a lactone skeleton are preferred.
[0090]
The content of the dissolution inhibitor in the positive photosensitive composition of the present invention is preferably 0 to 50% by weight, more preferably 0 to 30% by weight, and 0 to 20% by weight. Is particularly preferred.
[0091]
In addition, the positive photosensitive composition of the present invention may contain, for example, Victoria Pure Blue (42595), Crystal Violet (42555), Crystal Violet Lactone, Auramin O (41000), Catillon Brilliant Flavin (Basic). 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), Fast Black HB (26150), No. 13 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red B4401 (15850), Coloring agents such as pigments or dyes such as Fast Gen Blue TGR-L (74160) and Lionol Blue SM (26150) may be contained. Here, the number in the parenthesis means a color index (CI).
[0092]
The content of the colorant in the positive photosensitive composition of the present invention is preferably 0 to 50% by weight, more preferably 1 to 30% by weight, and 2 to 20% by weight. Particularly preferred.
[0093]
In addition to the above-mentioned components, the positive photosensitive composition of the present invention includes various commonly used additives such as a coatability improver, a developability improver, an adhesion improver, a sensitivity improver, and a sensitizer. The agent may further be contained in an amount of 10% by weight or less, preferably 0.1 to 5% by weight.
[0094]
The positive photosensitive composition of the present invention is usually coated on the surface of the support as a solution in which each of the components is dissolved in an appropriate solvent, and then heated and dried to form a photosensitive composition layer on the surface of the support. A positive photosensitive lithographic printing plate on which is formed.
[0095]
Here, the solvent is not particularly limited as long as it has sufficient solubility with respect to the components used and gives good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Cellosolve solvents such as acetate, propylene glycol such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether Solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl Ester solvents such as 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, cyclohexanone, methyl amyl ketone Ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, acetic acid, or a mixed solvent thereof, and those obtained by adding an aromatic hydrocarbon thereto. The use ratio of the solvent is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photosensitive composition.
[0096]
As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. The coating amount varies depending on the application, but the dry film thickness is usually in the range of 0.3 to 7 μm, preferably 0.5 to 5 μm, particularly preferably 1 to 3 μm. The drying temperature at that time is, for example, about 60 to 170 ° C., preferably about 70 to 150 ° C., and the drying time is, for example, about 5 seconds to 10 minutes, preferably about 10 seconds to 5 minutes. It is done.
[0097]
In addition, as the support, a metal plate such as aluminum, zinc, copper, steel, etc., a metal plate plated or vapor-deposited with aluminum, zinc, copper, iron, chromium, nickel, paper, paper coated with resin, aluminum, etc. Paper, plastic film, hydrophilized plastic film, glass plate, and the like with a metal foil attached thereto. Among them, an aluminum plate is preferable, and surface treatment such as graining treatment by electrolytic etching or brush polishing in hydrochloric acid or nitric acid solution, anodizing treatment in sulfuric acid solution, and sealing treatment as necessary is performed. An applied aluminum plate is more preferable. As the roughness of the support surface, average roughness R a as defined in JIS B0601, usually, 0.3 to 1.0 [mu] m, preferably about 0.4～0.8Myuemu.
[0098]
Examples of the light source for image exposure of the positive photosensitive composition layer in the present invention mainly include laser light sources such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, and ruby laser. In the case of forming an image by heat generated by absorbing light, a light source that generates a near infrared laser beam of 700 to 1300 nm is preferable, and examples thereof include solid lasers such as ruby laser, YAG laser, semiconductor laser, and LED. In particular, a small and long-life semiconductor laser or YAG laser is preferable. With these light sources, scanning exposure is usually performed, and then development is performed with a developer to form an image.
[0099]
The laser light source usually scans the surface of the photosensitive composition layer as a high-intensity light beam (beam) collected by a lens. The sensitivity characteristic (mJ) of the photosensitive composition layer according to the present invention is sensitive to the scanning. / cm 2) may be dependent on the light intensity of the laser beam for receiving (mJ / s · cm 2) . Here, the light intensity of the laser beam is obtained by dividing the amount of energy (mJ / s) per unit time of the laser beam measured by an optical power meter by the irradiation area (cm 2 ) of the laser beam on the surface of the photosensitive composition layer. Can be obtained. The irradiation area of the laser beam is usually defined as the area of the portion exceeding the 1 / e 2 intensity of the laser peak intensity, but can be measured by exposing a photosensitive composition exhibiting a reciprocity law in a simple manner. .
[0100]
In the present invention, the light intensity of the light source is preferably 2.0 × 10 6 mJ / s · cm 2 or more, and more preferably 1.0 × 10 7 mJ / s · cm 2 or more. When the light intensity is in the above range, the sensitivity characteristics of the positive photosensitive composition layer in the present invention can be improved, and the scanning exposure time can be shortened, which is a great advantage in practice.
[0101]
Examples of the developer used for developing the positive photosensitive material obtained by image exposure of the positive photosensitive lithographic printing plate of the present invention include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tribasic sodium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate Inorganic alkali salts such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanol Triethanolamine, monoisopropanolamine, an alkali developer comprising an aqueous solution of about 0.1 to 5% by weight of an organic amine compound diisopropanolamine used. Among them, alkali metal silicates such as sodium silicate and potassium silicate which are inorganic alkali salts are preferable. In addition, surfactants, such as anionic surfactant, nonionic surfactant, and amphoteric surfactant, and organic solvents, such as alcohol, can be added to a developing solution as needed.
[0102]
The development is usually carried out by immersion development, spray development, brush development, ultrasonic development or the like, preferably at a temperature of about 10 to 50 ° C., particularly preferably about 15 to 45 ° C.
[0103]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[0104]
Reference example 1
An aluminum plate (thickness 0.24 mm) was degreased at 60 ° C. for 1 minute in a 5 wt% sodium hydroxide aqueous solution, and then at a temperature of 28 ° C. in a hydrochloric acid aqueous solution having a concentration of 0.5 mol / liter. The electrolytic etching treatment was performed under the conditions of a current density of 60 A / dm 2 and a treatment time of 40 seconds. Next, desmutting treatment was performed in a 4 wt% aqueous sodium hydroxide solution at 60 ° C for 12 seconds, and then in a 20 wt% sulfuric acid solution, the temperature was 20 ° C, the current density was 3.5 A / dm 2 , and the treatment time was 1 minute. Anodizing treatment was performed. Further, hot water sealing treatment was performed with hot water at 80 ° C. for 20 seconds to produce an aluminum plate for a lithographic printing plate support. The average roughness Ra of the plate measured by a surface roughness meter (“SE-3DH” manufactured by Kosaka Laboratory Ltd.) was 0.60 μm.
[0105]
On the surface of the obtained aluminum plate support, it consists of a polycondensate of formaldehyde and a mixed phenol having a mixing ratio of phenol: m-cresol: p-cresol of 20:50:30 in molar ratio as an alkali-soluble resin. 100 parts by weight of novolak resin (M W 7,000), 3 parts by weight of a cyanine dye having a substituent containing a chain thioether bond as a photothermal conversion substance, and 10 parts by weight of crystal violet lactone, methyl cellosolve 900 A coating solution prepared by stirring at room temperature for 10 minutes in a part by weight was applied using a wire bar, dried at 100 ° C. for 1 minute, and then heat-treated at 55 ° C. for 16 hours to obtain a coating amount of 2 A positive photosensitive lithographic printing plate having a positive photosensitive composition layer of 0.5 g / m 2 was prepared. The dye used was completely dissolved by stirring for 10 minutes, and a positive photosensitive lithographic printing plate having a uniform positive photosensitive composition layer was obtained.
[0106]
Embedded image
About the obtained positive photosensitive lithographic printing plate, a 200-line, 1-99% network with various exposure energies using an exposure apparatus (“Trend Setter 3244T” manufactured by Creo Co., Ltd.) using a semiconductor laser of 830 nm as a light source. The dot image is exposed and then developed at 28 ° C. using an alkaline developer (10-fold diluted solution of “DP-4” manufactured by Fuji Photo Film Co., Ltd.) to reproduce a 1-99% dot image. A printing plate was prepared. The sensitivity at that time was determined as the exposure amount at which a 3% halftone dot image was reproduced, and was found to be 200 mJ / cm 2 .
[0108]
Reference example 2
A positive photosensitive lithographic printing plate is produced in the same manner as in Reference Example 1 except that a cyanine dye having the following formula having a substituent containing a chain thioether bond is used as the photothermal conversion substance in the photosensitive composition layer. And developed. When the sensitivity at that time was determined as the exposure amount at which a 3% halftone image was reproduced, it was 140 mJ / cm 2 .
[0109]
Embedded image
Example 3
A positive photosensitive lithographic printing plate was prepared in the same manner as in Reference Example 1 except that a cyanine dye having the following formula having a substituent containing a cyclic ether bond was used as the photothermal conversion material in the photosensitive composition layer. Developed. When the sensitivity at that time was determined as an exposure amount at which a 3% halftone image was reproduced, it was 170 mJ / cm 2 .
[0111]
Embedded image
Example 4
A positive photosensitive lithographic printing plate was prepared in the same manner as in Reference Example 1 except that a cyanine dye having the following formula having a substituent containing a cyclic ether bond was used as the photothermal conversion material in the photosensitive composition layer. Developed. The sensitivity at that time was determined as an exposure amount at which a 3% halftone dot image was reproduced, and was found to be 150 mJ / cm 2 .
[0113]
Embedded image
Comparative Example 1
As the photothermal conversion material in the photosensitive composition layer, the outer using only cyanine dye having no substituent containing a chain thioether bonds in cyanine dyes used in Reference Example 1, in the same manner as in Reference Example 1 A positive photosensitive lithographic printing plate was produced, but coating defects due to dye crystal particles were observed in the photosensitive composition layer, and the lithographic printing plate was not practical.
[0115]
Comparative Example 2
As the photothermal conversion material in the photosensitive composition layer, the outer using only cyanine dye having no substituent containing a chain thioether bonds in cyanine dyes used in Reference Example 2, in the same manner as in Reference Example 1 A positive photosensitive lithographic printing plate was produced, but coating defects due to dye crystal particles were observed in the photosensitive composition layer, and the lithographic printing plate was not practical.
[0116]
【The invention's effect】
According to the present invention, a positive photosensitive composition and a positive photosensitive composition that are highly sensitive to light in the near-infrared region, have excellent contrast between an image area and a non-image area, and thus have a wide range of development conditions. Sexual lithographic printing plates can be provided. Furthermore, since the positive photosensitive composition of the present invention is excellent in solubility in a solvent, it is possible to efficiently form a photosensitive composition layer by coating on the surface of a support as a solution, and to improve productivity. An excellent lithographic printing plate can be provided.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000250762A JP3949882B2 (en) | 1999-08-23 | 2000-08-22 | Positive photosensitive composition and positive photosensitive lithographic printing plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23521799 | 1999-08-23 | ||
| JP11-235217 | 1999-08-23 | ||
| JP2000250762A JP3949882B2 (en) | 1999-08-23 | 2000-08-22 | Positive photosensitive composition and positive photosensitive lithographic printing plate |
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| Publication Number | Publication Date |
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| JP2001142202A JP2001142202A (en) | 2001-05-25 |
| JP3949882B2 true JP3949882B2 (en) | 2007-07-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60025283T2 (en) | 1999-10-19 | 2006-08-24 | Fuji Photo Film Co., Ltd., Minami-Ashigara | Photosensitive composition and planographic printing plate using this composition |
| EP3130465B1 (en) * | 2015-08-12 | 2020-05-13 | Agfa Nv | Heat-sensitive lithographic printing plate precursor |
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