JP4615673B2 - Positive photosensitive composition and positive photosensitive lithographic printing plate - Google Patents
Positive photosensitive composition and positive photosensitive lithographic printing plate Download PDFInfo
- Publication number
- JP4615673B2 JP4615673B2 JP2000142956A JP2000142956A JP4615673B2 JP 4615673 B2 JP4615673 B2 JP 4615673B2 JP 2000142956 A JP2000142956 A JP 2000142956A JP 2000142956 A JP2000142956 A JP 2000142956A JP 4615673 B2 JP4615673 B2 JP 4615673B2
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- JP
- Japan
- Prior art keywords
- positive photosensitive
- photosensitive composition
- meth
- group
- resin
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 60
- 238000007639 printing Methods 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 27
- 229920000178 Acrylic resin Polymers 0.000 claims description 25
- 239000004925 Acrylic resin Substances 0.000 claims description 25
- 229920003986 novolac Polymers 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 description 38
- 239000000975 dye Substances 0.000 description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 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 14
- 150000001875 compounds Chemical class 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 125000005843 halogen group Chemical group 0.000 description 10
- -1 o-nitrobenzyl Chemical group 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000463 material 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-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
- 125000003545 alkoxy group Chemical group 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
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000004151 quinonyl group Chemical group 0.000 description 4
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 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
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 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
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 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
- 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 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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 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
- 239000007848 Bronsted acid Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 238000007743 anodising Methods 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 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
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film 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
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000010979 ruby Substances 0.000 description 2
- 229910001750 ruby Inorganic materials 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 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
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 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
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-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
- 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
- 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
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
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- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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- Materials For Photolithography (AREA)
- Printing Plates And Materials Therefor (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、感光性平版印刷版、簡易校正印刷用プルーフ、配線板やグラビア用銅エッチングレジスト、フラットディスプレイ製造に用いられるカラーフィルター用レジスト、ＬＳＩ製造用フォトレジスト等に使用される、主として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−ニトロベンジ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、加熱により溶解性を増す特定重合体化合物を含む組成物（特公昭４６−２７９１９号公報）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】
近年、レーザー感光又は感熱を利用した画像形成方法として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、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、光酸発生剤、及びバインダーを含む画像形成材料が、又、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画像形成材料が、又、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た画像形成材料が、更に、特開平７−２８５２７５号公報には、結着剤、光を吸収し熱を発生する物質、及び熱分解性でありかつ分解しない状態では結着剤の溶解性を実質的に低下させる物質を含む画像形成材料が、それぞれ開示されている。
【０００５】
又、これら従来の技術が、紫外線領域の光に対しても感応し、白色蛍光灯下における取扱時に反応が進行してしまい、そのため安定した品質のものが得られ難いという問題があるのに対して、特開平９−４３８４７号公報には、アルカリ現像液に対して難溶性の樹脂と赤外線吸収剤を含有し、赤外線照射等により加熱されて結晶性を変化させてアルカリ可溶性となるが紫外線照射では変化しないポジ型組成物が、又、ＷＯ９７／３９８９４号明細書には、水性現像可能なポリマーと該ポリマーの水性現像性を抑止する化合物を含有し、加熱により水性現像性が向上するが紫外線照射では変化しない熱感受性のポジ型組成物が、それぞれ開示されている。
【０００６】
これら特開平９−４３８４７号公報及びＷＯ９７／３９８９４号明細書に開示されるポジ型組成物は、露光により化学変化を生じる化合物を含有しその化学変化によって露光部と非露光部の溶解性に差異を生ぜしめる前述の従来技術における組成物とは異なり、化学変化以外の変化によって溶解性に差異を生ぜしめるものであると共に、紫外線領域の光に感受性を有する化合物を含まないため、白色蛍光灯下における取扱性に優れる等の利点を有する。
【０００７】
しかしながら、本発明者等の検討によれば、前述の従来技術は、露光後に加熱処理を要するネガ型感光性組成物においては、その処理条件によって得られる画像が必ずしも安定していない欠点を有する。又、露光後の加熱処理を要しないポジ型感光性組成物においては、感度、及び画像部（非露光部）と非画像部（露光部）とのコントラストが不十分で、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ない等の問題を有しており、特に、化学変化以外の変化によって露光部と非露光部の溶解性に差異を生ぜしめるような、特開平９−４３８４７号公報及びＷＯ９７／３９８９４号明細書に開示されるポジ型組成物においては、その傾向が顕著であることが判明した。
【０００８】
これに対して、本願出願人は、紫外線領域の光に感受性を有する化合物を含有せず、近赤外線領域の光に対す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、前述の問題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た（特開平１０−２６８５１２号公報）。
【０００９】
該特開平１０−２６８５１２号公報には、アルカリ可溶性樹脂としてノボラック樹脂やアクリル酸誘導体の共重合体が開示されているが、具体的にはノボラック樹脂を使用した例が示されているにすぎない。
又、特開平１０−２８２６４３号公報には、光熱変換物質及びアルカリ可溶性樹脂を含有するポジ型感光性組成物が更に有機酸を含むことで未露光部の残膜率が改善されることが開示され、ノボラック樹脂に有機酸としてポリアクリル酸を併用した例が示されているが、感光層の更なる高感度化を考慮すると、残膜率の更なる改善が望まれる。
【００１０】
一方、特開平１１−４４９５６号公報には、光を吸収して熱を発生する物質及び、フェノール性水酸基を有するアルカリ水溶液可溶性樹脂とスルホンアミド基、フェノール性水酸基含有アクリルアミド等の特定の共重合成分を含む共重合体とを５０：５０〜５：９５の範囲で含む赤外線レーザー用ポジ型感光性組成物によれば画像強度が向上し現像ラチチュードが改善することが記載され、ノボラック樹脂とアクリルアミド等を共重合成分とするある種のアクリル系共重合体を併用した例等も示されている
しかしながら、感度と残膜率の点で、今だ不十分である。
【００１１】
【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、紫外線領域の光に対しては感応せず、白色蛍光灯下における取扱性に優れると共に、感度、耐薬品性、及び画像部と非画像部とのコントラストに優れ、画像部の残膜率も十分に保持される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。
【００１２】
【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、（メタ）アクリル酸成分が１〜４０モル％のアクリル系共重合体を、ノボラック樹脂に対して特定割合で含有するポジ型感光性組成物ならびにそれを支持体上に設けてなるポジ型感光性平版印刷版により上記目的が達成されることを見い出し本発明を完成するに至った。
即ち本発明は、（Ａ）ノボラック樹脂、（Ｂ）アクリル系樹脂及び（Ｃ）光熱変換物質を含有するポジ型感光性組成物において、該アクリル系樹脂が共重合成分として（メタ）アクリル酸及び（メタ）アクリル酸エステルを含み、該（メタ）アクリル酸成分が１〜４０モル％の範囲である共重合体であって、該アクリル系樹脂と該ノボラック樹脂との重量比（％）が、１〜４０：９９〜６０の範囲にあることを特徴とするポジ型感光性組成物、及び支持体上に該ポジ型感光性組成物からなる層を有する感光性平版印刷版を要旨とする。
【００１３】
【発明の実施の形態】
先ず、本発明のポジ型感光性組成物における（Ａ）成分としてのノボラック樹脂は、フェノール性水酸基含有アルカリ可溶性樹脂として、この種感光性組成物のバインダー樹脂に慣用されているものであって、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、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、フロログルシノール、４，４’−ビフェニルジオール、２，２−ビス（４’−ヒドロキシフェニル）プロパン等のフェノール類の少なくとも１種を、酸性触媒下、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することが好ましく、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。
【００１４】
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（以下、単に重量平均分子量という）が、好ましくは１，５００〜２０，０００、更に好ましくは２，０００〜１５，０００、特に好ましくは３，０００〜１２，０００のものが用いられる。重量平均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。
【００１５】
次に本発明組成物の第２の必須成分である（Ｂ）アクリル系樹脂について説明する。アクリル系樹脂とは一般にアクリル酸、メタクリル酸又はこれらのエステルの単独重合体又はこれを共重合成分として含む共重合体であるが、本発明においては、かかるアクリル系樹脂が、共重合成分として（メタ）アクリル酸及び（メタ）アクリル酸エステルを含んでおり、該（メタ）アクリル酸成分が１〜４０モル％の範囲である共重合体（以下、本発明のアクリル系樹脂ということがある）である必要がある。尚、本明細書において、アクリル及びメタアクリルを総称して（メタ）アクリルと称する。又、共重合成分として、（メタ）アクリル酸及び（メタ）アクリル酸エステルを含むとは、アクリル酸及びメタアクリル酸の少なくとも１種と、アクリル酸及び（メタ）アクリル酸の少なくとも１種とを夫々共重合成分として含むことを意味する。
該（メタ）アクリル酸エステルは置換基があっても良いアルキルエステルまたはアリールエステルであって該アルキルとしては、例えば、メチル、エチル、ｎ−プロピル、ｎ−ブチル、ｉｓｏ−ブチル、ｔ−ブチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、２−エチルヘキシル等炭素数１〜１０のアルキル基が挙げられ、該アリールとしては、例えば、フェニル、１−ナフチル、２−ナフチル等炭素数６〜１０のアリール基が挙げられる。前記したあっても良い置換基としては、水酸基、アルコキシ基、ハロゲン原子、フェニル基、ジメチルアミノ基、エチレンオキサイド基、ビニル基、ｏ−カルボキシベンゾイルオキシ基などが挙げられる。
【００１６】
該アクリル系樹脂を構成する（メタ）アクリル酸の含量は１〜４０モル％の範囲でなければならない。従って、他の共重合成分が実質的に（メタ）アクリル酸エステルからなる場合はその含有量は９９〜６０モル％の範囲である。更に、より好ましい含有量は、（メタ）アクリル酸が２〜２０モル％、（メタ）アクリル酸エステルが９８〜８０モル％であり、特に好ましくは前者が３〜１５モル％、後者が９７〜８５モル％である。（メタ）アクリル酸の含量が上記範囲より過小の場合、アルカリ現象性が低下し、過大の場合、残膜率が低下し不利となる。
【００１７】
これらの（メタ）アクリル酸および（メタ）アクリル酸エステルからなるアクリル系樹脂はそれ自体で好ましい物性、例えば、好ましい現像許容度をもたらすが、更に、第三の共重合成分を共重合させる事によりその他の諸物性を改善または修飾が可能であり望ましい。その諸物性には、例えば、耐薬品性、耐刷性、感度、現像性等が含まれる。前記の第三の共重合成分としては、アクリロニトリル、スチレン、無水マレイン酸、マレイミド、アクリルアミド、ビニルアセテート、Ｎ−ビニルピロリドンの中から少なく一種を選択することが好ましい。これら第三の共重合成分を用いる場合、それのアクリル系樹脂中の含有量は４０モル％以下でなければならない。それが過大の場合、しばしば諸物性のバランスがくずれる傾向が見られる。第三の共重合成分を含有する場合の第三の共重合成分の含有量はより好ましくは５〜３０モル％であり、その場合の（メタ）アクリル酸の含有量は２〜２０モル％、（メタ）アクリル酸エステルの含有量は９３〜５０モル％である。
【００１８】
尚、本発明のアクリル系樹脂の重量平均分子量は、好ましくは５，０００〜２００，０００更に好ましくは１０，０００〜１００，０００、特に好ましくは１０，０００〜５０，０００のものが用いられる。該分子量が少なすぎると十分な塗膜が得られず、大きすぎると現像性が劣る傾向がある。
以上述べた本発明のアクリル系樹脂とノボラック樹脂との配合比率は重量でアクリル系樹脂１〜４０％、ノボラック樹脂９９〜６０％の範囲において使用する。アクリル系樹脂の配合量が過小の場合、残膜率の改善効果が認められず、過多の場合は、感度、現像性が低下し不利となる。
【００１９】
尚、本発明の感光性組成物には、本発明の性能を損わない範囲で本発明のノボラック樹脂及びアクリル系樹脂以外のアルカリ可溶性樹脂を含んでいてもよい。
次に、本発明のポジ型感光性組成物における（Ｃ）成分について述べる。これら光熱変換物質としては、吸収した光を熱に変換し得る化合物であれば特に限定されないが、波長域６５０〜１３００ｎｍの近赤外線領域の一部又は全部に吸収帯を有する有機又は無機の顔料や染料、有機色素、金属、金属酸化物、金属炭化物、金属硼化物等が挙げられる中で、光吸収色素が特に有効である。これらの光吸収色素は、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。
【００２０】
これらの光吸収色素としては、窒素原子、酸素原子、又は硫黄原子等を含む複素環等がポリメチン（−ＣＨ＝）n で結合された、広義の所謂シアニン系色素が代表的なものとして挙げられ、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）、オキサゾール系（所謂、オキサシアニン系）、アミノベンゼン系（所謂、ポリメチン系）、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、アミニウム系、イモニウム系、フタロシアニン系、アントラキノン系等が挙げられ、中で、キノリン系、インドール系、ベンゾチアゾール系、アミノベンゼン系、ピリリウム系、又はチアピリリウム系、アミニウム系、イモニウム系色素が好ましい。
【００２１】
本発明においては、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。
【００２２】
【化１】
〔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 は置換基を有していてもよいトリ、ペンタ、又はヘプタメチン基を示し、該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。Ｘ- は対アニオンを示す。〕
【００２４】
ここで、式(Ia)、(Ib)、及び(Ic)中のＲ1 及びＲ2 における置換基としては、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 における置換基としては、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、アルキル基、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。
【００２５】
又、インドール系、ベンゾチアゾール系色素及びベンゾオキサ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。
【００２６】
【化２】
〔式(II)中、Ｙ1 及びＹ2 は各々独立して、ジアルキルメチレン基、硫黄原子又は酸素原子を示し、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 は置換基を有していてもよいトリ、ペンタ、又はヘプタメチン基を示し、該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。Ｘ- は対アニオンを示す。〕
【００２８】
ここで、式(II)中のＲ3 及びＲ4 における置換基としては、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 における置換基としては、アルキル基、アミノ基、又はハロゲン原子等が挙げられ、ベンゼン環における置換基としては、アルキル基、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。
【００２９】
又、アミノベンゼン系色素としては、特に、下記一般式(III) で表されるものが好ましい。
【００３０】
【化３】
〔式(III) 中、Ｒ5 、Ｒ6 、Ｒ7 、及びＲ8 は各々独立して、アルキル基を示し、Ｒ9 及びＲ10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、Ｌ3 は置換基を有していてもよいモノ、トリ、又はペンタメチン基を示し、該トリ又はペンタメチン基上の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。Ｘ- は対アニオンを示す。〕
【００３２】
ここで、式(III) 中のＲ9 及びＲ10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、アルキル基、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、Ｌ3 における置換基としては、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、アルキル基、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。
【００３３】
又、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(IVa) 、(IVb) 、又は(IVc) で表されるものが好ましい。
【００３４】
【化４】
〔式(IVa) 、(IVa) 、及び(IVc) 中、Ｙ3 及びＹ4 は各々独立して、酸素原子又は硫黄原子を示し、Ｒ11、Ｒ12、Ｒ13、及びＲ14は各々独立して、水素原子又はアルキル基、又は、Ｒ11とＲ13、及びＲ12とＲ14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、Ｌ4 は置換基を有していてもよいモノ、トリ、又はペンタメチン基を示し、該トリ又はペンタメチン基上の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。Ｘ- は対アニオンを示す。〕
【００３６】
ここで、式(IVa) 、(IVa) 、及び(IVc) のＬ4 における置換基としては、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、ナフチル基等のアリール基等が挙げられる。
【００３７】
更に、アミニウム系、及びイモニウム系色素としては、Ｎ，Ｎ−ジアリールイミニウム塩骨格を少なくとも１個有するものが好ましく、特に、下記一般式(Va)、又は(Vb)で表されるものが好ましい。
【００３８】
【化５】
〔式(Va)、及び(Vb)中、Ｒ15、Ｒ16、Ｒ17、Ｒ18、Ｒ19、Ｒ20、Ｒ21、及びＲ22は各々独立して、水素原子、アルキル基、又はフェニル基を示し、キノン環及びベンゼン環は置換基を有していてもよい。Ｘ- は対アニオンを示す。尚、式(Vb)中の電子結合（─）は他の電子結合との共鳴状態を示す。〕
【００４０】
ここで、式(Va)、及び(Vb)中のキノン環及びベンゼン環における置換基としては、アルキル基、アルコキシ基、アシル基、ニトロ基、又はハロゲン原子等が挙げられる。
【００４１】
尚、前記一般式(Ia 〜c)、(II)、(III) 、(IVa〜c)、及び(Va 〜b)における対アニオンＸ- としては、例えば、Ｃｌ- 、Ｂｒ- 、Ｉ- 、ＣｌＯ4 - 、ＰＦ6 - 、及び、ＢＦ4 - 等の無機硼酸等の無機酸アニオン、ベンゼンスルホン酸、ｐ−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、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酸等の有機酸アニオンを挙げることができる。
【００４２】
以上、前記一般式(Ia 〜c)で表されるキノリン系色素、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、前記一般式(III) で表されるアミノベンゼン系色素、前記一般式(IVa〜c)で表されるピリリウム系又はチアピリリウム系色素、及び前記一般式(Va 〜b)で表されるアミニウム系又はイモニウム系色素の各具体例を以下に示す。
【００４３】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
【化１４】
【化１５】
【化１６】
以上説明した光熱変換物質の本発明の組成物への添加量は成分（Ａ）と（Ｂ）の樹脂成分の総量に対し０．１〜３０重量％、好ましくは０．５〜２０重量％、特に好ましくは１〜１２重量％である。
【００５５】
尚、本発明のポジ型感光性組成物には、前記三成分の他に、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、（Ａ）ノボラック樹脂、（Ｂ）アクリル系樹脂及び（Ｃ）光熱変換物質からなる混合物のアルカリ現像液に対する溶解性を低下させる溶解抑止剤を含有するのが好ましい。かかる溶解抑止剤は、具体的には（Ａ）成分の前記ノボラック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と推定される化合物であり、又、かかる溶解抑止剤は、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のが好ましい。
【００５６】
その溶解抑止剤としては、例えば、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し着色剤を兼ねた酸発色性色素、同じく特開２０００−１０５４５４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。
【００５７】
本発明のポジ型感光性組成物にお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。
【００５８】
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。
【００５９】
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、０．５〜３０重量％であるのが更に好ましく、１〜２０重量％であるのが特に好ましい。
【００６０】
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、好ましくは１０重量％以下、更に好ましくは５重量％以下の範囲で含有されていてもよい。
【００６１】
尚、本発明のポジ型感光性組成物は、オニウム塩、ジアゾニウム塩及びキノンジアジド化合物を含有しないことにより、紫外光に対して実質的に感受性を有さない。より具体的には、３６０〜４５０ｎｍの波長の光による照射の前後で、アルカリ現像液に対する溶解性に有意差を生ぜず、実用的な意味での画像形成機能を有さないことを意味する。
換言すれば、本発明でのポジ型感光性組成物は、白色蛍光灯（三菱電機（株）製３６Ｗ白色蛍光灯ネオルミスーパーＦＬＲ４０Ｓ−Ｗ／Ｍ／３６）下、４００ルクスの光強度において１０時間放置しても、アルカリ現像液に対する溶解性に実質的有意差を生じない性質を有するものである。尚、溶解性に実質的有意差を生じないとは、１０時間放置の前後で、アルカリ現像液に対する溶解性がほとんど変化しないことを意味する。
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。
【００６２】
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。
【００６３】
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、３〜７０ｍｇ／ｄｍ2、好ましくは５〜５０ｍｇ／ｄｍ2、特に好ましくは１０〜３０ｍｇ／ｄｍ2の範囲とする。尚、その際の乾燥温度としては、例えば、３０〜１７０℃程度、好ましくは４０〜１５０℃程度が採られる。
【００６４】
尚、本発明の効果を一層確実ならしめるために、例えば、４０〜１００℃程度、好ましくは４０〜７０℃程度の温度で、１分〜５０時間程度、好ましくは３０分〜２０時間程度の加熱処理を施すことが好ましい。
【００６５】
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。
【００６６】
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、６５０〜１３００ｎｍ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。
【００６７】
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。
【００６８】
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 以上とすることが特に好ましい。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る、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。
【００６９】
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。
【００７０】
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。
【００７１】
【実施例】
以下、本発明を実施例によりさら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。
【００７２】
実施例１〜８、比較例１〜３
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２５℃、電流密度６０Ａ／ｄｍ2 、処理時間３０秒の条件で電解エッチング処理を行った。次いで５重量％の水酸化ナトリウム水溶液中で６０℃、１０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３Ａ／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。
【００７３】
得られたアルミニウム板支持体表面に下記の試料感光液をワイヤーバーを用いて塗布し、８５℃で２分間乾燥させた後、５５℃で安定化させて塗膜量２．２ｇ／ｍ2のポジ型感光組成物層を有するポジ型感光性平版印刷版を作製した。
試料感光液：
（Ａ）ノボラック樹脂（フェノール／ｍ−クレゾール／ｐ−クレゾール＝５０／３０／２０、重量平均分子量＝９，０００住友ジュレズ社製）・・・１００重量部より下記（Ｂ）成分の配合量を差し引いた量
（Ｂ）アクリル系樹脂・・・表−１の表中に配合樹脂及び配合量（重量部）として記載
（Ｃ）光熱変換物質：前記II−９・・・・３重量部
着色剤：エチルバイオレット・・・・・３重量部
溶媒：メチルセロソルブ・・・・・・９０重量部
【００７４】
得られたポジ型感光性平版印刷版を回転ドラムに取り付け、ドラムを回転させながら、黄色灯下で、波長８３０ｎｍ、出力４０ｍＷの半導体レーザー（アプライドテクノ社製）を２５μｍのビームスポット径にて照射することにより走査露光し、次いで、アルカリ現像液（コニカ社製「ＳＤＲ−１」の６倍希釈液）に２８℃で浸漬した後、軽いこすりを加え現像を行った。
【００７５】
この際、１２０ｍＪ／ｃｍ2 及び２４０ｍＪ／ｃｍ2 の露光エネルギー（感度）で露光し、現像時間を変えることで２５μｍ幅のポジ画像を得た場合の残膜率を測定した。尚、該感度は得られたポジ画像が２５μｍ幅を与えるときのドラムの最大回転数から求めた。残膜率は大きい程良い成績を示している。
【００７６】
尚、残膜率は、得られたポジ画像について、非露光部における現像前後の反射濃度を反射濃度計（マクベス社製「ＲＤ−５１４」）を用いて測定し、感光性組成物層形成前の支持体表面の反射濃度の値を差引いたそれぞれの値の比から残膜率（％）を求めた。
なお配合樹脂の共重合比と重量平均分子量(Ｍｗ）を表の下に記載した。
表の結果より、アクリル酸が過多の場合（比較例−２）やアクリル系樹脂配合量が過多の場合（比較例−３）、望ましくない結果を与えることが理解される。
【００７７】
【表１】
なお上記の略号はＭＭＡ：メチルメタクリレート、ＭＭＡ：メタクリル酸、ＡＡ：アクリル酸、ＡＮ：アクリロニトリルを示す。
【００７９】
実施例−９
配合樹脂の成分としてのアクリロニトリル共重合成分の効果を調べる為、実施例−３（アクリロニトリル不含有）及び７（アクリロニトリル含有）で用いた感光性平版印刷版試料と同一のものをプレートクリーナーであるソルフィット溶媒（東華色素社製）に１分間浸漬した。その結果、両試料共ほぼ良好な耐薬品性を示し、余り大きな変化は認められなかったが、実施例−７の試料の方が実施例−３の試料より残膜率に於いてより優れていた。
尚、前記で得られたポジ型感光性平版印刷版は、白色蛍光灯（三菱電機社製３６Ｗ白色蛍光灯「ネオルミスーパーＦＬＲ４０Ｓ−Ｗ／Ｍ／３６」）の４００ルクスの光強度照射下に１０時間放置した後、前記と同様の現像処理を行った場合、いずれの実施例及び比較例においても実質的な膜減りはなく、白色蛍光灯下における取扱性は良好であった。
【００８０】
【発明の効果】
本発明によれば、紫外線領域の光に対しては感応せず、白色蛍光灯下における取扱性に優れると共に、近赤外線領域の光に対して感応し、感度、耐薬品性、及び画像部と非画像部とのコントラストに優れ、画像部の残膜率も十分に保持される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。[0001]
BACKGROUND OF THE INVENTION
The present invention is mainly used in photosensitive lithographic printing plates, proofs for simple proof printing, copper etching resists for wiring boards and gravure, color filter resists used in flat display production, photoresists for LSI production, 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 indenecarboxylic acid by light irradiation, an organic polymer substance having an o-nitrobenzyl ester group, or by light A composition comprising a compound that generates an acid (photoacid generator) and a compound that is hydrolyzed by an acid and becomes alkali-soluble, and a composition containing a specific polymer compound that increases solubility upon heating (Japanese Patent Publication No. 46-27919) ) Etc. are known.
[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]
In recent years, a technique in which a chemically amplified photoresist is combined with a long-wavelength light-absorbing dye as an image forming method using laser exposure or heat sensitivity has been widely used. For example, JP-A-6-43633 discloses a specific squarylium dye. An image forming material containing a photoacid generator and a binder, and JP-A-7-20629 discloses an image forming material containing an infrared absorbing dye, a latent Bronsted acid, a resole resin, and a novolac resin. JP-A-7-271029 discloses an image forming material using an s-triazine compound in place of the latent Bronsted acid, and JP-A-7-285275 discloses a binder, an optical material. An image forming material comprising a substance that absorbs heat and generates heat, and a substance that is thermally decomposable and substantially reduces the solubility of the binder when not decomposed It has been disclosed, respectively.
[0005]
In addition, these conventional techniques are sensitive to light in the ultraviolet region, and the reaction proceeds during handling under a white fluorescent lamp, so that it is difficult to obtain a stable quality product. JP-A-9-43847 contains a resin that is hardly soluble in an alkali developer and an infrared absorber, and is heated by infrared irradiation or the like to change its crystallinity and become alkali-soluble. The positive type composition that does not change is contained in WO97 / 39894, and contains an aqueous developable polymer and a compound that inhibits the aqueous developability of the polymer. Heat sensitive positive compositions that do not change upon irradiation are each disclosed.
[0006]
These positive compositions disclosed in JP-A-9-43847 and WO97 / 39894 contain a compound that undergoes a chemical change upon exposure, and the chemical change causes a difference in solubility between the exposed and unexposed areas. Unlike the composition in the prior art described above, which causes a difference in solubility due to a change other than a chemical change and does not contain a compound sensitive to light in the ultraviolet region, It has advantages such as excellent handleability.
[0007]
However, according to the study by the present inventors, the above-described conventional technique has a defect that an image obtained depending on the processing conditions is not always stable in a negative photosensitive composition that requires heat treatment after exposure. Further, in a positive photosensitive composition that does not require a heat treatment after exposure, sensitivity and contrast between an image part (non-exposed part) and a non-image part (exposed part) are insufficient, and as a result, non-image The film is not sufficiently removed, and the remaining film ratio of the image area is not sufficiently maintained.In particular, a change other than a chemical change causes a difference in solubility between the exposed area and the unexposed area. In the positive compositions disclosed in Japanese Patent Application Laid-Open Nos. 9-43847 and WO97 / 39894, the tendency has been found to be remarkable.
[0008]
On the other hand, the applicant of the present invention does not contain a compound sensitive to light in the ultraviolet region and is a simple system that cannot expect photochemical changes between a photothermal conversion substance and an alkali-soluble resin with respect to light in the near infrared region. , The previous questionThe titleIt has been found that a photosensitive composition capable of forming a resolved positive image is obtained (Japanese Patent Laid-Open No. 10-268512).
[0009]
Japanese Patent Laid-Open No. 10-268512 discloses a novolak resin or a copolymer of an acrylic acid derivative as an alkali-soluble resin, but only a specific example using a novolak resin is shown. .
Japanese Laid-Open Patent Publication No. 10-282463 discloses that a positive photosensitive composition containing a photothermal conversion substance and an alkali-soluble resin further contains an organic acid, thereby improving the remaining film ratio in the unexposed area. In addition, an example in which polyacrylic acid is used as an organic acid in combination with a novolak resin is shown, but further improvement in the remaining film ratio is desired in consideration of further increase in sensitivity of the photosensitive layer.
[0010]
On the other hand, JP-A-11-44956 discloses a substance that absorbs light and generates heat, and a specific copolymer component such as an alkaline aqueous solution-soluble resin having a phenolic hydroxyl group, a sulfonamide group, and a phenolic hydroxyl group-containing acrylamide According to a positive photosensitive composition for infrared lasers containing a copolymer containing 50:50 to 5:95, it is described that image strength is improved and development latitude is improved, novolak resin and acrylamide, etc. There are also examples of using some acrylic copolymers with a copolymer component as a copolymer.
However, the sensitivity and the remaining film rate are still insufficient.
[0011]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described conventional technology, is insensitive to light in the ultraviolet region, has excellent handleability under a white fluorescent lamp, and has sensitivity, chemical resistance, and image area. It is an object of the present invention to provide a positive photosensitive composition and a positive photosensitive lithographic printing plate that are excellent in contrast with the non-image area and have a sufficient remaining film ratio in the image area.
[0012]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventor has a positive photosensitive composition containing an acrylic copolymer having a (meth) acrylic acid component of 1 to 40 mol% in a specific ratio with respect to the novolak resin. The present invention has been completed by finding that the above object is achieved by a positive photosensitive lithographic printing plate comprising a product and a support provided thereon.
That is, the present invention relates to a positive photosensitive composition containing (A) a novolak resin, (B) an acrylic resin, and (C) a photothermal conversion substance, wherein the acrylic resin is used as a copolymerization component (meth) acrylic acid and A copolymer containing a (meth) acrylic acid ester, wherein the (meth) acrylic acid component is in the range of 1 to 40 mol%, and the weight ratio (%) between the acrylic resin and the novolak resin is The gist of the present invention is a positive photosensitive composition having a range of 1 to 40:99 to 60, and a photosensitive lithographic printing plate having a layer made of the positive photosensitive composition on a support.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
First, the novolak resin as the component (A) in the positive photosensitive composition of the present invention is commonly used as a phenolic hydroxyl group-containing alkali-soluble resin in the binder resin of this type of photosensitive composition, 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, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, 4,4′-biphenyldiol, 2,2-bis (4 ′) -Hydroxyphenyl) propane At least one kind of diols may be used under an acidic catalyst, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural, etc. Or a resin polycondensed with at least one of ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, wherein in the present invention, phenol as phenols, o-cresol, Preferred are polycondensates of m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol and formaldehyde, acetaldehyde, propionaldehyde as aldehydes or ketones, especially Mixed phenol having a 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 to 20: 0 to 20 Or a polycondensate of phenol and m-cresol: p-cresol mixed phenols having a molar ratio of 1 to 100: 0 to 70: 0 to 60 and formaldehyde. In addition, it is preferable that the positive photosensitive composition of this invention contains the solvent inhibitor mentioned later, and in that case, m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcinol The mixing ratio is 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 to 10 in molar ratio. A polycondensate of 100: 0 to 60: 0 to 40 mixed phenols with formaldehyde is preferred.
[0014]
The novolak resin has a polystyrene-reduced weight average molecular weight (hereinafter simply referred to as a weight average molecular weight) measured by gel permeation chromatography, preferably 1,500 to 20,000, more preferably 2,000 to 15,000, Particularly preferably, 3,000 to 12,000 are used. If the weight average molecular weight is smaller than the above range, a sufficient coating film as a resist cannot be obtained. If the weight average molecular weight is larger than the above range, the solubility in an alkali developer is reduced, and the non-image area is insufficiently omitted. It tends to be difficult to obtain a resist pattern.
[0015]
Next, (B) acrylic resin, which is the second essential component of the composition of the present invention, will be described. The acrylic resin is generally a homopolymer of acrylic acid, methacrylic acid or an ester thereof, or a copolymer containing this as a copolymer component. In the present invention, such an acrylic resin is used as a copolymer component ( A copolymer containing (meth) acrylic acid and a (meth) acrylic acid ester, wherein the (meth) acrylic acid component is in the range of 1 to 40 mol% (hereinafter sometimes referred to as the acrylic resin of the present invention). Need to be. In this specification, acrylic and methacryl are collectively referred to as (meth) acryl. Moreover, as a copolymerization component, (meth) acrylic acid and (meth) acrylic acid ester include at least one of acrylic acid and methacrylic acid, and at least one of acrylic acid and (meth) acrylic acid. It means that each is included as a copolymerization component.
The (meth) acrylic acid ester is an alkyl ester or aryl ester which may have a substituent. Examples of the alkyl include methyl, ethyl, n-propyl, n-butyl, iso-butyl, t-butyl, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl. Examples of the aryl include 6 to 10 carbon atoms such as phenyl, 1-naphthyl and 2-naphthyl. Of the aryl group. Examples of the substituent that may be mentioned include a hydroxyl group, an alkoxy group, a halogen atom, a phenyl group, a dimethylamino group, an ethylene oxide group, a vinyl group, and an o-carboxybenzoyloxy group.
[0016]
The content of (meth) acrylic acid constituting the acrylic resin must be in the range of 1 to 40 mol%. Accordingly, when the other copolymer component is substantially composed of (meth) acrylic acid ester, the content thereof is in the range of 99 to 60 mol%. Furthermore, more preferable content is 2-20 mol% of (meth) acrylic acid, 98-80 mol% of (meth) acrylic acid ester, Most preferably, the former is 3-15 mol% and the latter is 97- 85 mol%. When the content of (meth) acrylic acid is excessively smaller than the above range, the alkali phenomenon is decreased.
[0017]
An acrylic resin composed of these (meth) acrylic acid and (meth) acrylic acid ester itself has preferable physical properties, for example, preferable development tolerance, but further, by copolymerizing a third copolymer component. It is desirable that other physical properties can be improved or modified. The physical properties include, for example, chemical resistance, printing durability, sensitivity, developability and the like. As the third copolymer component, it is preferable to select at least one of acrylonitrile, styrene, maleic anhydride, maleimide, acrylamide, vinyl acetate, and N-vinylpyrrolidone. When these third copolymerization components are used, their content in the acrylic resin must be 40 mol% or less. When it is excessive, there is often a tendency for the balance of physical properties to be lost. The content of the third copolymer component in the case of containing the third copolymer component is more preferably 5 to 30 mol%, and the content of (meth) acrylic acid in that case is 2 to 20 mol%, Content of (meth) acrylic acid ester is 93-50 mol%.
[0018]
The weight average molecular weight of the acrylic resin of the present invention is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, particularly preferably 10,000 to 50,000. If the molecular weight is too small, a sufficient coating film cannot be obtained, and if it is too large, developability tends to be inferior.
The blend ratio of the acrylic resin and the novolak resin of the present invention described above is used in the range of 1 to 40% acrylic resin and 99 to 60% novolak resin by weight. When the blending amount of the acrylic resin is too small, the effect of improving the remaining film rate is not recognized, and when it is excessive, the sensitivity and developability are lowered and disadvantageous.
[0019]
The photosensitive composition of the present invention may contain an alkali-soluble resin other than the novolak resin and acrylic resin of the present invention within a range not impairing the performance of the present invention.
Next, the component (C) in the positive photosensitive composition of the present invention will be described. These photothermal conversion materials are not particularly limited as long as they are compounds capable of converting absorbed light into heat, but organic or inorganic pigments having an absorption band in a part or all of the near infrared region in the wavelength range of 650 to 1300 nm, Among dyes, organic pigments, metals, metal oxides, metal carbides, metal borides and the like, light absorbing pigments are particularly effective. These light-absorbing dyes efficiently absorb light in the above-mentioned wavelength range, but hardly absorb light in the ultraviolet region, or are not substantially sensitive to absorption, and are weak by ultraviolet rays contained in white light. Is a compound having no action of modifying the photosensitive composition.
[0020]
As these light-absorbing dyes, a heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or the like is polymethine (—CH═).nTypical examples include so-called cyanine dyes in a broad sense, which are bonded to each other. Specific examples include quinoline (so-called cyanine-based), indole (so-called indocyanine), and benzothiazole. System (so-called thiocyanine system), oxazole system (so-called oxacyanine system), aminobenzene system (so-called polymethine system), pyrylium system, thiapyrylium system, squarylium system, croconium system, azurenium system, aminium system, imonium system, phthalocyanine And quinoline, indole, benzothiazole, aminobenzene, pyrylium, or thiapyrylium, aminium, and imonium dyes.
[0021]
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.
[0022]
[Chemical 1]
[In formulas (Ia), (Ib), and (Ic), R1And R2Each independently has 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 substituent. Represents a good phenyl group, L1Represents a tri, penta, or heptamethine group which may have a substituent, and two substituents on the penta or heptamethine group are connected to each other to form a C5-C7 cycloalkene ring. In addition, the quinoline ring may have a substituent, and in this case, two adjacent substituents may be connected to each other to form a condensed benzene ring. X-Represents a counter anion. ]
[0024]
Where R in the formulas (Ia), (Ib), and (Ic)1And R2Examples of the substituent in the group include an alkoxy group, a phenoxy group, a hydroxy group, and a phenyl group.1Examples of the substituent in the group include an alkyl group, an amino group, and a halogen atom, and examples of the substituent in the quinoline ring include an alkyl group, an alkoxy group, a nitro group, and a halogen atom.
[0025]
As the indole, benzothiazole dyes and benzoxazole dyes, those represented by the following general formula (II) are particularly preferable.
[0026]
[Chemical formula 2]
[In formula (II), Y1And Y2Each independently represents a dialkylmethylene group, a sulfur atom or an oxygen atom;ThreeAnd RFourEach independently has 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 substituent. Represents a good phenyl group, L2Represents a tri, penta, or heptamethine group which may have a substituent, and two substituents on the penta or heptamethine group are connected to each other to form a C5-C7 cycloalkene ring. Alternatively, the condensed benzene ring may have a substituent, and in this case, two adjacent substituents may be connected to each other to form a condensed benzene ring. X-Represents a counter anion. ]
[0028]
Here, R in the formula (II)ThreeAnd RFourExamples of the substituent in the group include an alkoxy group, a phenoxy group, a hydroxy group, and a phenyl group.2Examples of the substituent in the group include an alkyl group, an amino group, and a halogen atom, and examples of the substituent in the benzene ring include an alkyl group, an alkoxy group, a nitro group, and a halogen atom.
[0029]
As the aminobenzene dye, those represented by the following general formula (III) are particularly preferable.
[0030]
[Chemical 3]
[In formula (III), RFive, R6, R7And R8Each independently represents an alkyl group, R9And RTenEach independently represents an aryl group, a furyl group or a thienyl group which may have a substituent, and LThreeRepresents a mono-, tri-, or pentamethine group which may have a substituent, and two substituents on the tri- or pentamethine group are connected to each other to form a C5-C7 cycloalkene ring. In addition, the quinone ring and the benzene ring may have a substituent. X-Represents a counter anion. ]
[0032]
Here, R in the formula (III)9And RTenSpecifically, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, and the like can be mentioned. An alkyl group, an alkoxy group, a dialkylamino group, a hydroxy group, or a halogen atom;ThreeExamples of the substituent in the group include an alkyl group, an amino group, and a halogen atom, and examples of the substituent in the quinone ring and the benzene ring include an alkyl group, an alkoxy group, a nitro group, and a halogen atom.
[0033]
As the pyrylium-based and thiapyrylium-based dyes, those represented by the following general formula (IVa), (IVb), or (IVc) are particularly preferable.
[0034]
[Formula 4]
[In formula (IVa), (IVa) and (IVc), YThreeAnd YFourEach independently represents an oxygen atom or a sulfur atom, and R11, R12, R13And R14Each independently represents a hydrogen atom or an alkyl group, or R11And R13And R12And R14May be linked to each other to form a cycloalkene ring having 5 or 6 carbon atoms.FourRepresents a mono-, tri-, or pentamethine group which may have a substituent, and two substituents on the tri- or pentamethine group are connected to each other to form a C5-C7 cycloalkene ring. Alternatively, the pyrylium ring and the thiapyrylium ring may have a substituent, and in this case, two adjacent substituents may be connected to each other to form a condensed benzene ring. X-Represents a counter anion. ]
[0036]
Where L in formulas (IVa), (IVa), and (IVc)FourExamples of the substituent in the group include an alkyl group, an amino group, and a halogen atom, and examples of the substituent in the pyrylium ring and the thiapyrylium ring include an aryl group such as a phenyl group and a naphthyl group.
[0037]
Further, as the aminium-based and imonium-based dyes, those having at least one N, N-diaryliminium salt skeleton are preferable, and those represented by the following general formula (Va) or (Vb) are particularly preferable. .
[0038]
[Chemical formula 5]
[In the formulas (Va) and (Vb), R15, R16, R17, R18, R19, R20, Rtwenty oneAnd Rtwenty twoEach independently represents a hydrogen atom, an alkyl group, or a phenyl group, and the quinone ring and the benzene ring may have a substituent. X-Represents a counter anion. In addition, the electronic bond (-) in Formula (Vb) shows the resonance state with another electronic bond. ]
[0040]
Here, examples of the substituent in the quinone ring and the benzene ring in the formulas (Va) and (Vb) include an alkyl group, an alkoxy group, an acyl group, a nitro group, and a halogen atom.
[0041]
Incidentally, the counter anion X in the general formulas (Ia to c), (II), (III), (IVa to c), and (Va to b)-For example, Cl-, Br-, I-, ClOFour -, PF6 -And BFFour -Inorganic acid anions such as inorganic boric acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, acetic acid, and methyl, ethyl, propyl, butyl, phenyl, methoxyphenyl, naphthyl, difluorophenyl, pentafluorophenyl, Examples thereof include organic acid anions such as organic boric acid having an organic group such as thienyl and pyrrolyl.
[0042]
The quinoline dyes represented by the general formulas (Ia to c), the indole or benzothiazole dyes represented by the general formula (II), and the aminobenzene dyes represented by the general formula (III) Specific examples of the pyrylium or thiapyrylium dyes represented by the general formulas (IVa to c) and the aminium or imonium dyes represented by the general formulas (Va to b) are shown below.
[0043]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
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The amount of the photothermal conversion substance described above added to the composition of the present invention is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total amount of the resin components (A) and (B). Particularly preferred is 1 to 12% by weight.
[0055]
In addition to the above three components, the positive photosensitive composition of the present invention includes (A) a novolak resin, (B) for the purpose of increasing the difference in solubility in an alkaline developer between an exposed area and an unexposed area. It is preferable to contain a dissolution inhibitor that lowers the solubility of the mixture of the acrylic resin and (C) the photothermal conversion substance in an alkaline developer. Specifically, the dissolution inhibitor is a compound presumed to form a hydrogen bond with the novolak resin of the component (A) to reduce the solubility of the resin. It is preferable that it hardly absorbs light in the infrared region and is not decomposed by light in the near infrared region.
[0056]
Examples of the dissolution inhibitor include sulfonic acid esters, phosphoric acid esters, aromatic carboxylic acid esters, aromatic disulfones, carboxylic acid anhydrides, aromatic ketones, aromatics described in detail in JP-A-10-268512. Alkali aldehydes, aromatic amines, aromatic ethers, and the like, which are also described in detail in JP-A-11-190903, also have a lactone skeleton, an N, N-diarylamide skeleton, a diarylmethylimino skeleton, and also serve as a colorant Examples thereof include acid coloring dyes and nonionic surfactants described in detail in JP-A-2000-105454.
[0057]
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.
[0058]
In addition, the positive photosensitive composition of the present invention may include, 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).
[0059]
The content of the colorant in the positive photosensitive composition of the present invention is preferably 0 to 50% by weight, more preferably 0.5 to 30% by weight, and 1 to 20% by weight. Is particularly preferred.
[0060]
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 the range of preferably 10% by weight or less, more preferably 5% by weight or less.
[0061]
In addition, the positive photosensitive composition of this invention does not have a substantially sensitivity with respect to an ultraviolet light by not containing an onium salt, a diazonium salt, and a quinonediazide compound. More specifically, it means that there is no significant difference in solubility in an alkali developer before and after irradiation with light having a wavelength of 360 to 450 nm, and there is no practical image forming function.
In other words, the positive photosensitive composition of the present invention is 10 at a light intensity of 400 lux under a white fluorescent lamp (36W white fluorescent lamp Neorumi Super FLR40S-W / M / 36 manufactured by Mitsubishi Electric Corporation). Even if it is allowed to stand for a long time, it has the property that it does not cause a substantially significant difference in solubility in an alkali developer. Note that the fact that there is no substantial difference in solubility means that the solubility in an alkali developer hardly changes before and after standing for 10 hours.
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.
[0062]
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 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, etc. 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.
[0063]
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 3 to 70 mg / dm.2, Preferably 5 to 50 mg / dm2, Particularly preferably 10-30 mg / dm2The range. In addition, as drying temperature in that case, about 30-170 degreeC, for example, Preferably about 40-150 degreeC is taken.
[0064]
In order to make the effect of the present invention more reliable, for example, heating at a temperature of about 40 to 100 ° C., preferably about 40 to 70 ° C., for about 1 minute to 50 hours, preferably about 30 minutes to 20 hours. It is preferable to perform the treatment.
[0065]
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. Further, as the roughness of the support surface, the average roughness R defined in JIS B0601aIn general, the thickness is about 0.3 to 1.0 μm, preferably about 0.4 to 0.8 μm.
[0066]
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 with heat generated by absorbing light, a light source that generates a near infrared laser beam of 650 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.
[0067]
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. / Cm2) Is the light intensity (mJ / s · cm) of the received laser beam.2). Here, the light intensity of the laser beam is the amount of energy (mJ / s) per unit time of the laser beam measured by an optical power meter, and the irradiation area of the laser beam on the surface of the photosensitive composition layer (cm2) Can be obtained by dividing by. The irradiation area of the laser beam is usually 1 / e of the laser peak intensity.2Although it is defined by the area of the portion exceeding the strength, it can also be measured by exposing a photosensitive composition showing a reciprocity law.
[0068]
In the present invention, the light intensity of the light source is 2.0 × 106mJ / s · cm2It is preferable to make it more than 1.0 × 107mJ / s · cm2The above is particularly preferable. When the light intensity is in the above range, the scanning exposure time that can improve the sensitivity characteristics of the positive photosensitive composition layer in the present invention can be shortened, which is a great practical advantage.
[0069]
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.
[0070]
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.
[0071]
【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.
[0072]
Examples 1-8, Comparative Examples 1-3
An aluminum plate (thickness 0.24 mm) was degreased in a 5% by weight sodium hydroxide aqueous solution at 60 ° C. for 1 minute, and then in a hydrochloric acid aqueous solution having a concentration of 0.5 mol / liter, a temperature of 25 ° C. , Current density 60A / dm2The electrolytic etching treatment was performed under the condition of a treatment time of 30 seconds. Subsequently, desmutting treatment was performed at 60 ° C. for 10 seconds in a 5 wt% sodium hydroxide aqueous solution, and then in a 20 wt% sulfuric acid solution at a temperature of 20 ° C. and a current density of 3 A / dm.2The anodizing treatment was performed under the condition of a treatment time of 1 minute. 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.
[0073]
The following sample photosensitive solution was applied to the surface of the obtained aluminum plate support using a wire bar, dried at 85 ° C. for 2 minutes, stabilized at 55 ° C., and the coating amount was 2.2 g / m.2A positive photosensitive lithographic printing plate having a positive photosensitive composition layer was prepared.
Sample photosensitive solution:
(A) Novolak resin (phenol / m-cresol / p-cresol = 50/30/20, weight average molecular weight = 9,000, manufactured by Sumitomo Jurez Co., Ltd.)... Subtracted amount
(B) Acrylic resin: listed as compounded resin and compounded amount (parts by weight) in Table-1
(C) Photothermal conversion material: II-9, 3 parts by weight
Colorant: Ethyl violet 3 parts by weight
Solvent: 90 parts by weight methyl cellosolve
[0074]
The obtained positive photosensitive lithographic printing plate is attached to a rotating drum, and while rotating the drum, a semiconductor laser (manufactured by Applied Techno) with a wavelength of 830 nm and an output of 40 mW is irradiated with a beam spot diameter of 25 μm under a yellow lamp. Then, it was scanned and exposed, and then immersed in an alkaline developer (6-fold diluted solution of “SDR-1” manufactured by Konica) at 28 ° C., and then developed by adding light rubbing.
[0075]
At this time, 120 mJ / cm2And 240 mJ / cm2The remaining film ratio was measured when a positive image having a width of 25 μm was obtained by changing the development time. The sensitivity was obtained from the maximum number of rotations of the drum when the obtained positive image gave a width of 25 μm. The larger the remaining film rate, the better the results.
[0076]
The residual film ratio was measured by using a reflection densitometer (“RD-514” manufactured by Macbeth Co., Ltd.) for the reflection density before and after development in the non-exposed portion of the obtained positive image, and before forming the photosensitive composition layer. The residual film ratio (%) was determined from the ratio of the values obtained by subtracting the value of the reflection density on the support surface.
The copolymerization ratio and weight average molecular weight (Mw) of the blended resin are listed below the table.
From the results of the table, it is understood that when acrylic acid is excessive (Comparative Example-2) or when the amount of the acrylic resin is excessive (Comparative Example-3), an undesirable result is given.
[0077]
[Table 1]
The above abbreviations indicate MMA: methyl methacrylate, MMA: methacrylic acid, AA: acrylic acid, AN: acrylonitrile.
[0079]
Example-9
In order to investigate the effect of the acrylonitrile copolymer component as a component of the compounded resin, the same photosensitive lithographic printing plate sample as used in Examples 3 (not containing acrylonitrile) and 7 (containing acrylonitrile) was used as a plate cleaner. It was immersed for 1 minute in a fitting solvent (manufactured by Toka Dye). As a result, both samples showed almost good chemical resistance, and no significant change was observed, but the sample of Example-7 was superior to the sample of Example-3 in the remaining film ratio. It was.
The positive-type photosensitive lithographic printing plate obtained above was subjected to light intensity irradiation of 400 lux of a white fluorescent lamp (36W white fluorescent lamp “Neolmi Super FLR40S-W / M / 36” manufactured by Mitsubishi Electric Corporation). When the same development treatment as described above was performed after leaving for 10 hours, there was no substantial film loss in any of the examples and comparative examples, and the handleability under a white fluorescent lamp was good.
[0080]
【The invention's effect】
According to the present invention, it is not sensitive to light in the ultraviolet region, has excellent handleability under a white fluorescent lamp, is sensitive to light in the near infrared region, has sensitivity, chemical resistance, and an image portion. It is possible to provide a positive photosensitive composition and a positive photosensitive lithographic printing plate that are excellent in contrast with non-image areas and have a sufficient remaining film ratio in the image areas.
Claims (6)
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| ATE528135T1 (en) | 2002-02-08 | 2011-10-15 | Fujifilm Corp | IMAGE RECORDING MATERIAL AND METHOD FOR PRODUCING |
| DE60314794T2 (en) * | 2002-03-20 | 2008-04-10 | Fujifilm Corp. | IR photosensitive composition |
| JP2003345014A (en) | 2002-05-28 | 2003-12-03 | Fuji Photo Film Co Ltd | Photosensitive composition |
| JP4064841B2 (en) * | 2003-02-27 | 2008-03-19 | 富士フイルム株式会社 | Image recording material |
| JP2006293162A (en) | 2005-04-13 | 2006-10-26 | Fuji Photo Film Co Ltd | Lithographic printing original plate |
| TW202124471A (en) | 2019-11-14 | 2021-07-01 | 德商馬克專利公司 | Dnq-type photoresist composition including alkali-soluble acrylic resins |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58122533A (en) * | 1982-01-14 | 1983-07-21 | Somar Corp | Photosensitive material |
| JPH07285275A (en) * | 1994-04-18 | 1995-10-31 | Fuji Photo Film Co Ltd | Image recording material |
| JPH10239832A (en) * | 1996-12-25 | 1998-09-11 | Konica Corp | Manufacture of photosensitive planographic printing plate and image forming material |
| JP2000122278A (en) * | 1998-10-21 | 2000-04-28 | Okamoto Kagaku Kogyo Kk | Photosensitive composition and photosensitive planographic printing plate |
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| JP3779444B2 (en) * | 1997-07-28 | 2006-05-31 | 富士写真フイルム株式会社 | Positive photosensitive composition for infrared laser |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58122533A (en) * | 1982-01-14 | 1983-07-21 | Somar Corp | Photosensitive material |
| JPH07285275A (en) * | 1994-04-18 | 1995-10-31 | Fuji Photo Film Co Ltd | Image recording material |
| JPH10239832A (en) * | 1996-12-25 | 1998-09-11 | Konica Corp | Manufacture of photosensitive planographic printing plate and image forming material |
| JP2000122278A (en) * | 1998-10-21 | 2000-04-28 | Okamoto Kagaku Kogyo Kk | Photosensitive composition and photosensitive planographic printing plate |
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