JPS63223637A - Photosensitive planographic printing plate - Google Patents
Photosensitive planographic printing plateInfo
- Publication number
- JPS63223637A JPS63223637A JP5728287A JP5728287A JPS63223637A JP S63223637 A JPS63223637 A JP S63223637A JP 5728287 A JP5728287 A JP 5728287A JP 5728287 A JP5728287 A JP 5728287A JP S63223637 A JPS63223637 A JP S63223637A
- Authority
- JP
- Japan
- Prior art keywords
- group
- photosensitive
- atom
- printing plate
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007639 printing Methods 0.000 title claims abstract description 83
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 23
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 150000003459 sulfonic acid esters Chemical class 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 5
- 238000011282 treatment Methods 0.000 abstract description 19
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract 2
- 239000012965 benzophenone Substances 0.000 abstract 2
- DNKNHOROYCLEPN-UHFFFAOYSA-N azido n-diazosulfamate Chemical compound [N-]=[N+]=NOS(=O)(=O)N=[N+]=[N-] DNKNHOROYCLEPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 33
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 30
- 239000000976 ink Substances 0.000 description 23
- 238000011161 development Methods 0.000 description 18
- -1 o-naphthoquinone diazide sulfonic acid ester Chemical class 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229920003986 novolac Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 108091008695 photoreceptors Proteins 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 238000000866 electrolytic etching Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 4
- XZSZONUJSGDIFI-UHFFFAOYSA-N n-(4-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(O)C=C1 XZSZONUJSGDIFI-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 3
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000010407 anodic oxide Substances 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- HRBFQSUTUDRTSV-UHFFFAOYSA-N benzene-1,2,3-triol;propan-2-one Chemical compound CC(C)=O.OC1=CC=CC(O)=C1O HRBFQSUTUDRTSV-UHFFFAOYSA-N 0.000 description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 125000004957 naphthylene group Chemical group 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- KRICVHCCEHYUJT-UHFFFAOYSA-N n-(4-cyano-3-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(C#N)C(O)=C1 KRICVHCCEHYUJT-UHFFFAOYSA-N 0.000 description 2
- NYJIXHQKWMNVNP-UHFFFAOYSA-N n-(5-hydroxynaphthalen-1-yl)-2-methylprop-2-enamide Chemical compound C1=CC=C2C(NC(=O)C(=C)C)=CC=CC2=C1O NYJIXHQKWMNVNP-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UYBDKTYLTZZVEB-UHFFFAOYSA-N (2,3,4,5,6-pentahydroxyphenyl)-phenylmethanone Chemical compound OC1=C(O)C(O)=C(O)C(O)=C1C(=O)C1=CC=CC=C1 UYBDKTYLTZZVEB-UHFFFAOYSA-N 0.000 description 1
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical class ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- VZQBDGHUOBRFAA-UHFFFAOYSA-N 2-(2,6-dihydroxyphenyl)benzaldehyde Chemical compound C1(O)=C(C(O)=CC=C1)C1=CC=CC=C1C=O VZQBDGHUOBRFAA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- IKWOMDFVBQDYNQ-UHFFFAOYSA-N 3-hydroxy-2-methyl-n-phenylprop-2-enamide Chemical compound OC=C(C)C(=O)NC1=CC=CC=C1 IKWOMDFVBQDYNQ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- MGUKYHHAGPFJMC-UHFFFAOYSA-N 4-[3-(4-hydroxy-2,5-dimethylphenyl)-1,1-dioxo-2,1$l^{6}-benzoxathiol-3-yl]-2,5-dimethylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C)C=2)C)=C1C MGUKYHHAGPFJMC-UHFFFAOYSA-N 0.000 description 1
- JSZNEHKRXXALJZ-UHFFFAOYSA-N 4-amino-2-hydroxybenzonitrile Chemical compound NC1=CC=C(C#N)C(O)=C1 JSZNEHKRXXALJZ-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 5-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=CC2=C1O ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 101100438426 Drosophila melanogaster Art4 gene Proteins 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- WZKXBGJNNCGHIC-UHFFFAOYSA-N Leucomalachite green Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=CC=C1 WZKXBGJNNCGHIC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 241000277331 Salmonidae Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 102100031296 Tsukushi Human genes 0.000 description 1
- 101710086958 Tsukushi Proteins 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940118056 cresol / formaldehyde Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- OUGJKAQEYOUGKG-UHFFFAOYSA-N ethyl 2-methylidenebutanoate Chemical compound CCOC(=O)C(=C)CC OUGJKAQEYOUGKG-UHFFFAOYSA-N 0.000 description 1
- JVICFMRAVNKDOE-UHFFFAOYSA-M ethyl violet Chemical compound [Cl-].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 JVICFMRAVNKDOE-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- ZLSPCFYPYRYKNF-UHFFFAOYSA-N formaldehyde;4-octylphenol Chemical compound O=C.CCCCCCCCC1=CC=C(O)C=C1 ZLSPCFYPYRYKNF-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- YDKJSAXEBRKYLM-UHFFFAOYSA-N n-(3-methoxyphenyl)prop-2-enamide Chemical compound COC1=CC=CC(NC(=O)C=C)=C1 YDKJSAXEBRKYLM-UHFFFAOYSA-N 0.000 description 1
- PJASPDPXLKIZHB-UHFFFAOYSA-N n-(3-nitrophenyl)prop-2-enamide Chemical compound [O-][N+](=O)C1=CC=CC(NC(=O)C=C)=C1 PJASPDPXLKIZHB-UHFFFAOYSA-N 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003960 organic solvent Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000004385 trihaloalkyl group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-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
- 239000006097 ultraviolet radiation absorber Substances 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
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
Abstract
Description
［産業上の利用分野］
本発明はポジ型感光性平版印刷版に関し、更に詳しくは
、特定のｏ−ナフトキノンジアジドスルホン酸エステル
と特定の構造単位を有する樹脂とを組み合せた感光層を
有するポジ型感光性平版印刷版に関する。
［従来の技術］
ポジ型感光性平版印刷版とは一般に、親水性支持体上に
露光により可溶化するインキ受容性感光層を形成したも
のである。この感光層に画像露光を行ない現像すると、
画線部を残して、非画線部は除去されるので、画像が形
成される。印刷においては、画像部が親油性で非画像部
が親木性であるという性質上の差が利用される。
一般に平版印刷版には、耐刷力、耐薬品性、現像ラチチ
ュード、インキ受容性、感度等が必要であるが、特にポ
ジ型の場合には、良好な耐薬品性、耐刷力、現像ラチチ
ュードが望まれている。ここで耐薬品性とは、印刷時に
使われる種々の薬品、例えばイソプロピルアルコール、
インキ、整面液、プレートクリーナー等に対する適性で
ある。
感光層としては、Ｏ−ナフトキノンシアシト化合物が広
く使用されているが、それ自体は高分子化合物ではない
ので、ノボラック樹脂等と混合したり、あるいは縮合反
応させたりして、機械的強度の向上が図られている。樹
脂が結合したＯ−ナフトキノンシアシト化合物の例とし
て、特公昭４３−２８４０３号はピロガロールとアセト
ンとの重縮合樹脂のｏ−ナフトキノンジアジドスルホン
酸エステルを開示している。しかしこれは比較的良好な
性能を示すものの、バインダーとして通常のノボラック
樹脂１例えばｍ−クレゾールノボラック樹脂を使用した
場合は、特にＵＶインキを使用すると耐刷力が不足する
という欠点を有する。
そのため、耐刷力、耐薬品性等の上記諸物件を一層向上
するために、種々の感光体およびバインダーを含有する
感光性組成物が提案された。
特開昭５５−７６３４６号に開示された感光性組成物は
、レゾルシノール又はその誘導体とピロガロールとアセ
トンとの共縮合重合により得られたポリヒドロキシフェ
ニル化合物と、ハロゲノスルホニル基を有する０−キノ
ンジアジド化合物とを縮合させて得られる感光性樹脂と
、バインダーとしてフェノール・ホルムアルデヒド樹脂
等のアルカリ可溶性樹脂とを含有する。また特公昭５６
−５４６２１号に開示された感光性組成物は、０−キノ
ンジアジド化合物感光体と、フェノールとｍ−、ｐ−混
合クレゾールとアルデヒドとを共縮合させてなる樹脂の
バインダーとを含有する。しかし、これらの感光性組成
物においては、依然バインダーとしていわゆるノボラッ
ク樹脂が使用されているために、画像部の感光層の皮膜
強度が低く、耐刷力が劣るという欠点があった。
そこで、耐刷力を向上させる方法として露光、現像後、
高温で加熱処理する方法（バーニング処理と呼ばれる）
が一般に用いられている。ところがバーニング処理を行
なうと、加熱時に画像部の感光層より樹脂のモノマー成
分が非画像部等に付着したりして、印刷時に地汚れを発
生しやすくなるという問題がある。
一方、特公昭５２−２８４０１号に開示の感光性組成物
は、Ｏ−ナフトキノシアシトスルホン酸誘導体からなる
感光性付与剤と下記一般式（式中、Ｒ１およびＲ２は水
素原子、アルキル基またはカルボン酸基であり、Ｒ３は
水素原子、ハロゲン原子またはアルキル基、Ｒ４は水素
原子、アルキル基、フェニル基またはアラルキル基であ
り、Ｘは窒素原子と芳香族環炭素原子とを連結する２価
の有機基、ｎは０またはｌ、Ｙは置換基を有してもよい
フェニレン基または置換基を有してもよいナフチレン基
をあられす、）
により表わされる構造単位を有するアクリル系高分子化
合物からなるバインダーとを含有する。この感光性組成
物はバインダーとしてノボラック樹脂の代わりに上記構
造単位を有する高分子化合物を使用しているので、良好
な感光層皮膜強度及び耐刷性を有する。
［発明が解決しようとする問題点］
しかしながら、特公昭５２−２８４０１号の感光性組成
物からなる感光層を有するポジ型感光性平版印刷版は、
通常の印刷では比較的良好な耐刷力と耐薬品性を示すに
もかかわらず、ＵＶ印刷においては依然不十分であるこ
とがわかった。また現像ラチチュードが狭いという欠点
も認められた、ここでＵＶ印刷とは紫外線吸収剤を含む
インキ（ＵＶインキ）を用いて行なう印刷をいう、ＵＶ
印刷に適さない理由は、ＵＶ印刷に使用されるインキや
薬剤に対して感光層の耐薬品性が低いことにあることが
わかった。
そこで、本発明者は、先に上記アクリル系バインダーと
、感光体として多価フェノールとアルデヒト又はケトン
との重縮合樹脂のｏ−ナフトキノンジアジドスルホン酸
エステルとを組み合せることにより現像ラチチュードと
、ＵＶインキ適性か改良された感光性組成物を提案した
（特願昭６１−１２１１７９号）。
本発明者らは、更に現像ラチチュードが改善され、また
ボールペン適性も良好な感光性組成物を提供すべく検討
を重ねた。
なお、ボールペン適性とは以下のことを指す。
感光性平版印刷版に複数のフィルム原稿を位置を変えて
次々と焼付けする所謂多面焼付けを行なう際、フィルム
原稿間の位置合せのため、原稿の位置を感光層にマーク
することがある。この際、マークする筆記具には通常油
性ボールペンが用いられているが、ボールペンのインキ
の溶剤が、有機溶媒、特にグリコール系等の高沸点溶媒
の場合、そのインキによって感光性平版印刷版の感光性
組成物からなる感光層が侵食され、溶解してしまう。マ
ークした個所が画像部である場合、このまま現像処理す
ると画像部のマーク跡の感光層が除去されて、このマー
ク跡が印刷時に印刷物に再現されてしまうという支障が
生じることがある。このため、ボールペンのインキに対
して侵食されにくい性質をボールペン適性と呼び、この
ような適性を有する感光性組成物が望まれている。
即ち、本発明の目的は、耐薬品性が極めて良好で、バー
ニング処理を行なうことなくＵｖインキ印刷も可能な、
耐刷力に優れたポジ型感光性平版印刷版を提供すること
である。
また別の目的は、感度に優れかつ現像ラチチュードが広
いポジ型感光性平版印刷版を提供することにある。
更に別の目的はボールペン適性が良好なポジ型感光性平
版印刷版を提供することにある。
［問題点を解決するための手段］
本発明者等は、上記従来の感光性組成物の欠点につき鋭
意検討を行なった結果、感光性付与剤としてｏ−ナフト
キノンジアジドスルホン酸の誘導体の低分子でもある特
定のもの、具体的にはポリヒドロキシベンゾフェノンの
Ｏ−ナフトキノンシアシトスルホン酸エステルを使用す
れば、ＵＶ印刷における耐薬品性及び耐刷力に優れ、か
つ現像ラチチュード、ボールペン適性にも優れたポジ型
感光性平版印刷版が得られることを見出し本発明に至っ
た。
すなわち、本発明のポジ型感光性平版印刷版は。
（Ａ）ポリヒドロキシベンゾフェノンのｏ−ナフトキノ
ンジアジドスルホン酸エステルと、（Ｂ）下記一般式Ｃ
Ｉ）により表わされる構造単位を有する高分子化合物、
（式中、Ｒ，およびＲ２は水素原子、ハロゲン原子、ア
ルキル基、アリール基またはカルボン酸基てあり、Ｒ３
は水素原子、ハロゲン原子、アルキル基またはアリール
基であり、Ｒ４は水素原子、アルキル基、アリール基ま
たはアラルキル基であり、Ｙは置換基を有してもよい芳
香族基であり、Ｘは窒素原子と前記芳香族基の炭素原子
とを連結する２価の有機基であり、ｎはＯ〜５の整数で
ある。）
とを含有する感光層を支持体上に有することを特徴とす
る。
以下、本発明の詳細な説明する。
本発明の（Ａ）ｏ−ナフトキノンシアシトスルホン酸エ
ステルに使用するポリヒドロキシベンゾフェノンとして
は、ジヒドロキシベンゾフェノン、トリヒドロキシベン
ゾフェノン、テトラヒドロキシベンゾフェノン、ペンタ
ヒドロキシベンゾフェノン、オクタヒドロキシベンゾフ
ェノン、またはその誘導体、例えばハロゲン原子、アル
キル基、アリール基、アラルキル基、カルボン酸基の置
換体等が挙げられる。好ましくはトリヒドロキシベンゾ
フェノンまたはテトラヒドロキシベンゾフェノンであり
、より好ましくは２，３．４−）−ジヒドロキシベンゾ
フェノン、２，３，４．４’ −テトラヒドロキシベン
ゾフェノンが挙げられる。
又、０〜ナフトキノンシアシトスルホン酸エステルの例
としては、１．２−ナフトキノン−２−ジアジド−５−
スルホン酸クロライド、１．２−ナフトキノン−２−ジ
アジド−４−スルホン酸クロライドや１．２−ナフトキ
ノン−２−ジアジド−６−スルホン酸クロライド等が挙
げられる。
このポリヒドロキシベンゾフェノンのｏ−ナフトキノン
ジアジドスルホン酸エステルは、炭酸アルカリまたはト
リエチルアミン等を触媒にして、公知の方法で合成され
る。
このエステル化体の実質縮合率（フェノールのＯＨ基１
個に対す′る０−ナフトキノンシアシトスルホニルクロ
ライトの割合）は３０〜１００ ｍ 。
交％が好ましく、より好ましくは４０〜９９ｍ０文％、
更に好ましくは５０〜８８ ｍ ｏ １％である。３０
ｍｏ１％未満の場合、ボールペン適性が低下する。
上記（Ａ）は感光性組成物中、５〜５０ ｗ ｔ％、好
ましくはｌＯ〜４０ ｗ ｔ％の範囲で使用する。
また、感光体としてポリヒドロキシベンゾフェノンのエ
ステル化体以外のものを、本発明の効果を損なわない程
度に、必要に応じて添加することは勿論可能であり、具
体的には分子量が夫々５００〜５０００程度のピロガロ
ール・アセトン樹脂のエステル化物、レゾルシン−ベン
ズアルデヒド樹脂のエステル化物、クレゾール樹脂のエ
ステル化物等の公知のｏ−ナフトキノンジアジドスルホ
ン酸エステルを感光性組成物中５０ ｗ ｔ％以下の範
囲で併用してもよい。
また、本発明の（Ｂ）で示される高分子化合物は、下記
一般式（Ｉ）
（式中、Ｒ，およびＲ２は水素原子、ハロゲン原子、ア
ルキル基、アリール基またはカルボン酸基であり％ Ｒ
３は水素原子、ハロゲン原子、アルキル基またはアリー
ル基てあり、Ｒ４は水素原子、アルキル基、アリール基
またはアラルキル基であり、Ｙは置換基を有してもよい
芳香族基であり、Ｘは窒素原子と前記芳香族基の炭素原
子とを連結する２価の有機基であり、ｎは０〜５の整数
である。）
により表わされる構造単位を有する高分子化合物で、上
記構造単位のみの繰り返し構造を有する単独重合体でも
よいが、上記構造単位の他に１種又は２種以上の単量体
単位を有する共重合体でもよい。
上記構造単位において、Ｒ８およびＲ２は水素原子、メ
チル基やエチル基等のアルキル基、またはカルボン酸基
が好ましく、より好ましくは水素原子である。Ｒ３は水
素原子、臭素や塩素等のハロゲン原子、またはメチル基
やエチル基等のアルキル基が好ましく、より好ましくは
水素原子またはメチル基である。Ｒ４は水素原子、また
はメチル基、エチル基等のアルキル基が好ましく、より
好ましくは水素原子である。Ｙは、好ましくは置換基を
有してもよいフェニレン基またはナフチレン基であり、
置換基としてはメチル基やエチル基等のアルキル基等、
臭素や塩素等のハロゲン原子、カルボン酸基、メトキシ
基やエトキシ基等のアルコキシ基、水酸基、スルホン酸
基、シアノ基、ニトロ基、アシル基等がある。より好ま
しくは。
Ｙは無置換かまたはメチル基を有するフェニレン基また
はナフチレン基である。Ｘは窒素原子と芳香族炭素とを
連結する２価の有機基であるが、アルキレン基が好まし
く、またｎはθ〜５、好ましくは０〜３、より好ましく
は０である。
共重合体型の構造を有する本発明の高分子化合物におい
て、前記式て示される構造単位と組合わせて用いること
ができる単量体単位としては、例えばエチレン、プロピ
レン、イソブチレン、ブタジェン、イソプレン等のエチ
レン系不飽和オレフィン類、例えばスチレン、α−メチ
ルスチレン。
ｐ−メチルスチレン、ｐ−クロロスチレン等のスチレン
類、例えばアクリル酸、メタクリル酸等のアクリル酸類
、例えばイタコン酸、マレイン酸、無水マレイン酸等の
不飽和脂肪族ジカルボン酸類、例えばアクリル酸メチル
、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル
酸イソブチル。
アクリル酸ドデシル、アクリル酸２−クロロエチル、ア
クリル酸フェニル、α−クロロアクリル酸メチル、メタ
クリル酸メチル、メタクリル酸エチル、エタクリル酸エ
チル等のα−メチレン脂肪族モノカルボン酸のエステル
類、例えばアクリロニトリル、メタアクリロニトリル等
のニトリル類、例えばアクリルアミド等のアミド類、例
えばアクリルアニリド、Ｐ−クロロアクリルアニリド、
ｍ−ニトロアクリルアニリド、ｍ−メトキシアクリルア
ニリド等のアニリド類、例えば酢酸ビニル、プロピオン
酸ビニル、ベンジェ酸ビニル、醋酸ビニル等のビニルエ
ステル類、例えばメチルビニルエーテル、エチルビニル
エーテル、イソブチルビニルエーテル、β−クロロエチ
ルビニルエーテル等のビニルエーテル類、塩化ビニル、
ビニリデンクロライド、ビニリデンシアナイト、例えば
ｌ−メチル−１′−メトキシエチレン、１．１’−ジメ
トキシエチレン、１．２−ジメトキシエチレン、ｌ、ｌ
’−ジメトキシカルボニルエチレン、ｌ−メチル−１′
−二トロエチレン等のエチレン誘導体類、例えばＮ−ビ
ニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルイ
ンドール、Ｎ−ビニルピロールン、Ｎ−ビニルピロリド
ン等のＮ−ビニル化合物、等のビニル系単量体がある。
これらのビニル系単量体は不飽和二重結合が開裂した構
造で高分子化合物中に存在する。
上記の単量体のうち、構造単位（Ｉ）と組合せて用いる
ものとして、（メタ）アクリル酸類、脂肪族モノカルボ
ン酸のエステル類、ニトリル類が総合的にみて優れた性
能を示し好ましい。より好ましくは、メタクリル酸、メ
タクリル酸メチル、アクリロニトリル、アクリル酸エチ
ル等である。
これらの単量体は高分子化合物中にブロックまたはラン
ダムのいずれの状態で結合していてもよい。
本発明の高分子化合物ＣＢ）の代表的な例を挙げる。な
お下記に例示の化合物において、Ｍｗは重量平均分子量
、Ｍｎは数平均分子量、ｓ、ｋ。
Ｊｌ、ｍおよびｎは、それぞれ構造単位のモル％を表わ
す。
（Ｒ１、Ｒｆは水素原子、アルキル基、へ０ゲン原子、
■−１θ〜６（ｌｓｏｉ Ｘ、ｎｍ４Ｇ〜９０＊ｏＪＬ
＄）（Ｉｌ＋ ””−Ｒ３は水素原子、 アルキル
基、 へＵゲン原子、膳−１０〜６０ｓｏｊＬ Ｘ、ｎ
ｍ１（１−６０ｍｏｉ ％％ｌ −１０〜６ＯＩｌＯ交
２）
（Ｘｔｌアルキル 基、へＵゲン 原子）（ｎｉ は
水素原子、 アルキル基、 ハロゲン原子、−ｍｌＧ
〜６０煽ｏ９．Ｚ、ｎ冒４０〜９０１０見２）（Ｘｕ
フルキル 基、へＵゲノ 原子）（ｎｔ は水素原子
、 アルキル基、 へＵタン原子、■−１Ｏ〜６０ｍｏ
ＪＬ ＄、ｎ−１０〜６０ｍｏｊＬ Ｌ見ｍｌＱ 〜
６０ｍｏＪＬ り（Ｒ１〜 Ｒ５は水素原子、アルキ
ル基、へＵゲン原子、■−１０〜６（ｌｓｏｆＬＸ％ｎ
ｍ１Ｏ〜６０ｍｏｌ ’Ｉｎ、見−２０ ｍａｎ
Ｎ以下）
Ｎ
（Ｒ１〜 Ｒ４は水素原子、 アルキル基、 へ■ゲン
原子、ｌ＝ １０〜６０ｍｏｆｆｉ ＬｎｍｌＯ〜６
０ｍｏＪＬ Ｌ見−０〜２０ｍｏ見、ｋ＝１Ｏ〜６０ｍ
ｏｊＬＸ ）
−ｍ−÷Ｃ１１，−ＣＲ，±「−
（ｎｔ 〜 Ｒ４は水素原子、アルキル基、へロゲン原
子、■ｍ １０〜６０ｍｏｊＬ ＄％ｎ−１０〜６０
ｓｏＪＬ １％４１ ｍｌＯ〜６０ｍｏｂ 、ｋ−１０
〜６０ｍｏ見２）
ＣＮ Ｃ００ＩＩ
（Ｒｒ 〜 Ｒ，は水素原子、アルキル基、へ０ゲン原
子、１ｍ １（１−６０ｓｏＪＩ １％ｎ５ｌＯ〜６
０ｓｏＪＬ Ｚ％ｌ ｍｌＯ〜６０ｍｏｂ 、ｋｍｌＧ
〜６０ｍｏｉ Ｌｓｍ２０ｓｏＪＬ Ｚ以下）以上の
ａ）〜ｈ）のうち、ａ）、ｂ）、ｅ）、ｒ）及びｇ）が
特に好適である。
更に具体的には、
（Ｌ ＝２８０００、Ｌ／Ｍｎ−７，８、■：ｎ＝４
０：６０）（Ｌ＝４００００、Ｍ、／Ｍｎ−２，５、ｓ
：ｎｍ５０：５０）（Ｌ ＝ １８０００、Ｍ−／Ｍｆ
Ｉ−２，１，ｍ：ｎ：ｌｌ−３０：４０：３０）Ｃ１目
。
ｂ−３）
（Ｍ、＝２００００、Ｌ／ＭｆＩ−２，２、ｗ、：ｎ：
ｌ ：に−３０：３４：：１０：４）（１１０゜
？１１３
ｌ
（Ｌ＝４２０００、Ｍ、／Ｍ、−４，８、ｓ：、ｎｍ３
０ニア０）？Ｉｌ 、Ｉ
Ｏ■
（Ｍ−＝３：１０００、Ｌ／Ｍ、諺３．５、■：ｎ：見
鱒３０：３５：コ５）７１１゜
（Ｍ、 ＝５７０００、Ｌ／Ｍ、−２，９、醜：ｎ：
ＪＬ ＝２５：２５：５０）（Ｌ ＝２１０００、ｌ
１ｗ／Ｍ、雪？、２、ｍ：ｎ：ｊＬ ｓ５０：４５：５
）（Ｌ＝３３０００、Ｌ／Ｍ、−７，０、ｍ：ｎ”見
−３８：６０：２）ＣｆＬ Ｃ１１
ｓ ｃｌｆ。
−一＋Ｃ１１２Ｃｌ１ｈ−
Ｍ
（Ｌ ＝：１４０００、Ｌ／Ｍｎ−４，８、−：ｎ：
見 ： ｋ−２０：コ０：５：４５）一一一÷ｅ１１．
−Ｃ→Ｔ−
Ｎ
（Ｍｗ ＝ ：Ｉ２０００、Ｍｙ／Ｌ−４−４，ｗｓ
：ｎ ：見 ：に＝２０：３５：５：４０）（Ｌ ＝４
８０００％Ｍ、／Ｍｎ−５．：ｌ、ｍ：ｎ：ＪＬ ：に
＝３０：１Ｇ＝３０：３０）？１１３
（Ｍ、 ＝３５０００、Ｍ、／Ｍ、−７−９、ｔｉ：ｎ
：ｌ ：に：５−２０：１５：３０：コ３：２）（以下
、余白）
本発明の高分子化合物（Ｂ）はつぎのようにして合成す
ることができる。まず、α・β−不飽和酸クロライト類
、またはα・β−不飽和酸無木物類とフェノール性水酸
基を有する第１級、または第２級アミン類とを必要に応
じて塩基性触媒を用いて反応せしめ、前記一般式（Ｉ）
で示される構造単位を有する単量体を合成する。次にそ
の単量体を常法に従って単独重合させるか、あるいはそ
の単量体と少なくとも１種の他のビニル系単量体とを共
重合させ、本発明の高分子化合物を得ることができる。
この際各車量体の仕込みモル比および重合条件を種々変
えることにより、高分子化合物（Ｂ）の分子量ならびに
各構造単位のモル比を広範囲に設定することができる。
しかし、本発明の目的とする用途に有効に供するために
は、分子量はｓ、ｏｏｏ乃至１００，０００、好ましく
はｓ、ｏｏｏ〜５０，０００であり、前記一般式（■）
で示される構造単位のモル含有率は少なくとも１０モル
％、好ましくは１０〜５０モル％であるものが望ましい
。
ＣＢ）は感光性組成物中５０〜９５ ｗ ｔ％、好まし
くは６０〜９０ ｗ ｔ％の範囲て使用する。
本発明の感光層を形成する組成物中には、公知のアルカ
リ可溶性の高分子化合物を含有させることができる。ア
ルカリ可溶性の高分子化合物としてノボラック樹脂１例
えばフェノール・ホルムアルデヒド樹脂、クレゾール・
ホルムアルデヒド樹脂やフェノール変性キシレン樹脂、
ポリヒドロキシスチレン等があげられるが、このような
アルカリ可溶性の高分子化合物は全組成物の６０重量％
以下の添加量で用いられる。６０重量％を超えると感光
層においてＵＶインキやプレートクリーナー類に画線が
やられ易くなり、ＵＶインキを適用し難くなる。
ポジ型感光性平版印刷版は一般にそのほかに露光可視画
付与剤及び色素を含有する。露光可視画付与剤としては
、露光により酸を発生する物質、色素としてはこの酸と
塩を形成する化合物を用いるのが一般的である。
露光により酸を発生する化合物としては、下記一般式■
またはｍで示されるトリハロアルキル化合物またはジア
ゾニウム塩化合物が好ましい。
（ただし、Ｘ、は炭素原子数１〜３のトリハロアルキル
基であり、ＷはＮまたはＰてあり、２は０、ＳまたはＳ
ｅであり、ＹはＷと２を環化させるとともに発色団を有
する基である。）
（八「はアリール基であり、Ｘは無機化合物の対イオン
である。）
具体的には１式■のトリハロアルキル化合物としては、
例えば下記の一般式ｎ、、ｎｂ、ｎ。て表される化合物
がある。
［
ａ
（ただし、Ａは置換若しくは非置換アリール基又は複素
環式基であり、Ｂは水素又はメチル基であり、ｎは０〜
２の整数である。）
露光可視画付与剤の添加量は、感光層の全組成物の０．
０１〜２０重量％であるのが好ましく、より好ましくは
０．１〜ｌＯ重量％である。
一方１色素としては一般に酸により塩を形成する化合物
であればいずれも使用可能てあり、例えばトリフェニル
メタン系染料、シアニン染料、ジアゾ染料、スチリル染
料等が挙げられる。
具体的にはビクトリアピュアブルーＢＯＨ、エチルバイ
オレット、クリスタルバイオレット、ブリリアントグリ
ーン、ペイシックツクシン、エオシン、フェノールフタ
レイン、キシレノールブルー、コンゴーレッド、マラカ
イトグリーン、オイルブルー＃６０３、オイルピンク＃
３１２、クレゾールレウト、オーラミン、４−ｐ−ジエ
チルアミノフェニルイミノナフト、キノン、ロイコマラ
カイトグリーン、ロイコクリスタルバイオレット等が挙
げられる０色素の添加量は感光層の全組成物の約０．０
１−１０重量％が好ましく、より好ましくは０．０５〜
８重量％である。
本発明のポジ型感光性平版印刷版の感光層組成物中には
、その他に目的に応じて各種の添加剤を加えることがで
きる０例えば塗布性を向上させるために界面活性剤、感
度向上のために各種増感剤、塗膜の物性改良のために可
塑剤等、また、画像の印刷インキ着肉性な高めるために
、疎水性基を有する各種添加剤、例えばｐ−オクチルフ
ェノール−ホルマリンノボラック樹脂、ｐ−ｔ−ブチル
フェノール−ホルマリンノボラック樹脂、ｐ−ｔ−プチ
ルフェノール・ベンズアルデヒド樹脂、ロジン変性ノボ
ラック樹脂等の変性ノボラック樹脂、これらの変性ノボ
ラック樹脂のｏ−ナフトキノンジアジドスルホン酸エス
テル（ＯＨ基のエステル化率２０〜７０モル％）等を添
加することができる。これらの添加剤の含有量はその種
類と目的によって異なるが、概して感光層の全組成物に
対して０．０１〜２０重量％、好ましくは０．０５〜ｌ
Ｏ重量％である。
上記感光層組成物は、各種溶媒、例えばメチル（エチル
）セロソルブ、メチル（エチル）セロソルブアセテート
等のセロソルブ類、ジメチルホルムアミド、ジメチルホ
ルホシキド、ジオキサン、アセトン、シクロヘキサノン
、トリクロロエチレン等の塗布溶媒に溶解して支持体上
に塗布し、乾燥することにより形成される。
本発明のポジ型感光性平版印刷版の感光層は。
用途によっても異なるが、一般的に固形分として０．５
〜３．０ｇ／ｍ”となるように形成するのが好ましい。
本発明のポジ型感光性平版印刷版に用いる支持体として
は、アルミニウム板が好ましい、アルミニウム板に対し
ては、砂目立て処理、陽極酸化処理及び必要に応じて封
孔処理等の表面処理を施すのが好ましい、これらの処理
は公知の方法により行なうことができる。
砂目立て処理の方法としては、機械的方法及び電解によ
りエツチングする方法が挙げられる０機械的方法として
は、例えば、ボール研磨法、ブラシ研磨法、液体ホーニ
ングによる研磨法、パフ研磨法等が挙げられる。アルミ
ニウム材の組成等に応じて、上記の方法を単独または組
合わせて用いることができる。好ましいのは電解エツチ
ング法である。
電解エツチングは、リン酸、硫酸、塩酸、硝酸等の無機
酸を１種または２種以上含有する浴中にアルミニウム板
を浸漬することにより行なう、砂目立て処理の後、必要
に応じてアルカリあるいは酸の水溶液によってデスマッ
ト処理を行なって中和し、水洗する。
陽極酸化処理は、電解液として硫酸、クロム酸、シュウ
酸、リン酸、マロン酸等を１種または２種以上含む溶液
を用い、アルミニウム板を陽極にして電解することによ
り行なう、形成された陽極酸化皮膜量は１〜５０ ｍ
ｇ ／ ｄ ｍ ”が適当であり、好ましくはｌ Ｏ〜
４０ ｍ ｇ ／ ｄ ｍ ”である、ここで陽極酸化
皮膜量は１例えばアルミニウム液をリン酸クロム酸溶液
（８５％リン酸水溶液３５ｍ皇と、酸化クロム（ＶＩ）
２０ｇとを１文の水に溶解して生成）に浸漬して酸化皮
膜を溶解し、板の皮膜溶解前後の重量変化を測定するこ
とにより求めることがてきる。
封孔処理としては、沸騰水処理、水蒸気処理、ケイ酸ソ
ーダ処理、重クロム酸塩水溶液処理等がある。この他に
アルミニウム支持体に対して、水溶性高分子化合物や、
フッ化ジルコン酸等の金属塩の水溶液により下引処理を
施すこともできる。
このようにして得られたポジ型感光性平版印刷版は公知
の方法により使用することができる。典型的には、感光
性印刷版にポジ型フィルムを密着させ、超高圧水銀灯、
メタルハライドランプ等で露光し、メタケイ酸ソーダ、
メタケイ酸カリ、リン酸ソーダ、カセイソーダ等のアル
カリ水溶液により現像し、印刷版とする。
このようにして作製された平版印刷版は枚葉、オフ輪用
印刷機において使用することができる。
［実施ｇ４］
本発明を以下の実施例により更に詳細に説明する。
まず、本発明に使用する感光体およびバインダーの合成
例を以下に示す。
（バインダーの合成）
ｐ−ヒドロキシアニリン４００ｇ、ハイドロキノンモノ
メチルエーテル４ｇ、アセトン４ｆＬおよびピリジン３
６０ｇを混合し、寒剤を用いて外部より冷却し、内温か
一１Ｏ℃まで下がった時点でメタクリル酸クロライド４
２０ｇを攪拌下に滴下・した０反応温度が０゛℃以下に
なるよう滴下速度を調節し、滴下終了後０〜３℃で約２
時間攪拌した０次いで２５℃で２時間攪拌後反応液を１
／３位になるまで濃縮し、これを希塩酸（ｐＨ約１゜０
）１０１中に注入し、生じた沈殿を吸引濾過して白色の
固体を得た。この白色の固体を加温したメタノール２見
に溶解し、さらに５％炭酸ナトリラム水溶液を２文加え
て、４０°Ｃで３０分間攪拌した０次いで、暗赤色のこ
の溶液を５％塩酸水溶液ａＪＬ中に注入して多量の沈殿
を生成させ、これを吸引濾過し、乾燥して淡桃色の固体
を得た、これをエタノールと水との混合溶媒により再結
晶して、融点１５５〜１５６℃のｐ−ヒドロキシメタク
リルアニリドの無色針状晶４５０ｇを得た。
このようにして得たｐ−ヒドロキシメタクリルアニリド
（ＨｙＰＭＡ）５３ 、２ ｇ、アクリロニトリル（Ａ
Ｎ）１５．９ｇ、メタクリル酸メチル（ＭＭＡ）４０．
０ｇおよびα・α′−アゾビスイソブチロニトリル３ｇ
をエタノール溶媒２５０ｒｒＪｌ中に溶解し、窒素ガス
置換した後、７５℃で４時間加熱し、重合体溶液を得た
。この重合体溶液を３文の５％ＨＣ１水溶液中に注ぎ、
生じた白色の沈殿物を濾過し、乾燥して、白色重合体７
０ｇを得た。得られた重合体の分子量をＧＰＣで測定し
たら、Ｍｎが８６００１Ｍ、が１８０００であった。
企ｍス
合成例１で得たｐ−ヒドロキシメタクリルアニリド（Ｈ
ｙＰＭＡ）５３ 、１ ｇ、アクリロニトリル（ＡＮ）
１５．９ｇ、アクリル酸エチル（ＥＡ）４ｇ、メタクリ
ル酸メチル（ＭＭＡ）３６ｇおよびα・α′−アゾビス
イソブチロニトリル３ｇをエタノール１５０ｎｓＪｌ中
に溶解し、窒素ガス置換した後、７５℃で４時間加熱し
、重合体溶液を得た。
この重合体溶液を３１の５％ＨＣＩ水溶液中に注ぎ、生
じた白色の沈殿物を濾過し乾燥して、白色重合体６５ｇ
を得た。ＧＰＣで分子量を測定したら、Ｍイが９０９０
％Ｍ、が２００００であった。
ｍ−ヒドロキシ−ｐ−シアノアニリン４００ｇ、ハイド
ロキノンモノメチルエーテル４ｇ１アセトン４１および
ピリジン３６０ｇを混合し、寒剤を用いて外部より冷却
し、内温か一１０℃まで下がった時点でメタクリル酸ク
ロライド４２０ｇを攪拌下に滴下した。以下、合成例１
と同様にして、ｍ−ヒドロキシ−ｐ−シアノメタクリル
アニリド３５０ｇを得た。
このようにして得たｍ−ヒドロキシ−ｐ−シアノメタク
リルアニリド７６．８ｇ （０，３８モル）を、エチル
メタクリレート６８．４ｇ （０，６０モル）、アクリ
ル酸１．４４ｇ （０，０２モル）およびα・α′−ア
ゾビスイソブチロニトリル０．７ｇとともに、アセトン
：エタノール（１：２）の混合溶媒３００ｍＪＬ中に溶
解し、窒素ガス置換した後、６５℃で４時間加熱し１重
合体溶液を得た。この重合体溶液を３１の５％ＨＣ１水
溶液中に注ぎ、生じた白色の沈殿物を濾過し、乾燥して
、白色重合体７５ｇを得た。ＧＰＣで分子量を測定した
ら、Ｍ、が４７００、Ｍ、が３３０００であった。
合成例４
前記（ｇ−１）の高分子化合物の合成
５−アミノ−α−ナフトール２２７ｇ、へイドロキノン
モノメチルエーテル１ｇおよびピリジン２１を混合し、
寒剤を用いて一１θ℃に冷却して、メタクリル酸クロラ
イド１１０ｇを攪拌下に滴下した０滴下終了後０〜３℃
で２時間攪拌した。
次いで２５℃で２時間攪拌後、反応液を２０１の氷水中
に注入して沈殿を生成させ、これを濾過し、水洗して乾
燥した。得られた固体をメタノールと５％炭酸ナトリウ
ム水溶液の混合液（１：１）ＺＩｉ中に加えて４０℃で
３０分間攪拌した後、５％塩酸４文中に注入して多量の
沈殿を生成させた。これを吸引濾過後、エタノールで再
結晶して、融点２２３〜２２４℃のＮ−（５−ヒドロキ
シ−α−ナフチル）メタクリルアミド２１０ｇを得た。
このようにして得たＮ−（５−ヒドロキシ−α−ナフチ
ル）メタクリルアミド６８ｇ （０，３モル）を、２−
ヒドロキシエチルメタクリレート１０ｇ（０，１モル）
、メチルメタクリレート３０ｇ （０，３モル）、アク
リロニトリル１５゜９ｇ （０，３モル）およびα・α
′−アゾビスイソブチロニトリルｏ、５０ｇとともに、
アセトン：エタノール（１： ２）の混合溶媒２００
ｍ ｌ中に溶解した。得られた溶液を窒素ガス置換した
封管中で、６５℃で８時間加熱し、共重合体溶液を得た
。この共重合体溶液をメタノール１００ｍＪＬで希釈し
た後、水中に注入し、生じた沈殿物を濾過し、乾燥して
、白色重合体７０ｇを得た。ＧＰＣで分子量を測定した
ら、Ｍ、が９１００．Ｍ。
が４８０００であった。
塩見イしく江１
合成例１においてｐ−ヒドロキシメタクリルアニリドの
代わりに２−ヒドロキシエチルメタクリレートを使用し
た以外は、同一の条件で反応を行なった。得られた重合
体の分子量をＧＰＣで測定したら、Ｍｎが２３００、Ｍ
、が１５０００であった。
比較合成例２
ｍ−クレゾール９０ｇ、ｐ−クレゾール５６ｇ、フェノ
ール５４ｇ、３７％ホルムアルデヒド水溶液１０５ｇお
よびシュウ酸２．５ｇをオイルバスにセットした３頭プ
ルペン中に投入し、攪拌しながら昇温した。９０℃付近
で激しく発泡し一時的に冷却した後再び昇温し、内温な
１５０°Ｃにした。約３時間反応後、再び１７５℃まで
昇温し、水を留去した。２時間後２００℃に昇温すると
ともに、１００ｍｍＨｇまで減圧し、残留モノマーを留
去した。１０分後反応を止め、反応物をテフロン・バッ
トへ流し出し、固化させた。この樹脂の分子量をＧＰＣ
てポリスチレンを標準として測定した０Ｍｎ、Ｍｗの算
出は前述と同様にして行なった。その結果、Ｍ、は１３
５０、Ｍｗが６７５０であった。
（感光体の合成）
塩艷立度璽ユ
ピロガロール１００ｇおよびアセトン７００ｇをウォー
ターバス中にセットした３頭コルベン中に投入し、窒素
ガスを吹込んで、窒素置換を行なった後、オキシ塩化リ
ンｌＯｇを投入して重縮合反応を行なった０反応温度は
２０℃に保ち一昼夜反応を継続した０反応終了後、水３
０１中に強力に攪拌しながら生成物を徐々に投入し１重
縮合物を沈殿させた。
析出した樹脂を濾別し、水でほぼ中性になるまで洗浄し
た。沈殿物は４０°Ｃ以下で乾燥した。このようにして
淡褐色状の樹脂１００ｊＣを得た。
この樹脂の分子量を、ＧＰＣ（日立６３５型、カラム
ショデックス（Ｓｈｏｄｅｘ） Ａ ８０４、Ａ３０３
、八８０２の直列〕によりポリスチレンを標準として測
定したｅ Ｍｎ ｓ Ｍｙの算出は柘植等、日本化学会
誌、１９７２年（４月号）第８００頁に記載の方法によ
り、オリゴマー領域のピークをならす（ピークの山と谷
の中心を結ぶ）方法により行なった。その結果、Ｍ、は
２０００．ＭＷは３４００であった。
次にこの樹脂６０ｇをジオキサン７２０ｍＪｌに溶解し
、１．２−ナフトキノンシアシト−５−スルホニルクロ
ライド７０ｇを投入し、溶解後１３重量％の炭酸カリ水
溶液６０ｇを滴下し、４０〜ｓｏ’ｃで約１時間脳合反
応を行なわせた。得られた反応液を大量の希塩酸水（濃
塩酸１３ｍｊＬ、水３４１１）中に投入し、沈殿した樹
脂を濾別し、乾燥した。このようにして、ピロガロール
−アセトン樹脂の１．２−ナフトキノンシアシト−５−
スルホン酸エステルの黄色粉末樹脂５６ｇが得られた０
分析の結果、ＯＨ基の縮合率は２０％であることが判明
した。このエステル体の分子量を上記ＧＰＣにより測定
したところ、Ｍｎは２３００゜Ｍｗは３０３０であった
。
実施例１
厚さ０．２４ｍｍのアルミニウム板を５％水酸化ナトリ
ウム水溶液中で脱脂処理した後、０．３モル硝酸水溶液
中で、温度３０℃、電流密度５０Ａ／ｄｍ”、処理時間
３０秒間の条件で、電解エツチング処理を行なった０次
いで、５％水酸化す ・トリウム水溶液でデスマット処
理を施し、しかる後硫酸溶液中で陽極酸化処理を行なっ
た。陽極酸化皮膜量を前述の方法で測定したところ、２
０ｍ ｇ ／ ｄ ｍ ”であった０次に９０℃の熱水
溶液に浸漬し封孔処理を行なった。
このようにして得られたアルミニウム支持体に下記の組
成の感光性塗布液を回転塗布機を用いて塗布し、１００
℃で４分間乾燥し、膜厚２４ ｍ ｇ／ ｄ ｍ ２の
感光性平版印刷版を得た。
感光液１
２．３．４−トリヒドロキシベンゾフェノンと１．２−
ナフトキノンシアシト−５−スルホン酸クロライドとの
エステル化物（縮合率：９５ｎＪＬ％）
２０部合成例１のバインダー
８０部２−トリクロロメチル−５−〔β−（２
′−ベンゾフリル）ビニル）−１，３，４−オキサジア
ゾール ２部ビクトリ
アブルーＢＯＨ１部
ｐ−ｔ−オクチルフェノール・ホルムアルデヒドノボラ
ック樹脂（Ｍｗ＝１，３００）と１，２−ナフトキノン
シアシト−５−スルホン酸クロライドとのエステル化物
（縮合率：５０ｍｏＪＬ％）１部
無水グルタル酸 ３部メチルセ
ロソルブ ２００部エチルセロソルブ
５００部得られた感光性平版印刷版
を３にＷの超高圧水銀灯で６０ｃｍの距離から３０秒間
露光し、次にＰＳ版用ポジ型現像液“５ＤＰ−１”〔小
西六写真工業■製〕の９倍希釈液を用いて、２５℃で４
５秒間現像処理を行なった。得られた平版印刷版の感度
および耐薬品性を測定した。
Ｘ凰班遣
合成例１のバインダーの代わりに合成例２のバインダー
を使用した以外、実施例１と同一の方法により感光性塗
布液（感光液２）を調製し、これを用いて実施例１と同
一の方法で平版印刷版を作製し、同一の測定を行なった
。
ル艶１ユ
合成例１のバインダーの代わりに比較合成例２のバイン
ダーを使用した以外実施例１と同一の方法により感光性
塗布液（比較感光液１）を調製し、これを用いて実施例
１と同一の方法で平版印刷版を作製し、同一の測定を行
なった。
実施例１、実施例２および比較例１の測定結果を表１に
示す。
表 １
（注）（鳳）ノボラック樹脂
（諺）霞ｔＷ生は４１睨みこ１日浸漬後、画−ｌ称り損
傭−ｖ[Industrial Application Field] The present invention relates to a positive-working photosensitive lithographic printing plate, and more specifically, a positive-working photosensitive lithographic printing plate having a photosensitive layer combining a specific o-naphthoquinonediazide sulfonic acid ester and a resin having a specific structural unit. Related to photosensitive lithographic printing plates. [Prior Art] A positive-working photosensitive lithographic printing plate generally has an ink-receptive photosensitive layer formed on a hydrophilic support, which becomes solubilized by exposure to light. When this photosensitive layer is imaged and developed,
Since the non-image areas are removed while leaving the image areas, an image is formed. In printing, the difference in properties is utilized: the image area is oleophilic and the non-image area is oleophilic. In general, planographic printing plates require good printing durability, chemical resistance, development latitude, ink receptivity, sensitivity, etc., but especially in the case of positive type plates, good chemical resistance, printing durability, development latitude, etc. are required. is desired. Chemical resistance here refers to various chemicals used during printing, such as isopropyl alcohol,
Suitable for ink, surface preparation liquid, plate cleaner, etc. O-naphthoquinone cyasito compounds are widely used as photosensitive layers, but since they are not polymeric compounds themselves, they can be mixed with novolac resins or subjected to condensation reactions to improve mechanical strength. is planned. As an example of a resin-bonded O-naphthoquinone cyacyto compound, Japanese Patent Publication No. 43-28403 discloses an o-naphthoquinonediazide sulfonic acid ester of a polycondensation resin of pyrogallol and acetone. However, although this exhibits relatively good performance, it has the disadvantage that printing durability is insufficient, particularly when UV ink is used, when a normal novolac resin, such as m-cresol novolak resin, is used as a binder. Therefore, in order to further improve the above properties such as printing durability and chemical resistance, photosensitive compositions containing various photoreceptors and binders have been proposed. The photosensitive composition disclosed in JP-A-55-76346 comprises a polyhydroxyphenyl compound obtained by cocondensation polymerization of resorcinol or its derivative, pyrogallol, and acetone, and an 0-quinonediazide compound having a halogenosulfonyl group. It contains a photosensitive resin obtained by condensing the following, and an alkali-soluble resin such as phenol/formaldehyde resin as a binder. Also, special public service in 1984
The photosensitive composition disclosed in No. 54621 contains an 0-quinonediazide compound photoreceptor and a resin binder formed by co-condensing phenol, m- and p-mixed cresol, and aldehyde. However, these photosensitive compositions still use a so-called novolak resin as a binder, and therefore have the disadvantage that the film strength of the photosensitive layer in the image area is low and the printing durability is poor. Therefore, as a method to improve printing durability, after exposure and development,
Method of heat treatment at high temperatures (called burning treatment)
is commonly used. However, when the burning process is performed, there is a problem in that the monomer component of the resin adheres to non-image areas etc. from the photosensitive layer of the image area during heating, and background smear is likely to occur during printing. On the other hand, the photosensitive composition disclosed in Japanese Patent Publication No. 52-28401 uses a photosensitizer comprising an O-naphthoquinocyacytosulfonic acid derivative and the following general formula (wherein R1 and R2 are hydrogen atoms, alkyl groups or It is a carboxylic acid group, R3 is a hydrogen atom, a halogen atom, or an alkyl group, R4 is a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group, and X is a divalent group that connects a nitrogen atom and an aromatic ring carbon atom. From an acrylic polymer compound having a structural unit represented by an organic group, n is 0 or l, and Y is a phenylene group that may have a substituent or a naphthylene group that may have a substituent. Contains a binder. Since this photosensitive composition uses a polymer compound having the above structural unit as a binder instead of a novolak resin, it has good photosensitive layer film strength and printing durability. [Problems to be Solved by the Invention] However, the positive-working photosensitive lithographic printing plate having a photosensitive layer made of a photosensitive composition disclosed in Japanese Patent Publication No. 52-28401,
Although it showed relatively good printing durability and chemical resistance in normal printing, it was found that it was still insufficient in UV printing. In addition, the drawback of narrow development latitude was also recognized. Here, UV printing refers to printing performed using ink containing an ultraviolet absorber (UV ink).
It has been found that the reason why it is unsuitable for printing is that the photosensitive layer has low chemical resistance to the inks and chemicals used in UV printing. Therefore, the present inventor first combined the above-mentioned acrylic binder with an o-naphthoquinone diazide sulfonic acid ester of a polycondensation resin of polyhydric phenol and aldehyde or ketone as a photoreceptor to improve the development latitude and UV ink. A photosensitive composition with improved suitability was proposed (Japanese Patent Application No. 121179/1982). The present inventors have conducted repeated studies in order to provide a photosensitive composition that has further improved development latitude and is also suitable for ballpoint pens. Note that ballpoint pen aptitude refers to the following. When performing so-called multi-sided printing in which a plurality of film originals are successively printed on a photosensitive lithographic printing plate at different positions, the positions of the originals may be marked on the photosensitive layer in order to align the film originals. At this time, an oil-based ballpoint pen is usually used as the writing instrument for marking, but if the solvent of the ink of the ballpoint pen is an organic solvent, especially a high boiling point solvent such as a glycol-based solvent, the ink may affect the photosensitivity of the photosensitive lithographic printing plate. The photosensitive layer made of the composition is eroded and dissolved. If the marked area is an image area, if the development process is performed as it is, the photosensitive layer of the mark trace in the image area may be removed, causing a problem that the mark trace will be reproduced on the printed matter during printing. Therefore, the property of being resistant to erosion by ballpoint pen ink is called ballpoint pen suitability, and a photosensitive composition having such suitability is desired. That is, the object of the present invention is to provide a material that has extremely good chemical resistance and can be printed with UV ink without performing a burning process.
An object of the present invention is to provide a positive type photosensitive lithographic printing plate having excellent printing durability. Another object is to provide a positive-working photosensitive lithographic printing plate with excellent sensitivity and wide development latitude. Yet another object is to provide a positive-working photosensitive lithographic printing plate that is well suited for ballpoint pen use. [Means for Solving the Problems] As a result of intensive investigation into the drawbacks of the above-mentioned conventional photosensitive compositions, the present inventors have found that even low-molecular o-naphthoquinonediazide sulfonic acid derivatives can be used as photosensitizers. If you use a certain product, specifically O-naphthoquinone cyasitosulfonic acid ester of polyhydroxybenzophenone, you can create a positive that has excellent chemical resistance and printing durability in UV printing, as well as excellent development latitude and ballpoint pen suitability. The inventors discovered that a type photosensitive lithographic printing plate can be obtained, leading to the present invention. That is, the positive-working photosensitive lithographic printing plate of the present invention is as follows. (A) o-naphthoquinonediazide sulfonic acid ester of polyhydroxybenzophenone and (B) the following general formula C
I) A polymer compound having a structural unit represented by
is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, R4 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, Y is an aromatic group that may have a substituent, and X is a nitrogen atom. It is a divalent organic group that connects an atom and a carbon atom of the aromatic group, and n is an integer of O to 5. ) on a support. The present invention will be explained in detail below. The polyhydroxybenzophenone used in (A) o-naphthoquinone cyasitosulfonic acid ester of the present invention includes dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or a derivative thereof, such as a halogen atom, Examples include substituted products of alkyl groups, aryl groups, aralkyl groups, and carboxylic acid groups. Trihydroxybenzophenone or tetrahydroxybenzophenone is preferred, and 2,3,4-)-dihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone are more preferred. Further, as an example of 0-naphthoquinone cyacytosulfonic acid ester, 1,2-naphthoquinone-2-diazide-5-
Examples include sulfonic acid chloride, 1.2-naphthoquinone-2-diazide-4-sulfonic acid chloride, and 1.2-naphthoquinone-2-diazide-6-sulfonic acid chloride. This o-naphthoquinonediazide sulfonic acid ester of polyhydroxybenzophenone is synthesized by a known method using an alkali carbonate or triethylamine as a catalyst. The actual condensation rate of this esterified product (phenol OH group 1
The ratio of 0-naphthoquinone cyasitosulfonyl chlorite to 0-naphthoquinone cyanosulfonyl chlorite is 30 to 100 m. % is preferable, more preferably 40 to 99%,
More preferably, it is 50 to 88 m o 1%. 30
When the mo is less than 1%, suitability for ballpoint pens decreases. The above (A) is used in the photosensitive composition in an amount of 5 to 50 wt%, preferably 10 to 40 wt%. Furthermore, it is of course possible to add materials other than the esterified product of polyhydroxybenzophenone as a photoreceptor as necessary to the extent that the effects of the present invention are not impaired. Known o-naphthoquinonediazide sulfonic acid esters such as esterified products of pyrogallol acetone resin, esterified products of resorcinol-benzaldehyde resin, and esterified products of cresol resin are used together in the photosensitive composition in an amount of 50 wt% or less. It's okay. In addition, the polymer compound represented by (B) of the present invention has the following general formula (I) (wherein R and R2 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxylic acid group, and % R
3 is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; R4 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; Y is an aromatic group that may have a substituent; It is a divalent organic group that connects a nitrogen atom and a carbon atom of the aromatic group, and n is an integer of 0 to 5. ) A polymer compound having a structural unit represented by May be combined. In the above structural unit, R8 and R2 are preferably a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carboxylic acid group, and more preferably a hydrogen atom. R3 is preferably a hydrogen atom, a halogen atom such as bromine or chlorine, or an alkyl group such as a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group. R4 is preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group, and more preferably a hydrogen atom. Y is preferably a phenylene group or naphthylene group which may have a substituent,
Substituents include alkyl groups such as methyl and ethyl groups,
Examples include halogen atoms such as bromine and chlorine, carboxylic acid groups, alkoxy groups such as methoxy and ethoxy groups, hydroxyl groups, sulfonic acid groups, cyano groups, nitro groups, and acyl groups. More preferably. Y is an unsubstituted phenylene group or a naphthylene group having a methyl group. Although X is a divalent organic group that connects a nitrogen atom and an aromatic carbon, an alkylene group is preferable, and n is θ to 5, preferably 0 to 3, and more preferably 0. In the polymer compound of the present invention having a copolymer-type structure, examples of monomer units that can be used in combination with the structural unit represented by the above formula include ethylene, propylene, isobutylene, butadiene, isoprene, etc. Systemically unsaturated olefins, such as styrene, α-methylstyrene. Styrenes such as p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as methyl acrylate, acrylic Ethyl acid, n-butyl acrylate, isobutyl acrylate. Esters of α-methylene aliphatic monocarboxylic acids such as dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate, such as acrylonitrile, methacrylate, etc. Nitriles such as acrylonitrile, amides such as acrylamide, such as acrylanilide, P-chloroacrylanilide,
Anilides such as m-nitroacrylanilide and m-methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl acetate, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl Vinyl ethers such as vinyl ether, vinyl chloride,
Vinylidene chloride, vinylidene cyanite, such as l-methyl-1'-methoxyethylene, 1,1'-dimethoxyethylene, 1,2-dimethoxyethylene, l,l
'-dimethoxycarbonylethylene, l-methyl-1'
- Vinyl monomers such as ethylene derivatives such as ditroethylene, N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolene, and N-vinylpyrrolidone. There is. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved. Among the above-mentioned monomers, (meth)acrylic acids, esters of aliphatic monocarboxylic acids, and nitrites are preferable as they exhibit excellent performance overall. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate, and the like. These monomers may be bound in a block or random manner in the polymer compound. Representative examples of the polymer compound CB) of the present invention will be given below. In addition, in the compounds illustrated below, Mw is weight average molecular weight, Mn is number average molecular weight, s, k. Jl, m and n each represent mol% of the structural unit. (R1, Rf are hydrogen atoms, alkyl groups, hydrogen atoms,
■-1θ~6(lsoi X, nm4G~90*oJL
$) (Il+ ""-R3 is a hydrogen atom, an alkyl group, a hydrogen atom, 10 to 60 sojL X, n
m1 (1-60moi%%l -10~6OIlO cross 2) (Xtl alkyl group, hegen atom) (ni is hydrogen atom, alkyl group, halogen atom, -mlG
~60 fan o9. Z, n 40-9010 2) (Xu
(furkyl group, hydrogen atom) (nt is hydrogen atom, alkyl group, hydrogen atom, ■-1O~60mo
JL $, n-10~60mojL L-view mlQ ~
60moJL (R1 to R5 are hydrogen atoms, alkyl groups, hydrogen atoms, -10 to 6 (lsofLX%n
m1O~60mol'In, -20 man
N or less) N (R1 to R4 are hydrogen atoms, alkyl groups, hydrogen atoms, l = 10 to 60 moffi LnmlO to 6
0moJL L view - 0~20mo view, k=1O~60m
o jL
soJL 1%41mlO~60mob, k-10
~60mo2) CN C00II (Rr~R, is a hydrogen atom, an alkyl group, a hydrogen atom, 1m 1 (1-60soJI 1%n5lO~6
0soJL Z%l mlO~60mob, kmlG
~60moi Lsm20soJL Z or less) Among the above a) to h), a), b), e), r) and g) are particularly preferred. More specifically, (L = 28000, L/Mn-7, 8, ■: n = 4
0:60) (L=40000, M, /Mn-2,5, s
: nm50:50) (L = 18000, M-/Mf
I-2,1,m:n:ll-30:40:30) C1. b-3) (M,=20000,L/MfI-2,2,w,:n:
l:ni-30:34::10:4) (110°?113 l (L=42000, M, /M, -4,8, s:, nm3
0 near 0)? Il, I O■ (M-=3:1000, L/M, proverb 3.5, ■:n: trout 30:35:ko5) 711° (M, =57000, L/M, -2, 9.Ugly:n:
JL = 25:25:50) (L = 21000, l
1w/M, snow? , 2, m:n:jL s50:45:5
) (L=33000, L/M, -7,0, m:n”
-38:60:2) CfL C11
sclf. -1+C112Cl1h- M (L =:14000, L/Mn-4,8, -:n:
See: k-20:ko0:5:45) 111÷e11.
-C→T- N (Mw = :I2000, My/L-4-4, ws
:n :see :ni=20:35:5:40)(L=4
8000%M, /Mn-5. :l, m:n:JL:ni=30:1G=30:30)? 113 (M, =35000, M, /M, -7-9, ti:n
:l:ni:5-20:15:30:co3:2) (hereinafter, blank) The polymer compound (B) of the present invention can be synthesized as follows. First, α/β-unsaturated acid chlorites or α/β-unsaturated acid chlorites and primary or secondary amines having a phenolic hydroxyl group are mixed with a basic catalyst as necessary. The above general formula (I) is reacted using
A monomer having the structural unit shown is synthesized. Next, the monomer is homopolymerized according to a conventional method, or the monomer and at least one other vinyl monomer are copolymerized to obtain the polymer compound of the present invention. At this time, the molecular weight of the polymer compound (B) and the molar ratio of each structural unit can be set over a wide range by varying the charging molar ratio of each carmer and the polymerization conditions. However, in order to effectively serve the purpose of the present invention, the molecular weight is from s,ooo to 100,000, preferably from s,ooo to 50,000, and the general formula (■)
It is desirable that the molar content of the structural unit represented by is at least 10 mol%, preferably 10 to 50 mol%. CB) is used in the photosensitive composition in an amount of 50 to 95 wt%, preferably 60 to 90 wt%. The composition for forming the photosensitive layer of the present invention may contain a known alkali-soluble polymer compound. As an alkali-soluble polymer compound, novolak resin 1 such as phenol/formaldehyde resin, cresol/
formaldehyde resin, phenol-modified xylene resin,
Examples include polyhydroxystyrene, but such alkali-soluble polymer compounds account for 60% by weight of the total composition.
It is used in the following amounts. If it exceeds 60% by weight, UV ink or plate cleaners will easily cause streaks in the photosensitive layer, making it difficult to apply UV ink. Positive-working photosensitive lithographic printing plates generally also contain an exposure visible image-imparting agent and a dye. As the exposure visible image imparting agent, a substance that generates an acid upon exposure to light is generally used, and as the dye, a compound that forms a salt with this acid is generally used. As a compound that generates acid upon exposure to light, the following general formula ■
Or a trihaloalkyl compound or a diazonium salt compound represented by m is preferred. (However, X is a trihaloalkyl group having 1 to 3 carbon atoms, W is N or P, and 2 is 0, S or S
e, and Y is a group that cyclizes W and 2 and has a chromophore. ) (8 is an aryl group, and X is a counter ion of an inorganic compound.) Specifically, the trihaloalkyl compound of formula 1 is as follows:
For example, the following general formulas n, , nb, n. There is a compound represented by [ a (However, A is a substituted or unsubstituted aryl group or a heterocyclic group, B is hydrogen or a methyl group, and n is 0 to
It is an integer of 2. ) The added amount of the exposed visible image imparting agent is 0.000000000000000000000000000000,000,000,000,000.
It is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight. On the other hand, as the dye, any compound which generally forms a salt with an acid can be used, and examples thereof include triphenylmethane dyes, cyanine dyes, diazo dyes, and styryl dyes. Specifically, Victoria Pure Blue BOH, Ethyl Violet, Crystal Violet, Brilliant Green, Pesic Tsukushin, Eosin, Phenolphthalein, Xylenol Blue, Congo Red, Malachite Green, Oil Blue #603, Oil Pink #
312, cresol leut, auramine, 4-p-diethylaminophenyliminonaphtho, quinone, leucomalachite green, leuco crystal violet, etc.The amount of the dye added is approximately 0.0 of the total composition of the photosensitive layer.
1-10% by weight is preferable, more preferably 0.05-10% by weight.
It is 8% by weight. In addition, various additives may be added to the photosensitive layer composition of the positive photosensitive lithographic printing plate of the present invention depending on the purpose. For example, surfactants to improve coating properties, surfactants to improve sensitivity, various sensitizers, plasticizers, etc. to improve the physical properties of the coating film, and various additives with hydrophobic groups, such as p-octylphenol-formalin novolac resin, to improve the ink receptivity of printing inks for images. , pt-butylphenol-formalin novolak resin, pt-butylphenol benzaldehyde resin, rosin-modified novolac resin, and other modified novolak resins; o-naphthoquinonediazide sulfonic acid esters (esterification of OH groups) of these modified novolac resins; 20 to 70 mol%), etc. can be added. The content of these additives varies depending on their type and purpose, but is generally 0.01 to 20% by weight, preferably 0.05 to 1% by weight, based on the total composition of the photosensitive layer.
O% by weight. The photosensitive layer composition can be dissolved in various solvents, such as cellosolves such as methyl (ethyl) cellosolve and methyl (ethyl) cellosolve acetate, and coating solvents such as dimethylformamide, dimethylformamide, dioxane, acetone, cyclohexanone, and trichloroethylene. It is formed by coating it on a support and drying it. The photosensitive layer of the positive-working photosensitive lithographic printing plate of the present invention is as follows. Although it varies depending on the application, the solid content is generally 0.5
3.0 g/m''. As the support for the positive photosensitive lithographic printing plate of the present invention, an aluminum plate is preferable. The aluminum plate may be subjected to graining treatment, It is preferable to perform surface treatments such as anodizing treatment and, if necessary, sealing treatment.These treatments can be performed by known methods.Mechanical methods and electrolytic etching are methods for graining treatment. Mechanical methods include, for example, ball polishing, brush polishing, liquid honing, puff polishing, etc. Depending on the composition of the aluminum material, the above methods may be used alone or They can be used in combination. Electrolytic etching is preferred. Electrolytic etching involves immersing an aluminum plate in a bath containing one or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining treatment, if necessary, a desmut treatment is performed with an aqueous alkali or acid solution, neutralized, and washed with water.Anodizing treatment is performed using sulfuric acid, chromic acid, oxalic acid, or phosphoric acid as an electrolyte. The amount of anodic oxide film formed is 1 to 50 m by electrolysis using a solution containing one or more types of malonic acid, etc., and using an aluminum plate as an anode.
g/d m” is suitable, preferably l O ~
40 mg/d m'', where the amount of anodized film is 1. For example, aluminum solution is mixed with phosphoric acid chromic acid solution (35 m of 85% phosphoric acid aqueous solution and chromium oxide (VI)
It can be determined by dipping the plate in a solution of 20 g (produced by dissolving 20 g in 1 cup of water) to dissolve the oxide film and measuring the change in weight of the plate before and after the film is dissolved. Pore sealing treatments include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, and the like. In addition, water-soluble polymer compounds,
Subbing treatment can also be performed using an aqueous solution of a metal salt such as fluorinated zirconate. The positive-working photosensitive planographic printing plate thus obtained can be used by a known method. Typically, a positive film is attached to a photosensitive printing plate, and an ultra-high pressure mercury lamp,
After exposure with a metal halide lamp, etc., sodium metasilicate,
It is developed with an alkaline aqueous solution of potassium metasilicate, sodium phosphate, caustic soda, etc. to form a printing plate. The lithographic printing plate produced in this way can be used in sheet-fed and off-wheel printing presses. [Example g4] The present invention will be explained in more detail by the following examples. First, synthetic examples of the photoreceptor and binder used in the present invention are shown below. (Binder synthesis) 400 g of p-hydroxyaniline, 4 g of hydroquinone monomethyl ether, 4 fL of acetone, and 3 liters of pyridine.
Mix 60g of methacrylic acid chloride, cool it from the outside using a cryogen, and when the internal temperature drops to -10℃, add methacrylic acid chloride 4.
20g was added dropwise under stirring.The dropping rate was adjusted so that the reaction temperature was below 0°C.
After stirring for 2 hours at 25°C, the reaction solution was stirred for 1 hour.
Concentrate until the concentration is 1/3, and add dilute hydrochloric acid (pH approx. 1.0
) 101, and the resulting precipitate was filtered with suction to obtain a white solid. This white solid was dissolved in two portions of warm methanol, two more 5% aqueous sodium carbonate solutions were added, and the mixture was stirred for 30 minutes at 40°C.This dark red solution was then dissolved in 5% aqueous hydrochloric acid solution aJL. A large amount of precipitate was produced, which was suction filtered and dried to obtain a pale pink solid. This was recrystallized from a mixed solvent of ethanol and water to produce a p -450 g of colorless needle-like crystals of hydroxymethacrylanilide were obtained. 53.2 g of p-hydroxy methacrylanilide (HyPMA) thus obtained, acrylonitrile (A
N) 15.9g, methyl methacrylate (MMA) 40.
0g and α・α′-azobisisobutyronitrile 3g
was dissolved in 250 rr Jl of ethanol solvent, and after purging with nitrogen gas, the solution was heated at 75° C. for 4 hours to obtain a polymer solution. This polymer solution was poured into three volumes of 5% HC1 aqueous solution,
The resulting white precipitate was filtered and dried to obtain white polymer 7.
Obtained 0g. When the molecular weight of the obtained polymer was measured by GPC, it was found that Mn was 86,001M and 18,000. p-hydroxy methacrylanilide (H
yPMA)53, 1 g, acrylonitrile (AN)
15.9 g of ethyl acrylate (EA), 4 g of methyl methacrylate (MMA), and 3 g of α・α′-azobisisobutyronitrile were dissolved in 150 nsJl of ethanol, and after purging with nitrogen gas, the mixture was heated at 75°C for 4 hours. The mixture was heated for a period of time to obtain a polymer solution. This polymer solution was poured into 5% HCI aqueous solution of No. 31, and the white precipitate formed was filtered and dried to obtain 65 g of white polymer.
I got it. When I measured the molecular weight by GPC, Mi was 9090.
%M was 20,000. Mix 400 g of m-hydroxy-p-cyanoaniline, 4 g of hydroquinone monomethyl ether, 41 g of acetone, and 360 g of pyridine, cool from the outside using a cryogen, and when the internal temperature has dropped to -10°C, add 420 g of methacrylic acid chloride with stirring. dripped. Below, Synthesis Example 1
In the same manner as above, 350 g of m-hydroxy-p-cyanomethacrylanilide was obtained. 76.8 g (0.38 mol) of m-hydroxy-p-cyanomethacrylanilide thus obtained were mixed with 68.4 g (0.60 mol) of ethyl methacrylate, 1.44 g (0.02 mol) of acrylic acid and 1 Polymer solution was dissolved in 300 mJL of a mixed solvent of acetone:ethanol (1:2) with 0.7 g of α・α'-azobisisobutyronitrile, purged with nitrogen gas, and heated at 65°C for 4 hours. I got it. This polymer solution was poured into a 5% HCl aqueous solution of 31, and the resulting white precipitate was filtered and dried to obtain 75 g of a white polymer. When the molecular weight was measured by GPC, M was 4,700 and M was 33,000. Synthesis Example 4 Synthesis of the polymer compound of (g-1) 227 g of 5-amino-α-naphthol, 1 g of hydroquinone monomethyl ether and 21 pyridine were mixed,
It was cooled to -1θ℃ using a cryogen, and 110g of methacrylic acid chloride was added dropwise with stirring. After the completion of the dropwise addition, the temperature was 0 to 3℃.
The mixture was stirred for 2 hours. After stirring at 25° C. for 2 hours, the reaction solution was poured into 201 ice water to generate a precipitate, which was filtered, washed with water, and dried. The obtained solid was added to a mixture of methanol and 5% sodium carbonate aqueous solution (1:1) ZIi, stirred at 40°C for 30 minutes, and then poured into 4 volumes of 5% hydrochloric acid to generate a large amount of precipitate. . After suction filtration, this was recrystallized from ethanol to obtain 210 g of N-(5-hydroxy-α-naphthyl)methacrylamide having a melting point of 223 to 224°C. 68 g (0.3 mol) of N-(5-hydroxy-α-naphthyl) methacrylamide thus obtained was added to 2-
10 g (0.1 mol) of hydroxyethyl methacrylate
, 30 g (0.3 mol) of methyl methacrylate, 15°9 g (0.3 mol) of acrylonitrile and α・α
'-Azobisisobutyronitrile o, along with 50g,
Acetone:ethanol (1:2) mixed solvent 200
Dissolved in ml. The obtained solution was heated at 65° C. for 8 hours in a sealed tube purged with nitrogen gas to obtain a copolymer solution. This copolymer solution was diluted with 100 mJL of methanol and poured into water, and the resulting precipitate was filtered and dried to obtain 70 g of a white polymer. When the molecular weight was measured by GPC, M was 9100. M. was 48,000. Shiomi Ishikue 1 The reaction was carried out under the same conditions as in Synthesis Example 1 except that 2-hydroxyethyl methacrylate was used instead of p-hydroxymethacrylanilide. When the molecular weight of the obtained polymer was measured by GPC, Mn was 2300, M
, was 15,000. Comparative Synthesis Example 2 90 g of m-cresol, 56 g of p-cresol, 54 g of phenol, 105 g of a 37% formaldehyde aqueous solution, and 2.5 g of oxalic acid were placed in a three-head pull pen set in an oil bath, and the temperature was raised while stirring. It foamed violently at around 90°C, and after being temporarily cooled, the temperature was raised again to an internal temperature of 150°C. After reacting for about 3 hours, the temperature was raised again to 175°C, and water was distilled off. After 2 hours, the temperature was raised to 200°C, the pressure was reduced to 100 mmHg, and the residual monomer was distilled off. After 10 minutes, the reaction was stopped, and the reaction product was poured into a Teflon vat and solidified. The molecular weight of this resin was determined by GPC.
The calculations of 0Mn and Mw, which were measured using polystyrene as a standard, were performed in the same manner as described above. As a result, M is 13
50, Mw was 6750. (Synthesis of photoreceptor) 100 g of upirogallol and 700 g of acetone were placed in a three-headed kolben set in a water bath, nitrogen gas was blown in to replace the nitrogen, and 10 g of phosphorus oxychloride was added. The reaction temperature was kept at 20℃ and the reaction was continued all day and night. After the reaction, 3
The product was gradually introduced into 01 with strong stirring to precipitate a single polycondensate. The precipitated resin was filtered off and washed with water until it became almost neutral. The precipitate was dried below 40°C. In this way, a light brown resin 100jC was obtained. The molecular weight of this resin was determined by GPC (Hitachi model 635, column
Shodex A 804, A303
, 8802 in series] using polystyrene as a standard, e Mn s My was calculated using the method described in Tsuge et al., Journal of the Chemical Society of Japan, April issue, 1972, p. 800, by smoothing the peak in the oligomer region ( This was done by connecting the center of the peak and the center of the valley. As a result, M is 2000. MW was 3400. Next, 60 g of this resin was dissolved in 720 mJl of dioxane, 70 g of 1,2-naphthoquinone cyato-5-sulfonyl chloride was added, and after dissolving, 60 g of a 13% by weight aqueous potassium carbonate solution was added dropwise, and the mixture was heated at 40 to Brain fusion reaction was performed for 1 hour. The obtained reaction solution was poured into a large amount of diluted hydrochloric acid water (concentrated hydrochloric acid 13 mjL, water 3411), and the precipitated resin was filtered off and dried. In this way, the 1,2-naphthoquinone cyato-5-
56 g of yellow powder resin of sulfonic acid ester was obtained.
As a result of analysis, it was found that the condensation rate of OH groups was 20%. When the molecular weight of this ester was measured by the above-mentioned GPC, Mn was 2300° and Mw was 3030. Example 1 An aluminum plate with a thickness of 0.24 mm was degreased in a 5% aqueous sodium hydroxide solution, and then treated in a 0.3 molar nitric acid aqueous solution at a temperature of 30°C, a current density of 50 A/dm, and a treatment time of 30 seconds. The material was electrolytically etched under the following conditions, then desmutted with a 5% hydroxide/thorium aqueous solution, and then anodized in a sulfuric acid solution.The amount of anodic oxide film was measured using the method described above. Tokoro, 2
The aluminum support thus obtained was coated with a photosensitive coating solution having the following composition using a rotary coating machine. 100
It was dried at ℃ for 4 minutes to obtain a photosensitive lithographic printing plate having a film thickness of 24 mg/dm2. Photosensitive solution 1 2.3.4-trihydroxybenzophenone and 1.2-
Esterified product of naphthoquinone cyasito-5-sulfonic acid chloride (condensation rate: 95nJL%)
20 parts Binder of Synthesis Example 1
80 parts 2-trichloromethyl-5-[β-(2
'-Benzofuryl) vinyl)-1,3,4-oxadiazole 2 parts Victoria Blue BOH 1 part pt-octylphenol formaldehyde novolak resin (Mw = 1,300) and 1,2-naphthoquinone cyato-5-sulfone Esterified product with acid chloride (condensation rate: 50moJL%) 1 part Glutaric anhydride 3 parts Methyl cellosolve 200 parts Ethyl cellosolve 500 parts The obtained photosensitive lithographic printing plate was heated at 30 cm using a W ultra-high pressure mercury lamp from a distance of 60 cm. Exposure for seconds, then develop at 25°C for 40 minutes using a 9-fold dilution of the positive developing solution for PS plates "5DP-1" (manufactured by Konishiroku Photo Industry).
Development processing was performed for 5 seconds. The sensitivity and chemical resistance of the obtained lithographic printing plate were measured. A photosensitive coating liquid (photosensitive liquid 2) was prepared in the same manner as in Example 1, except that the binder of Synthesis Example 2 was used instead of the binder of Synthesis Example 1, and this was used to prepare Example 1. A lithographic printing plate was prepared in the same manner as described above, and the same measurements were performed. A photosensitive coating liquid (comparative photosensitive liquid 1) was prepared in the same manner as in Example 1, except that the binder of Comparative Synthesis Example 2 was used instead of the binder of Synthesis Example 1, and this was used in Examples. A lithographic printing plate was prepared in the same manner as in Example 1, and the same measurements were performed. Table 1 shows the measurement results of Example 1, Example 2, and Comparative Example 1. Table 1 (Note) (Otori) Novolac resin (proverb) Kasumi tW raw material is soaked for 1 day after soaking for 41 hours.
【を目視で観察して求めた一計価は１０点法によ
る（１０点は極めて良好、５点は画線部のかなりの損傷
（小点は消失）、０点は画線部消失を表わす）。
（りＡＢＣケミカル社ツし
く４） コダック社製。
（ＩＩ ＩＪｖインキ用（東洋インキ社製）。
ｔａ＋ ＵＶインキ用（東華色素社製）。
（７）小西六社製。
表１から本発明の印刷版は耐薬品性（含ＵＶインキ適性
）が極めて良好であることがわかる。
１１班１
実施例１の平版印刷版の印刷適性、現像性および耐刷力
について試験をした。
印刷適性については、平版印刷版な枚葉オフセット印刷
機にかけ、上質紙に印刷を行なって地汚れの有無を調べ
ることにより評価した。印刷の結果、地汚れは全く発生
せず、良好な印刷物を得ることができた。これにより印
刷適性が優れていることがわかる。
現像性を評価するために、４０°Ｃの温度、８０％の湿
度で７日間感光性平版印刷版の強制劣化を行ない、その
後で露光し、４ｍ”／ｉの５ＤＰ−１疲労現像液（７倍
希釈）で現像し、印刷を行なった。その結果地汚れは発
生せず、良好な印刷物が得られた。これにより現像性に
優れていることがわかる。
さらに耐刷力を評価するために、下記の条件でυＶイン
キによる印刷を行なった。
（ＵＶインキによる印刷条件）
印刷機 ：ハマダ、１−ＣＤＸ−９００印刷インキ
：東洋ンラッシュドライー０Ｌ−紅Ａｐ （東洋イ
ンキ社製）
レジューサー：東洋フラッシュトライレジューサ−０Ｐ
（東洋インキ社製）
プレートクリ
ーナー ：東洋フラッシュトライプレートクリーナ
ー （東洋インキ社製）
紙 ：上質紙
印刷スピード： ７０００枚／時
その結果、３万枚を刷了し、印刷物は地汚れもなく良好
であった。
これに対し、比較例１の平版印刷版を用いて、同一条件
でＵＶ印刷を行なったところ、印刷開始後まもなく印刷
版の画像が消失した。
比較例２
実施例１のバインダーを合成例１のものから比較合成例
１のものに変更しくｐ−ヒドロキシメタクリルアニリド
（ＨｙｆｌＭＡ）単位を２−ヒドロキシエチルメタクリ
レートに変更し）、その他は実施例１と同じ組成にして
（比較感光液２）、感光性平版印刷版を得た。実施例１
と同様に露光・現像を行なったが、現像できなかった。
これによりフェノール性水酸基が必須であることがわか
る。
塩蚊亘１
感光体を、２，３．４−）リヒトロキシベンゾフェノン
のエステル化物から、比較合成例１の感光体（ピロガロ
ール・アセトン樹脂のキノンジアジドエステル化物、Ｍ
、＝３０３０．Ｍｎ＝２３００、Ｑエステル化率＝２０
％）に変更した以外、実施例１と同一の方法により感光
性塗布液（比較感光液３）を調製し、これを用いて実施
例１と同一の方法で重版印刷版を作製した。結果を表２
に示した。
ここでボールペン耐性を検討するために露光および現像
処理前の前記感光性平版印刷版材料（Ｇ）上にボールペ
ン（ｉ）（ゼブラ社製、ＺＥＢＲＡ Ｎ５１００黒色
）、ボールペン（ｉｉ）（）ンボ鉛筆社製、ＧＯＬＦ青
）及びボールペン（ｉｉｉ）（パイロット萬年筆社製パ
イロットＢＳ−青）の３種のボールペンを用いて線を描
き、１０分間放置後、露光を行なわず前述の標準現像処
理を行なった。ボールペン耐性の評価は、筆跡後の感光
層の侵食程度を各々３ランクで判定した。
（以下、余白）
表２
Ａ印は画像部の侵食が僅かである。
Ｂ印は同上侵食が認められ、感光層の下の支持体の砂目
がやや露出している。
Ｃ印は同上侵食が著しく認められ、感光層の下の支持体
の砂目が完全に露出している。
ことを意味する。
又、アンダー現像性において、
０印は非画像部の感光層が完全に溶解除去されている。
Δ印は同上一部残存している。
Ｘ印は同上はとんど溶解していない。
ことを意味する。
又、オーバー現像性において、数値は標準現像とのベタ
段数差を意味し、−印は画像部の侵食が著しく、ベタ段
数がほとんど判定できない程オーバー現像性が悪いとい
うことを意味する。
以上より、感光体として２，３．４−トリヒドロキシベ
ンゾフェノンを使用すると現像ラチチュードとボールペ
ン適性が優れていることがわかる。
叉】ｕ１４
厚さ０．２９ｍｍのアルミニウム板を５％水酸化ナトリ
ウム水溶液中で脱脂処理した後、０．５モル塩酸水溶液
中で温度２５℃、電流密度６０Ａ／ｄｍ”、処理時間３
０秒間の条件で、電解エツチング処理を行なった０次い
で、５％水酸化ナトリウム水溶液でデスマット処理を施
し、しかる後硫酸溶液中で陽極酸化処理を行なった。陽
極酸化皮膜量を前述の方法で測定したところ、２０ｍｇ
／ ｄ ｍ ”であった。
次に９０℃の熱水溶液に浸漬し、封孔処理を行なった。
このようにして得られたアルミニウム支持体に下記の組
成の感光性塗布液を回転塗布機を用いて塗布し、１００
℃で４分間乾燥し、膜厚２４ｍｇ／ ｄ ｍ ”の感光
性平版印刷版を得た。
（感光液−３）
２．３，４．４’−テトラヒドロキシベンゾフェノンと
ナフトキノン−（１，２）−ジアジド−５−スルホン酸
クロライドとのエステル化物（縮合率ニア５ｍｏ１％）
２０部合成例３のバインダー
７０部ノボラック樹脂（ｍ−クレゾール／ｐ−
クレゾール／フェノール＝ ４８ ／ ３２ ／ ２０
ｍ ｏ見％、Ｍｗ＝４０００）
１０部２−トリクロロメチル−５−（β−（２′−ベン
ゾフリル）ビニル）−１，３，４−オキサジアゾール
２部ビクトリアブルー
ＢＯＨ１，１部
ｐ−オクチルフェノール・ホルムアルデヒドのノボラッ
ク樹脂（Ｍｗ＝１２００．Ｍｎ＝５００）１部
無水テトラヒドロフタル酸 １部メチルセ
ロソルブ ２００部エチルセロソルブ
ＳＯＯ部実施例１と同様にして、得
られた平版印刷版の耐刷力を評価するために、ＵＶイン
キによる印刷を行なった。
印刷条件は実施例３と同様にして行なったところ、４万
枚刷了し印刷物は地汚れもなく良好であった。
実１己１旦
感光体の２０部の内、５部だけをピロガロール・アセト
ン樹脂のキノンジアジドエステル化物（Ｍｗ＝１６００
Ｍｎ＝８００．Ｑエステル化率３０％）に変更した
以外は、実施例４と同様に調製し、平版印刷版を作成し
た。
実施例４と同じ条件でＵＶ印刷を行なったところ、３万
枚刷了し良好な印刷物を得ることができた。
［発明の効果］
以上詳細に説明したように、本発明の感光性平版印刷版
は耐ＵＶインキ適性、現像ラチチュード、ボールペン適
性、耐薬品性が良好で、かつ感度も良好という優れた効
果を奏するものである。[A score determined by visual observation is based on a 10-point system (10 points are extremely good, 5 points are significant damage to the image area (small dots are lost), and 0 points represent loss of the image area. ). (ABC Chemical Company Tsushiku 4) Manufactured by Kodak. (II) For IJv ink (manufactured by Toyo Ink Co., Ltd.). ta+ For UV ink (manufactured by Toka Shiki Co., Ltd.). (7) Manufactured by Konishirokusha. From Table 1, the printing plate of the present invention has chemical resistance (suitability for UV inks included). It can be seen that the printing properties are extremely good.Group 11 The lithographic printing plate of Example 1 was tested for printability, developability, and printing durability.For the printability, the lithographic printing plate was run on a sheet-fed offset printing machine, Evaluation was carried out by printing on paper and examining the presence or absence of background smudge. As a result of printing, no background smear occurred and good printed matter could be obtained. This shows that the printing suitability is excellent. To evaluate the developability, photosensitive lithographic printing plates were forced to age for 7 days at a temperature of 40° C. and a humidity of 80%, after which they were exposed to light and treated with 4 m”/i of 5DP-1 fatigue developer ( 7 times diluted) and printed.As a result, no scumming occurred and good printed matter was obtained.This shows that the developability is excellent.Furthermore, to evaluate the printing durability. Printing was carried out with υV ink under the following conditions. (Printing conditions with UV ink) Printing machine: Hamada, 1-CDX-900 Printing ink: Toyoon Lash Dry 0L-BeniAp (manufactured by Toyo Ink Co., Ltd.) Juicer: Toyo Flash Tri Reducer-0P
(manufactured by Toyo Ink Co., Ltd.) Plate cleaner: Toyo Flash Tri Plate Cleaner (manufactured by Toyo Ink Co., Ltd.) Paper: High-quality paper Printing speed: 7,000 sheets/hour As a result, 30,000 sheets were printed, and the printed matter was in good condition with no background stains. there were. On the other hand, when UV printing was performed under the same conditions using the lithographic printing plate of Comparative Example 1, the image on the printing plate disappeared shortly after printing started. Comparative Example 2 The binder in Example 1 was changed from that in Synthesis Example 1 to that in Comparative Synthesis Example 1, and the p-hydroxymethacrylanilide (HyflMA) unit was changed to 2-hydroxyethyl methacrylate), and the other conditions were the same as in Example 1. A photosensitive lithographic printing plate was obtained using the same composition (comparative photosensitive liquid 2). Example 1
Exposure and development were carried out in the same manner as above, but development was not possible. This shows that the phenolic hydroxyl group is essential. Wataru Salt Mosquito 1 A photoreceptor was prepared from an esterified product of 2,3,4-)lihydroxybenzophenone to the photoreceptor of Comparative Synthesis Example 1 (quinonediazide esterified product of pyrogallol acetone resin, M
,=3030. Mn=2300, Q esterification rate=20
A photosensitive coating liquid (comparative photosensitive liquid 3) was prepared in the same manner as in Example 1, except that the coating liquid was changed to (%), and a reprint printing plate was produced using this in the same manner as in Example 1. Table 2 shows the results.
It was shown to. Here, in order to examine ballpoint pen resistance, ballpoint pens (i) (manufactured by Zebra Co., Ltd., ZEBRA N5100 black) and ballpoint pens (ii) () were applied to the photosensitive lithographic printing plate material (G) before exposure and development treatment. Lines were drawn using three types of ballpoint pens: a ballpoint pen (III) (Pilot BS-Blue, manufactured by Pilot Mannen Pen Co., Ltd.), and after being left for 10 minutes, the standard development process described above was performed without exposure. . The ballpoint pen resistance was evaluated by evaluating the degree of erosion of the photosensitive layer after handwriting, using three ranks. (Hereinafter referred to as margins) Table 2 Mark A indicates slight erosion in the image area. Mark B indicates erosion as above, and the grains of the support under the photosensitive layer are slightly exposed. Mark C shows significant erosion as above, and the grains of the support below the photosensitive layer are completely exposed. It means that. Regarding under-development, a mark of 0 indicates that the photosensitive layer in the non-image area has been completely dissolved and removed. Part of the Δ mark remains as above. The X mark indicates that the same as above is hardly dissolved. It means that. Regarding over-developability, the numerical value means the difference in the number of solid stages from standard development, and the - mark means that the erosion of the image area is so severe that the over-developability is so bad that the number of solid stages can hardly be determined. From the above, it can be seen that when 2,3,4-trihydroxybenzophenone is used as a photoreceptor, the development latitude and ballpoint pen suitability are excellent. ] u14 After degreasing an aluminum plate with a thickness of 0.29 mm in a 5% aqueous sodium hydroxide solution, it was degreased in a 0.5 M aqueous hydrochloric acid solution at a temperature of 25°C, a current density of 60 A/dm, and a treatment time of 3.
Electrolytic etching was performed for 0 seconds, followed by desmutting with a 5% aqueous sodium hydroxide solution, and then anodizing in a sulfuric acid solution. When the amount of anodic oxide film was measured using the method described above, it was found to be 20 mg.
/ d m''. Next, it was immersed in a hot aqueous solution at 90°C for pore sealing. A photosensitive coating liquid having the following composition was applied to the aluminum support thus obtained using a spin coating machine. Apply using 100
It was dried at ℃ for 4 minutes to obtain a photosensitive lithographic printing plate with a film thickness of 24 mg/dm''. (Photosensitive liquid-3) 2.3,4.4'-tetrahydroxybenzophenone and naphthoquinone-(1,2) - Esterified product with diazide-5-sulfonic acid chloride (condensation rate near 5 mo 1%)
20 parts Binder of Synthesis Example 3
70 parts novolac resin (m-cresol/p-
Cresol/phenol = 48/32/20
m o %, Mw = 4000)
10 parts 2-trichloromethyl-5-(β-(2'-benzofuryl)vinyl)-1,3,4-oxadiazole
2 parts Victoria Blue BOH 1 part p-octylphenol formaldehyde novolak resin (Mw = 1200. Mn = 500) 1 part tetrahydrophthalic anhydride 1 part methyl cellosolve 200 parts ethyl cellosolve SOO part Obtained in the same manner as in Example 1. In order to evaluate the printing durability of the lithographic printing plate obtained, printing was performed using UV ink. The printing conditions were the same as in Example 3, and 40,000 copies were printed, and the printed matter was in good condition with no scumming. Of the 20 parts of the photoreceptor, only 5 parts were made of a quinone diazide ester of pyrogallol acetone resin (Mw = 1600).
Mn=800. A lithographic printing plate was prepared in the same manner as in Example 4 except that the esterification rate was changed to 30%). When UV printing was carried out under the same conditions as in Example 4, 30,000 copies were printed and good quality printed matter was obtained. [Effects of the Invention] As explained in detail above, the photosensitive lithographic printing plate of the present invention exhibits excellent effects such as good UV ink resistance, development latitude, ballpoint pen suitability, and chemical resistance, as well as good sensitivity. It is something.
Claims (1)
ンジアジドスルホン酸エステルと、 （Ｂ）下記一般式〔 I 〕により表わされる構造単位を
有する高分子化合物、 ▲数式、化学式、表等があります▼・・・〔 I 〕 （式中、Ｒ＿１およびＲ＿２は水素原子、ハロゲン原子
、アルキル基、アリール基またはカルボン酸基であり、
Ｒ＿３は水素原子、ハロゲン原子、アルキル基またはア
リール基であり、Ｒ＿４は水素原子、アルキル基、アリ
ール基またはアラルキル基であり、Ｙは置換基を有して
もよい芳香族基であり、Ｘは窒素原子と前記芳香族基の
炭素原子とを連結する２価の有機基であり、ｎは０〜５
の整数である。） とを含有する感光層を支持体上に有することを特徴とす
るポジ型感光性平版印刷版。[Scope of Claims] (A) o-naphthoquinonediazide sulfonic acid ester of polyhydroxybenzophenone; (B) a polymer compound having a structural unit represented by the following general formula [I]; Yes▼...[I] (In the formula, R_1 and R_2 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxylic acid group,
R_3 is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; R_4 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; Y is an aromatic group that may have a substituent; It is a divalent organic group that connects the nitrogen atom and the carbon atom of the aromatic group, and n is 0 to 5.
is an integer. ) A positive-working photosensitive lithographic printing plate characterized by having a photosensitive layer on a support.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62057282A JP2551943B2 (en) | 1987-03-12 | 1987-03-12 | Photosensitive lithographic printing plate |
| EP19880302171 EP0287212B1 (en) | 1987-03-12 | 1988-03-11 | Positive photosensitive planographic printing plate |
| DE19883852559 DE3852559T2 (en) | 1987-03-12 | 1988-03-11 | Photosensitive positive planographic printing plate. |
| US07/789,550 US5182183A (en) | 1987-03-12 | 1991-11-08 | Positive photosensitive planographic printing plates containing specific high-molecular weight compound and photosensitive ester of O-napthoquinonediazidosulfonic acid with polyhydroxybenzophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62057282A JP2551943B2 (en) | 1987-03-12 | 1987-03-12 | Photosensitive lithographic printing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63223637A true JPS63223637A (en) | 1988-09-19 |
| JP2551943B2 JP2551943B2 (en) | 1996-11-06 |
Family
ID=13051181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62057282A Expired - Fee Related JP2551943B2 (en) | 1987-03-12 | 1987-03-12 | Photosensitive lithographic printing plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2551943B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63311247A (en) * | 1987-06-12 | 1988-12-20 | Konica Corp | Photosensitive composition |
| JPS6421440A (en) * | 1987-07-17 | 1989-01-24 | Mitsubishi Chem Ind | Photosensitive planographic printing plate |
| JPH02281257A (en) * | 1989-04-21 | 1990-11-16 | Konica Corp | Colored image forming material |
| EP0774692A2 (en) | 1995-11-17 | 1997-05-21 | Hoechst Aktiengesellschaft | Radiation-sensitive recording material for the production of planographic printing plates |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5055406A (en) * | 1973-09-21 | 1975-05-15 | ||
| JPS57111529A (en) * | 1980-10-23 | 1982-07-12 | Hoechst Ag | Photosensitive mixture, photosensitive copying material manufactured from said mixture and manufacture of printing block from said copying material |
| JPS5817112A (en) * | 1981-06-22 | 1983-02-01 | フイリツプ・エイ・ハント・ケミカル・コ−ポレイシヨン | Positive novolak photoresist composition and blend |
-
1987
- 1987-03-12 JP JP62057282A patent/JP2551943B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5055406A (en) * | 1973-09-21 | 1975-05-15 | ||
| JPS57111529A (en) * | 1980-10-23 | 1982-07-12 | Hoechst Ag | Photosensitive mixture, photosensitive copying material manufactured from said mixture and manufacture of printing block from said copying material |
| JPS5817112A (en) * | 1981-06-22 | 1983-02-01 | フイリツプ・エイ・ハント・ケミカル・コ−ポレイシヨン | Positive novolak photoresist composition and blend |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63311247A (en) * | 1987-06-12 | 1988-12-20 | Konica Corp | Photosensitive composition |
| JPS6421440A (en) * | 1987-07-17 | 1989-01-24 | Mitsubishi Chem Ind | Photosensitive planographic printing plate |
| JPH02281257A (en) * | 1989-04-21 | 1990-11-16 | Konica Corp | Colored image forming material |
| EP0774692A2 (en) | 1995-11-17 | 1997-05-21 | Hoechst Aktiengesellschaft | Radiation-sensitive recording material for the production of planographic printing plates |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2551943B2 (en) | 1996-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0769605B2 (en) | Photosensitive composition | |
| JPS6389864A (en) | Photosensitive lithographic printing plate | |
| EP0287212B1 (en) | Positive photosensitive planographic printing plate | |
| JPS63223637A (en) | Photosensitive planographic printing plate | |
| US5182183A (en) | Positive photosensitive planographic printing plates containing specific high-molecular weight compound and photosensitive ester of O-napthoquinonediazidosulfonic acid with polyhydroxybenzophenone | |
| JP2648981B2 (en) | Photosensitive lithographic printing plate | |
| JPH0658531B2 (en) | Photosensitive lithographic printing plate | |
| JPS60143345A (en) | Positive type lighographic printing plate material | |
| JPS63235936A (en) | Photosensitive planographic printing plate | |
| JP2551947B2 (en) | Photosensitive lithographic printing plate | |
| JP2603641B2 (en) | Photosensitive lithographic printing plate | |
| JP3743174B2 (en) | Photosensitive planographic printing plate | |
| JPH0416947A (en) | Photosensitive composition | |
| JPH0296757A (en) | Photosensitive planographic printing plate | |
| JPS63183441A (en) | Photosensitive composition having excellent chemical resistance and inking property | |
| JP2625743B2 (en) | Photosensitive lithographic printing plate | |
| JPS63198046A (en) | Photosensitive composition having excellent treating chemical resistant and ink forming properties | |
| JP2551948B2 (en) | Photosensitive lithographic printing plate | |
| JPH0296759A (en) | Photosensitive planographic printing plate | |
| JPS63314538A (en) | Photosensitive composition and photosensitive planographic printing plate | |
| JP2969021B2 (en) | Photosensitive lithographic printing plate | |
| JPS63214747A (en) | Photosensitive composition | |
| JPH04204453A (en) | Photosensitive composition | |
| JPH04155341A (en) | Photo sensitive flat printing form plate | |
| JP2596004B2 (en) | Photosensitive lithographic printing plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |