JPS6397945A - Photosensitive composition and photosensitive lithographic printing plate containing novel acid decomposable compound - Google Patents
Photosensitive composition and photosensitive lithographic printing plate containing novel acid decomposable compoundInfo
- Publication number
- JPS6397945A JPS6397945A JP24386286A JP24386286A JPS6397945A JP S6397945 A JPS6397945 A JP S6397945A JP 24386286 A JP24386286 A JP 24386286A JP 24386286 A JP24386286 A JP 24386286A JP S6397945 A JPS6397945 A JP S6397945A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- acid
- compd
- photosensitive
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 title claims description 85
- 239000000203 mixture Substances 0.000 title claims description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract 9
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 11
- 125000001424 substituent group Chemical group 0.000 abstract description 9
- 125000003172 aldehyde group Chemical group 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 150000001241 acetals Chemical group 0.000 description 11
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- -1 acetal compounds Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- HEVMDQBCAHEHDY-UHFFFAOYSA-N (Dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=CC=C1 HEVMDQBCAHEHDY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KZDFOVZPOBSHDH-UHFFFAOYSA-N 1,1-diethoxy-2-methylpropane Chemical compound CCOC(C(C)C)OCC KZDFOVZPOBSHDH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010033557 Palpitations Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 244000144985 peep Species 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は感光性平版印刷版および該印刷版に用いられる
感光性組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive lithographic printing plate and a photosensitive composition used in the printing plate.
［発明の背景コ
ポジ型感光性組成物としては、活性光線の照射により酸
を生成する第１の反応と、生成した酸による第２の反応
、すなわち酸分解反応とにより、露光部が現像液に可溶
化するという原理を利用したものが種々知られている。[Background of the Invention In a composite type photosensitive composition, the exposed area is exposed to a developer by a first reaction in which an acid is generated by irradiation with actinic rays and a second reaction by the generated acid, that is, an acid decomposition reaction. Various products are known that utilize the principle of solubilization.
第２の反応に用いられる酸分解化合物としては、特開昭
５３−１３３４２９号、特公昭５２−３６４４２号の明
ｍ書中に記載されているアセタール化合物、特開昭５３
−１３３４２９号の明１ＩＩｌ書中に記載されているケ
タール化合物などが挙げられる。The acid decomposition compounds used in the second reaction include acetal compounds described in the specifications of JP-A-53-133429 and JP-B-52-36442;
Examples thereof include the ketal compounds described in Mei Illl of No. 133429.
しかし、これらの感光性組成物は処理薬品に対する耐性
が低く、例えば、感光性平版印刷版に用いた場合、イン
キ盛りに使用する現像インキや印刷時に使用するクリー
ナー類で処理すると、小点（小さい網点）が消失する欠
点があった。また、耐刷力も低く、印刷枚数の多い印刷
には不向きであった。However, these photosensitive compositions have low resistance to processing chemicals. For example, when used in photosensitive lithographic printing plates, when treated with developing ink used for inking or cleaners used during printing, small dots (small The disadvantage was that halftone dots) disappeared. In addition, the printing durability was low, making it unsuitable for printing a large number of sheets.
［発明の目的］
従って、本発明の目的は、対処理薬品性および耐刷性に
優れた感光性平版印刷版、およびそれに用いられる新規
な酸分解化合物を含有する感光性組成物を提供すること
にある。[Object of the Invention] Therefore, the object of the present invention is to provide a photosensitive lithographic printing plate having excellent processing chemical resistance and printing durability, and a photosensitive composition containing a novel acid-decomposed compound used therein. It is in.
［発明の構成］
本発明の目的は、活性光線の照射により酸を発生する化
合物、および酸により分解し得る少なくとも１つのアセ
タール部分を有する化合物を含有する感光性組成物にお
いて、前記アセタール部分を形成する各ＯＨ基がフェノ
ール性ＯＨ基である感光性組成物、ざらに、支持体上に
上記感光性組成物から形成される感光性層を有する感光
性平版印刷版により達成された。[Structure of the Invention] An object of the present invention is to provide a photosensitive composition containing a compound that generates an acid upon irradiation with actinic rays and a compound having at least one acetal moiety that can be decomposed by the acid, in which the acetal moiety is formed. This was achieved by a photosensitive lithographic printing plate having a photosensitive composition in which each OH group is a phenolic OH group, and a photosensitive layer formed from the photosensitive composition on a support.
し発明の具体的構成］
本発明の感光性組成物は活性光線の照射により酸を発生
し得る化合物と酸により分解し得る化合物とを含有する
。Specific Structure of the Invention] The photosensitive composition of the invention contains a compound capable of generating an acid upon irradiation with actinic rays and a compound decomposed by the acid.
上記酸により分解し得る化合物は、具体的には酸によっ
て分解し得る、下記一般式［Ｉ］で示される構造単位を
少なくとも１つ含有する化合物である。Specifically, the acid-decomposable compound is a compound containing at least one structural unit represented by the following general formula [I], which is acid-decomposable.
一般式［工］
Ｘ−０−Ｃ−０−Ｙ
一般式［Ｉ］において、ＸおよびＹはそれぞれ、置換基
を有するものも含むアリール基を表わす。General formula [E] X-0-C-0-Y In the general formula [I], X and Y each represent an aryl group including one having a substituent.
またＲは置換基を有するものも含むアルキル基、アルケ
ニル基またはアリール基を表わす。Further, R represents an alkyl group, an alkenyl group, or an aryl group including those having substituents.
Ｘ、ＹおよびＲで表わされるアリール基としては、フェ
ニル基、ナフチル基等が挙げられ、アリール基の置換基
としては、アルキル基（例えば、メチル基、エチル基、
プロピル基、１−プロピル基、ブチル基、℃−ブチル基
、ｎ−アミル基、オクチル基、ドデシル基）、アルコキ
シ基（例えば、メトキシ基、エトキシ基、ブトキシ基）
、シアノ基、ニトロ基等が挙げられる。またこれらアリ
ール基の置換基はさらに置換基を有していてもよい。Examples of the aryl group represented by
propyl group, 1-propyl group, butyl group, °C-butyl group, n-amyl group, octyl group, dodecyl group), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group)
, a cyano group, a nitro group, and the like. Moreover, the substituents of these aryl groups may further have a substituent.
Ｒで表わされるアルキル基としては、メチル基、エチル
基、プロピル基、１−−プロピル基、ブチル基、し−ブ
チル基、ｎ−アミル基、オクチル基、ドデシル基、アル
ケニル基としては、プロペニル基、ブテニル基等が挙げ
られる。またアルキル基およびアルケニル基の置換基と
しては、アリール基（例えば、フェニル基）等が挙げら
れる。Examples of the alkyl group represented by R include methyl group, ethyl group, propyl group, 1-propyl group, butyl group, shi-butyl group, n-amyl group, octyl group, dodecyl group, and alkenyl group includes propenyl group. , butenyl group, etc. Further, examples of substituents for alkyl groups and alkenyl groups include aryl groups (eg, phenyl groups) and the like.
前記一般式［Ｉ］において、さらに好ましくは、Ｘおよ
びＹで表わされるアリール基が共に置換基を有ざない場
合または共に置換基を１つ有する場合である。In the general formula [I], it is more preferable that the aryl groups represented by X and Y both have no substituent or both have one substituent.
一般式［Ｉ］で表わされる化合物（以下、本発明の化合
物という。）は、例えば、１つのフェノール性ＯＨ基を
有する化合物（以下、ＯＨ基含有化合物という）の少な
くとも１つとアルデヒド基を有する化合物との脱水縮合
反応あるいはアセタールとＯＨ基含有化合物との交換反
応により合成し得る。The compound represented by the general formula [I] (hereinafter referred to as the compound of the present invention) is, for example, a compound having at least one compound having one phenolic OH group (hereinafter referred to as an OH group-containing compound) and an aldehyde group. It can be synthesized by a dehydration condensation reaction with an acetal or an exchange reaction between an acetal and an OH group-containing compound.
上記の反応については、特開昭５３−１３３４２９号お
よびＪ 、 Ｏｒａ、 Ｃｈｅｌｍ、、 ２５ 、５
２１（１９６０） 、Ｊ 。Regarding the above reaction, see JP-A-53-133429 and J. Ora, Chelm., 25, 5.
21 (1960), J.
Ｏｒｇ、 Ｃｈｅｍ、、 ２５．５２５（１９６０）
、Ｊ、 Ｏｒａ。Org, Chem, 25.525 (1960)
, J. Ora.
ＣｈｅＩＩｌ、、 ２４．１７３０１９５９）等に記
載されており、本発明の化合物は、これらに開示された
同様あるいは類似の反応によって合成することができる
。CheIIl, 24.17301959), etc., and the compound of the present invention can be synthesized by the same or similar reactions disclosed therein.
例えば、本発明の化合物は、アルデヒド基を有する化合
物およびアセタールを有する化合物から選ばれる少なく
とも１つの化合物とＯＨ基含有化合物とを溶媒中あるい
は溶媒を用いないで、６０〜１７０℃の温度、好ましく
は８０〜１５０℃の温度で１時間〜数時間反応させて得
ることができる。For example, the compound of the present invention can be prepared by combining at least one compound selected from aldehyde group-containing compounds and acetal-containing compounds and an OH group-containing compound at a temperature of 60 to 170°C, preferably in a solvent or without using a solvent. It can be obtained by reacting at a temperature of 80 to 150°C for one to several hours.
遊離したアルコール、水などの副生成物は場合により留
去する。この時酸性触媒、例えばｐ−トルエンスルホン
酸あるいは＠酸などの存在下に反応させることが好まし
い。また場合により減圧下もしくは窒素雰囲気下で反応
させても良い。また前記反応条件下で不活性な溶媒、例
えばベンゼン、トルエン、キシレン、ジオキサン、塩素
化炭化水素等を反応溶媒として用いることもできる。遊
離した反応水あるいは低沸点アルコールなどは場合によ
り、溶媒の１部と共に留去する。By-products such as liberated alcohol and water are optionally distilled off. At this time, it is preferable to carry out the reaction in the presence of an acidic catalyst such as p-toluenesulfonic acid or @acid. Further, depending on the case, the reaction may be carried out under reduced pressure or under a nitrogen atmosphere. Further, solvents that are inert under the above reaction conditions, such as benzene, toluene, xylene, dioxane, chlorinated hydrocarbons, etc., can also be used as the reaction solvent. The liberated reaction water or low-boiling alcohol may optionally be distilled off together with a portion of the solvent.
アルデヒド基又は、アセタールを有する化合物と前記Ｏ
Ｈ基含有化合物の反応における量比はアルデヒド基又は
、アセタールを有する化合物１モルに対してＯＨ基が合
計で２モルになるようにす。A compound having an aldehyde group or an acetal and the O
The quantitative ratio of the H group-containing compounds in the reaction is such that the total amount of OH groups is 2 moles per 1 mole of the compound having an aldehyde group or acetal.
るが、場合によっては、これとは異なる量比でも良い。However, depending on the case, a different ratio may be used.
また２種のＯＨ基含有化合物を用いる場合は、前記アル
デヒド基又は、アセタールを有する化合物及び２種のＯ
Ｈ基含有化合物の合計３つを同時に反応させても良いし
、場合によっては、まずアルデヒド基又は、アセタール
を有する化合物及び一方のＯＨ基含有化合物を反応させ
て、その後、生成物ともう一方のＯＨ基含有化合物を反
応させてもよい。３種以上のＯＨ基含有化合物を用いる
場合も同様に反応を行なわせることができる。In addition, when two types of OH group-containing compounds are used, the above-mentioned aldehyde group- or acetal-containing compound and two types of O
A total of three H group-containing compounds may be reacted simultaneously, or in some cases, a compound having an aldehyde group or acetal and one OH group-containing compound are first reacted, and then the product and the other compound are reacted. An OH group-containing compound may also be reacted. Even when three or more types of OH group-containing compounds are used, the reaction can be carried out in the same manner.
本発明の化合物を製造する際の脱水縮合反応あるいは交
換反応に用いられる前記ＯＨ基含有化合物として、特願
昭６０−２５１７４４号の明細書中（１２〜１３頁）に
記載されている１価、２価、３価および４価以上のフェ
ノール性ＯＨ基を有する化合物などを挙げることができ
る。As the OH group-containing compound used in the dehydration condensation reaction or exchange reaction in producing the compound of the present invention, the monovalent compound described in the specification of Japanese Patent Application No. 60-251744 (pages 12-13), Compounds having divalent, trivalent, and tetravalent or higher phenolic OH groups can be mentioned.
本発明の化合物を製造する際に用いられるアルデヒド基
を有する化合物としては、例えば以下の特願昭６１−１
５５４８１号の明細書中（１８〜１９頁）に記載されて
いる化合物が挙げられる。Examples of the compound having an aldehyde group used in producing the compound of the present invention include the following Japanese Patent Application No. 61-1
Examples include the compounds described in the specification of No. 55481 (pages 18 to 19).
また、アセタールの例としては、前記のアルデヒドのメ
タノールやエタノールなどの低級アルコールによるアセ
タールが挙げられる。具体的な例としては、イソブチル
アルデヒドジエチルアセタール、ｎ−カプロンアルデヒ
ドジエチルアセタール、ベンズアルデヒドジメチルアセ
タールが挙げられる。Further, examples of acetals include acetals of the above-mentioned aldehydes with lower alcohols such as methanol and ethanol. Specific examples include isobutyraldehyde diethylacetal, n-caproaldehyde diethylacetal, and benzaldehyde dimethylacetal.
以下、本発明の化合物の具体例を挙げるが、本発明の化
合物はこれらに限定されない。Specific examples of the compounds of the present invention are listed below, but the compounds of the present invention are not limited thereto.
一般式［＋１
Ｘ−０−Ｃ−０−Ｙ
覗
ｃ８
ｏＩＯ
ｏ１２
！’！Ｏ！３
Ｎｏ１４
Ｎｏ １５
ｏｉＴ
１≦Ａ、ζ≦１０
以１）蒼白
夫２
・１ノＬ
本発明の化合物の含有量は、本発明の感光性組成物の全
固形分に対し、５〜７０重量％が好ましく、特に好まし
くは１０〜５０１ｉｆｆｉ％である。General formula [+1 X-0-C-0-Y peep c8 oIO o12 ! '! O! 3 No. 14 No. 15 oiT 1≦A, ζ≦10 or less 1) Arobafu 2 ・1 noL The content of the compound of the present invention is 5 to 70% by weight based on the total solid content of the photosensitive composition of the present invention. is preferred, particularly preferably 10 to 501 iffi%.
又、前記本発明の化合物は単独で用いても良いし、２種
以上を混合して用いても良い。本発明の化合物の合成物
がいくつかの混合物として得られる場合は、混合物のま
ま用いても良いし、分離生成して用いてもよい。Further, the compounds of the present invention may be used alone or in combination of two or more. When the composite of several compounds of the present invention is obtained as a mixture, the mixture may be used as it is, or it may be separated and used.
本発明の感光性組成物には、さらに活性光線の照射によ
り酸を発生する化合物（以下、本発明の酸発生化合物と
いう。）を含有することが必須である。It is essential that the photosensitive composition of the present invention further contains a compound that generates an acid upon irradiation with actinic rays (hereinafter referred to as the acid-generating compound of the present invention).
本発明の酸発生化合物としては、各種の公知化合物及び
混合物が挙げられる。例えばジアゾニウム塩、ホスホニ
ウム塩、スルホニウム塩、及びヨードニウムのＢＦ悸−
１ＰＦｓ−１Ｓｂ Ｆｓ−１Ｓｔ Ｆ６−１ＣＩＯ＋−
などの塩、有機ハロゲン化合物、オルトキノン−ジアジ
ドスルホニルクロリド、及び有濾金属／有礪ハロゲン化
銀も活性光線の照射の際に酸を形成又は分離する活性光
線感受性成分であり、本発明の酸発生化合物として使用
することができる。原理的には遊離基形成性の光開始剤
として知られるすべての有機ハロゲン化合物は、ハロゲ
ン化水素酸を形成する化合物で、本発明の酸発生化合物
として使用することができる。The acid generating compound of the present invention includes various known compounds and mixtures. For example, diazonium salts, phosphonium salts, sulfonium salts, and iodonium BF palpitations.
1PFs-1Sb Fs-1St F6-1CIO+-
Salts such as salts, organic halogen compounds, orthoquinone-diazide sulfonyl chloride, and filtered metal/hardened silver halides are also actinic radiation-sensitive components that form or separate acids upon irradiation with actinic radiation; It can be used as a generating compound. All organic halogen compounds, which are known in principle as free-radical-forming photoinitiators, are compounds which form hydrohalic acids and can be used as acid-generating compounds according to the invention.
前記のハロゲン化水素酸を形成する化合物の例は米国特
許明細３第３，５１５，５５２号、同第３，５３６，４
８９号及び同第３．７７９．７７８号及び西ドイツ国特
許公開公報第２，２４３，６２１号に記載されているも
のが挙げられ、又、例えば西ドイツ国特許公開公報第２
．６１０，８４２号に記載の光分解により酸を発生させ
る化合物も使用することができる。Examples of compounds that form the aforementioned hydrohalic acids are U.S. Pat. Nos. 3,515,552 and 3,536,4
89 and 3.779.778 and West German Patent Application No. 2,243,621;
．． Compounds that generate acids upon photolysis as described in US Pat. No. 6,100,842 can also be used.
また更に特開昭５４−７４７２８号公報、特開昭５５−
２４１１３号公報、特開昭５５−７７７４２号公報、特
開昭６０−３６２６号公報、特開昭６０−１３８５３９
号公報に記載の２−ハロメチル−１，３，４−オキサジ
アゾール系化合物など具体的には、２−トリクロロメチ
ル−５−［β（２−ベンゾフリル）ビニル］１，３．４
−オキサジアゾールを使用することができる。Furthermore, JP-A-54-74728, JP-A-55-
24113, JP 55-77742, JP 60-3626, JP 60-138539
Specifically, the 2-halomethyl-1,3,4-oxadiazole-based compounds described in the above publication include 2-trichloromethyl-5-[β(2-benzofuryl)vinyl]1,3.4
-Oxadiazoles can be used.
本発明の酸発生化合物の具体例としては、特開昭５６−
１７３４５号公報に記載のものを挙げることができる。Specific examples of the acid generating compound of the present invention include JP-A-56-
Examples include those described in Japanese Patent No. 17345.
また、特開昭５０−３６２０９号公報に記載されている
０−ナフトキノンジアジド−４−スルホン酸ハロゲニド
も用いることができる。Further, 0-naphthoquinonediazide-4-sulfonic acid halide described in JP-A-50-36209 can also be used.
本発明の酸発生化合物は、その化学的性質及び本発明の
感光性組成物の組成あるいは物性によって広範囲に変え
ることができるが、本発明の感光性組成物の固形分の全
重量に対して約０．１〜約２０重句％の範囲が適当であ
り、好ましくは０．２〜１０重量％の範囲である。The acid-generating compound of the present invention can vary widely depending on its chemical properties and the composition or physical properties of the photosensitive composition of the present invention, but is approximately A range of 0.1 to about 20% by weight is suitable, preferably a range of 0.2 to 10% by weight.
本発明の感光性組成物には、前記の本発明の酸発生化合
物と前記の本発明の化合物とに加えて、ざらに実質的に
水に不溶でアルカリ性水溶液に可溶である高分子ｍ結合
剤を加えることが必要である。The photosensitive composition of the present invention contains, in addition to the acid generating compound of the present invention and the compound of the present invention, a polymeric m-bond that is substantially insoluble in water and soluble in an alkaline aqueous solution. It is necessary to add an agent.
本発明の高分子ｍ結合剤としてはフェノール性ＯＨ基を
有する化合物が好ましく、例えば以下のものを挙げるこ
とができる。As the polymeric binder of the present invention, compounds having a phenolic OH group are preferable, and examples thereof include the following.
アルケニルヒドロキシアリール、ヒドロキシアリールア
ルケニルアミドあるいはヒドロキシアリールアルケニル
エステルなどのフェノール性ＯＨ基を有する化合物の少
なくとも１つを単量体とする単一の重合体、共重合体あ
るいは他のビニル系単量体との共重合体である。A single polymer, copolymer or other vinyl monomer containing at least one monomer of a compound having a phenolic OH group such as alkenylhydroxyaryl, hydroxyarylalkenylamide or hydroxyarylalkenyl ester. It is a copolymer of
またノボラック樹脂を用いることもでき、好適なノボラ
ック樹脂としては、フェノール、０−クレゾール、ｍ−
クレゾール、ｐ−クレゾールのうちの少なくとも１種類
とホルムアルデヒドとから成るノボラック樹脂などが挙
げられる。Further, novolak resins can also be used, and suitable novolak resins include phenol, 0-cresol, m-
Examples include novolac resins made of formaldehyde and at least one of cresol and p-cresol.
前記のフェノール性ＯＨ基を有するポリビニル系の高分
子化合物やノボラック樹脂は単独で用いてもよいし、又
２種以上を混合して用いても良い。The polyvinyl polymer compound or novolak resin having a phenolic OH group may be used alone or in combination of two or more.
またこれらの高分子量結合剤が本発明の感光性組成物中
に含まれる含有量は３０〜９５重量％が好ましく、より
好ましくは５０〜９０重量％である。The content of these high molecular weight binders in the photosensitive composition of the present invention is preferably 30 to 95% by weight, more preferably 50 to 90% by weight.
本発明の感光性組成物には前記の本発明の酸発生化合物
、本発明の化合物、可溶性樹脂等の各々の素材の他、必
要に応じて更に染料、顔料等の色素、可塑剤などを添加
することができ、またさらに、使用目的に応じて必要で
あれば、増感剤（前記本発明の酸発生化合物の酸発生効
率を増大させる化合物）などを添加することもできる。In addition to the above-described materials such as the acid-generating compound of the present invention, the compound of the present invention, and the soluble resin, the photosensitive composition of the present invention may further contain pigments such as dyes and pigments, plasticizers, etc. Furthermore, if necessary depending on the purpose of use, a sensitizer (a compound that increases the acid generation efficiency of the acid generation compound of the present invention) or the like may be added.
本発明の感光性組成物においては、前記各成分を溶解す
る下記の溶媒に溶解させて、これらを適当な支持体の表
面に塗布乾燥させることにより、感光性層を設けて、本
発明の感光性組成物による感光性平版印刷版（以下、本
発明の感光性平版印刷版という。）を形成することがで
きる。In the photosensitive composition of the present invention, a photosensitive layer is provided by dissolving each of the above-mentioned components in the following solvents and coating and drying them on the surface of a suitable support. A photosensitive planographic printing plate (hereinafter referred to as the photosensitive planographic printing plate of the present invention) can be formed using the photosensitive composition.
本発明の感光性組成物の各成分を溶解する際に使用し得
る溶媒としては、メチルセロソルブ、メチルセロソルブ
アセテート、エチルセロソルブ、エチルセロソルブアセ
テート等のセロソルブ類、１．２−プロパンジオールモ
ノメチルエーテル又はそのアセテート、１．２−プロパ
ンジオールモノエチルエーテル又はそのアセテート、ジ
メチルホルムアミド、ジメチルスルホキシド、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
、メチルエチルケトン等が挙げられる。Solvents that can be used to dissolve each component of the photosensitive composition of the present invention include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, 1,2-propanediol monomethyl ether, and its like. Examples include acetate, 1,2-propanediol monoethyl ether or its acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone, and the like.
又、特開昭６０−２０８７５０号公報に記載の方法、す
なわち感光性組成物を有機溶剤に溶解し、該有機溶剤溶
液を水中で乳化分散後、有機溶剤を実質的に除去し、感
光性塗布液を製造する方法も使用できる。Alternatively, the method described in JP-A No. 60-208750, that is, the photosensitive composition is dissolved in an organic solvent, the organic solvent solution is emulsified and dispersed in water, the organic solvent is substantially removed, and the photosensitive coating is applied. Methods for producing liquids can also be used.
塗布方法は、従来公知の方法を用いることができる。As the coating method, a conventionally known method can be used.
本発明の感光性組成物を用いた感光性層を設ける支持体
は、アルミニウム、亜鉛、鋼、銅等の金属板、並びにク
ロム、亜鉛、銅、ニッケル、アルミニウム、鉄等がメッ
キ又は蒸着された金属板、紙、プラスチックフィルム及
びガラス板、樹脂が塗布された紙、アルミニウム等の金
汎箔が張られた紙、親水化処理したプラスチックフィル
ム等が挙げられる。このうち好ましいのは親水化処理し
たアルミニウム板である。本発明の感光性平版印刷版の
支持体として砂目立て処理、陽極酸化処理および必要に
応じて封孔処理等の表面処理が施されているアルミニウ
ム板を用いることがより好ましい。The support provided with the photosensitive layer using the photosensitive composition of the present invention may be a metal plate made of aluminum, zinc, steel, copper, etc., or a support plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include metal plates, paper, plastic films, glass plates, paper coated with resin, paper coated with gold foil such as aluminum, and plastic films treated to make them hydrophilic. Among these, preferred is an aluminum plate treated to make it hydrophilic. As the support for the photosensitive lithographic printing plate of the present invention, it is more preferable to use an aluminum plate that has been subjected to surface treatments such as graining, anodizing, and, if necessary, sealing.
本発明において、活性光線とは、本発明の感光性組成物
の酸発生化合物が酸形成するに充分な光線であればいず
れの光線でもよく、上記の活性光線を得ることのできる
露光手段としては、従来慣用の露光焼付装置を用いるこ
とができ、例えば、超高圧水銀灯、メタルハライドラン
プ、キセノンランプ、タングステンランプ等の光源によ
り露光する装置、あるいはレーザービームにより走査露
光する装置等が適宜用いられてよい。露光量は０．１
ｍＪ〜２０００ ｍＪの範囲で適宜選ぶことができる。In the present invention, the active light rays may be any light rays sufficient to cause the acid-generating compound of the photosensitive composition of the present invention to form an acid. A conventional exposure and printing apparatus can be used, for example, an apparatus that uses a light source such as an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, or a tungsten lamp, or an apparatus that performs scanning exposure using a laser beam may be used as appropriate. . The exposure amount is 0.1
It can be appropriately selected within the range of mJ to 2000 mJ.
本発明の感光性平版印刷版は、前記した露光焼付は装置
を用いて露光焼付し、次いで現像液にて現像され、未露
光部分のみが支持体表面に残り、ポジーポジ型レリーフ
像ができる。The photosensitive lithographic printing plate of the present invention is exposed and baked using the above-mentioned exposure baking apparatus, and then developed with a developer, so that only the unexposed areas remain on the surface of the support, forming a positive-positive type relief image.
本発明の感光性平版印刷版の現像には水系アルカリ現像
液を好適に用いることができ、例えば、水酸化ナトリウ
ム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、
メタケイ酸ナトリウム、メタケイ酸カリウム、第ニリン
酸ナトリウム、第三リン酸ナトリウム等のアルカリ金属
塩の水溶液が挙げられる。Aqueous alkaline developers can be suitably used for developing the photosensitive lithographic printing plate of the present invention, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Examples include aqueous solutions of alkali metal salts such as sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate.
［発明の効果］
本発明は、新規な酸分解化合物を含有することにより、
耐処理薬品性および耐刷性に著しく優れた感光性平版印
刷版、およびそれに用いる感光性組成物を得るという画
期的なものである。[Effect of the invention] By containing a novel acid-decomposed compound, the present invention has the following effects:
This is an epoch-making method in that it provides a photosensitive lithographic printing plate with extremely excellent processing chemical resistance and printing durability, and a photosensitive composition used therein.
［実施例］
以下、本発明の具体的実施例について詳）ホするが、本
発明の態様はこれらに限定されない。[Examples] Specific examples of the present invention will be detailed below, but the embodiments of the present invention are not limited thereto.
合成例１（例示化合物Ｎ０１１の合成）イソブチルアル
デヒドジエチルアセタール（東京化成工業（株）製）
１４．６（Ｊ （０，１モル）、ｐ−クレゾール（東
京化成工業（株）製） ２１．６ｇ（０，２モル）及び
ｐ−トルエンスルホンｌ ０．０２Ｑを窒素雰囲気下、
攪拌しながら１００℃′で１時間反応させ、その後１３
０℃まで徐々に温度を上げ、更に１３０℃で３時間反応
させた。反応により生成するエタノールはこの間に留去
される。冷却後、テトラヒドロフラン２００ｍ＋２及び
無水炭酸カリウム０、１ｉＪを加えて攪拌し、濾過した
。濾液から溶媒を減圧留去し、更に１３０℃減圧下に低
沸点成分を留去し、生成物を得た。ＩＲ，ＮＭＲ１元素
分析によりその構造が例示化合物Ｎｏ、１であることを
確認した。Synthesis Example 1 (Synthesis of Exemplary Compound N011) Isobutyraldehyde diethyl acetal (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
14.6 (J (0.1 mol)), 21.6 g (0.2 mol) of p-cresol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.02 Q of p-toluenesulfone under a nitrogen atmosphere.
React at 100°C for 1 hour with stirring, then 13
The temperature was gradually raised to 0°C, and the reaction was further carried out at 130°C for 3 hours. Ethanol produced by the reaction is distilled off during this time. After cooling, 200 m+2 of tetrahydrofuran and 0.1 iJ of anhydrous potassium carbonate were added, stirred, and filtered. The solvent was distilled off from the filtrate under reduced pressure, and low-boiling components were further distilled off under reduced pressure at 130°C to obtain a product. The structure was confirmed to be Exemplified Compound No. 1 by IR and NMR elemental analysis.
合成例２（例示化合物ＮＯ１２の合成）０−カプロンア
ルデヒドジエチルアセタール１ｙ．４ｇ （ ０．１
モル）、ｐ−クレゾール２１．６（１（０．２モル）を
合成例１と同様に反応させ生成物を得た。１．Ｒ． 、
ＮＭＲ，元素分析によりその構造が例示化合物Ｎ ｏ．
２であることを確認した。Synthesis Example 2 (Synthesis of Exemplified Compound NO12) 0-Capronaldehyde diethylacetal 1y. 4g (0.1
mol), p-cresol 21.6 (1 (0.2 mol)) was reacted in the same manner as in Synthesis Example 1 to obtain a product. 1.R.
According to NMR and elemental analysis, its structure was found to be that of Exemplified Compound No.
It was confirmed that it was 2.
合成例３（例示化合物Ｎ０．１２の合成）ベンズアルデ
ヒドジメチルアセタール１５．２ｇ（０．１モル）、ビ
スフェノールＡ（東京化成工業（株）製） ２２．８ｇ
（ ０．１モル）を合成例１と同様に反応させ生
成物を得た。Ｇ．Ｐ．Ｃ．により分子量を測定したとこ
ろ、重量平均分子ｆｆｉＭＷ ＝１、７００， Ｍｗ
／Ｍｎ ＝ ２．９であった。Synthesis Example 3 (Synthesis of Exemplary Compound No. 12) 15.2 g (0.1 mol) of benzaldehyde dimethyl acetal, 22.8 g of bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.)
(0.1 mol) was reacted in the same manner as in Synthesis Example 1 to obtain a product. G. P. C. When the molecular weight was measured, the weight average molecular weight ffiMW = 1,700, Mw
/Mn = 2.9.
合成例４（例示化合物Ｎｏ．１４の合成）ベンズアルデ
ヒドジメチルアセタール１５．２ｇ（０．１モル）、メ
トキシハイドロキノン１４．０（］（００．１モルを合
成例１と同様に反応させ、生成物を得た。Ｇ．Ｐ．Ｃ．
により分子量を測定したところＭＷ − １，４００、
Ｍｗ ／Ｍｎ − ４．０であった。Synthesis Example 4 (Synthesis of Exemplified Compound No. 14) 15.2 g (0.1 mol) of benzaldehyde dimethyl acetal and 14.0 (00.1 mol) of methoxyhydroquinone were reacted in the same manner as in Synthesis Example 1, and the product was Obtained.G.P.C.
When the molecular weight was measured by MW-1,400,
Mw/Mn-4.0.
実施例１
［感光性平版印刷版試料の作成］
厚さ０．２４ｎｏｎのアルミニウム板（材質１０５０、
調質Ｈ１６）を５％苛性ソーダ水溶液中で６０℃で１分
間脱脂処理を行った後、０．５モル１ｙの塩酸水溶液中
で温度；２５℃、電流密度；６０Ａ／ｄ１２、処理時間
；３０秒間の条件で電解エツチング処理を行った。次い
で、５％苛性ソーダ水澄液中で６０℃、１０秒間のデス
マット処理を施した後、２０％硫酸溶液中で温度：２０
”Ｃ、電流密度：３Ａ／ｄ１＝、処理時間：１分間の条
件で陽極酸化処理を行った。更に又、３０℃の熱水で２
０秒間、熱水封孔処理を行い、平版印刷版材料用支持体
のアルミニウム板を作製した。Example 1 [Preparation of photosensitive lithographic printing plate sample] An aluminum plate with a thickness of 0.24 non (material: 1050,
After degreasing H16) in a 5% caustic soda aqueous solution at 60°C for 1 minute, it was degreased in a 0.5 mol 1y hydrochloric acid aqueous solution at a temperature of 25°C, a current density of 60 A/d12, and a treatment time of 30 seconds. Electrolytic etching treatment was performed under the following conditions. Next, after desmutting in a 5% caustic soda aqueous solution at 60°C for 10 seconds, desmutting was performed in a 20% sulfuric acid solution at a temperature of 20°C.
"C, anodization treatment was performed under the conditions of current density: 3A/d1 = treatment time: 1 minute.Furthermore, 2
Hot water sealing treatment was performed for 0 seconds to produce an aluminum plate as a support for lithographic printing plate material.
次にこのアルミニウム板に下記組成の感光性組成物塗布
液を回転塗布機を用いて塗布し、９０℃で４分間乾燥し
、ポジ型感光性平版印刷版試料を得た。Next, a photosensitive composition coating solution having the following composition was applied to this aluminum plate using a rotary coater and dried at 90° C. for 4 minutes to obtain a positive-working photosensitive lithographic printing plate sample.
（感光性組成物塗布液組成）
・合成例３により得た化合物ＮＯ，１２２，１４ｇ・ｍ
−クレゾールとｐ−クレゾール
とホルムアルデヒドの共重縮合樹脂
（Ｉｌｌ−クレゾール及びｐ−クレゾールの各々のモル
比が６：４．１ｆｆｉ平均分子伍１ｙ１ｗ−１０，００
０、分散度ＭＷ ／Ｍｎ ＝ ６．７、Ｍｎ ；数平均
分子量）’ ５．７４ｇ・ビクト
リアピュアブルーＢＯＨ
（採土ケ谷化学〈株）製） ０．０５（］
・］２−トリクロロメチルー５−β−
（２−ベンゾフリル）ビニル］１゜
３．４−オキサジアゾール［特開昭
６０−１３８５３９号公報に記載の例示化合物（１）］
０．２７Ｑ・エチルセロソル
ブ １００１ｇかくして得られた感
光性平版印刷版にステップタブレット（イーストマン・
コダック社製Ｎ ｏ、 ２、濃度差０．１５ずつで２１
段階のグレースケール）、及び絵柄の入ったポジ型フィ
ルムを害着して、４ＫＷメタルハライドランプを光源と
して１ｍの距離から露光を行い、その後５ＤＲ−１（小
西六写真工業（株）製）の８倍希釈水溶液で現像を行い
、前記ステップタブレットの５段目が完全に現像された
平版印刷版を得た。(Photosensitive composition coating liquid composition) Compound NO, 122, 14 g m obtained in Synthesis Example 3
- Copolycondensation resin of cresol, p-cresol and formaldehyde (molar ratio of each of Ill-cresol and p-cresol is 6:4.1ffi, average molecular weight 1y1w-10,00
0, dispersity MW /Mn = 6.7, Mn; number average molecular weight)' 5.74g Victoria Pure Blue BOH (manufactured by Odugaya Chemical Co., Ltd.) 0.05 (]
・]2-Trichloromethyl-5-β-(2-benzofuryl)vinyl]1゜3.4-oxadiazole [Exemplary compound (1) described in JP-A-60-138539]
0.27Q Ethyl Cellosolve 1001g Step tablets (Eastman
Kodak No. 2, 21 with a concentration difference of 0.15 each
A positive film with a pattern (gray scale) and a pattern was attached and exposed from a distance of 1 m using a 4KW metal halide lamp as a light source. Development was performed with a twice diluted aqueous solution to obtain a lithographic printing plate in which the fifth stage of the step tablet was completely developed.
このようにして得られた平版印刷版を用いて５万枚の印
刷を行ったところ、画線部のハイライト部分の網点が消
失することもなく、鮮明な印刷物を得ることができた。When 50,000 sheets were printed using the lithographic printing plate thus obtained, clear printed matter could be obtained without any disappearance of the halftone dots in the highlighted areas of the image area.
実施例２
例示化合物Ｎｏ、１４の合成（合成例４）により得た化
合物を使用して実施例１と同様に感光性組成物塗布液を
作製し、また感光性平版印刷版を作製して製版し、現像
された平版印刷版を得た。Example 2 A photosensitive composition coating solution was prepared in the same manner as in Example 1 using the compound obtained by the synthesis of Exemplified Compound No. 14 (Synthesis Example 4), and a photosensitive lithographic printing plate was also prepared. A developed planographic printing plate was obtained.
このようにして得られた平版印刷版を用いて実施例１と
同様に５万枚の印刷を行ったところ実施例１と同様鮮明
な印刷物を得ることができた。Using the lithographic printing plate thus obtained, 50,000 sheets were printed in the same manner as in Example 1, and as in Example 1, clear printed matter could be obtained.
比較例１
酸分解化合物として、下記構造単位を有する化合物
（比較化合物）
（特開昭５３ｉ３３４２９＠公報に記載の方法により合
成したもの）を用いて塗布液を調製し、平版印刷版とし
て実施例１と同様に作製して、印刷を行ったとこる約３
０，０００枚印刷した所で印刷物のベタ部に着肉不良が
生じ、さらに平網にもかすれが生じ良好な印刷物を得る
ことができなかった。Comparative Example 1 A coating solution was prepared using a compound (comparative compound) having the following structural unit as an acid-decomposed compound (synthesized by the method described in JP-A-53-33429@publication), and a lithographic printing plate was prepared in Example 1. Approximately 3 images were created and printed in the same manner as above.
After printing 0,000 sheets, poor inking occurred in the solid areas of the printed matter, and the flat screen also became blurred, making it impossible to obtain good printed matter.
Claims (2)
よび酸により分解し得る少なくとも１つのアセタール部
分を有する化合物を含有する感光性組成物において、前
記アセタール部分を形成する各ＯＨ基がフェノール性Ｏ
Ｈ基であることを特徴とする感光性組成物。(1) In a photosensitive composition containing a compound capable of generating an acid upon irradiation with actinic rays and a compound having at least one acetal moiety capable of being decomposed by an acid, each OH group forming the acetal moiety is phenolic. O
A photosensitive composition characterized by having an H group.
る化合物、および酸により分解し得る少なくとも１つの
アセタール部分を有する化合物を含有する感光性組成物
から形成される感光性層を有する感光性平版印刷版にお
いて、前記アセタール部分を形成する各ＯＨ基がフェノ
ール性ＯＨ基であることを特徴とする感光性平版印刷版
。(2) Having a photosensitive layer formed from a photosensitive composition containing a compound capable of generating an acid upon irradiation with actinic rays and a compound having at least one acetal moiety capable of being decomposed by an acid on a support. A photosensitive planographic printing plate, wherein each OH group forming the acetal moiety is a phenolic OH group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24386286A JPS6397945A (en) | 1986-10-14 | 1986-10-14 | Photosensitive composition and photosensitive lithographic printing plate containing novel acid decomposable compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24386286A JPS6397945A (en) | 1986-10-14 | 1986-10-14 | Photosensitive composition and photosensitive lithographic printing plate containing novel acid decomposable compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6397945A true JPS6397945A (en) | 1988-04-28 |
Family
ID=17110074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24386286A Pending JPS6397945A (en) | 1986-10-14 | 1986-10-14 | Photosensitive composition and photosensitive lithographic printing plate containing novel acid decomposable compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6397945A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01106041A (en) * | 1987-09-13 | 1989-04-24 | Hoechst Ag | Positive type radiosensitive mixture and positive type radiosensitive recording material and making thereof |
| JPH01106040A (en) * | 1987-09-13 | 1989-04-24 | Hoechst Ag | Positive type radiosensitive mixture and positive type radiosensitive recording material and manufacture of said recording material |
| US6828078B2 (en) | 2000-08-29 | 2004-12-07 | Jsr Corporation | Composition having refractive index sensitively changeable by radiation and method for forming refractive index pattern |
| US7071255B2 (en) | 2001-02-19 | 2006-07-04 | Jsr Corporation | Radiation-sensitive composition capable of having refractive index distribution |
| US7108954B2 (en) | 2000-12-11 | 2006-09-19 | Jsr Corporation | Radiation-sensitive composition changing in refractive index and method of changing refractive index |
| US7125647B2 (en) | 2001-03-13 | 2006-10-24 | Jsr Corporation | Radiation-sensitive composition changing in refractive index and utilization thereof |
| US7205085B2 (en) | 2001-08-01 | 2007-04-17 | Jsr Corporation | Composition having permitivity being radiation-sensitively changeable and method for forming permitivity pattern |
-
1986
- 1986-10-14 JP JP24386286A patent/JPS6397945A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01106041A (en) * | 1987-09-13 | 1989-04-24 | Hoechst Ag | Positive type radiosensitive mixture and positive type radiosensitive recording material and making thereof |
| JPH01106040A (en) * | 1987-09-13 | 1989-04-24 | Hoechst Ag | Positive type radiosensitive mixture and positive type radiosensitive recording material and manufacture of said recording material |
| US6828078B2 (en) | 2000-08-29 | 2004-12-07 | Jsr Corporation | Composition having refractive index sensitively changeable by radiation and method for forming refractive index pattern |
| US7108954B2 (en) | 2000-12-11 | 2006-09-19 | Jsr Corporation | Radiation-sensitive composition changing in refractive index and method of changing refractive index |
| US7071255B2 (en) | 2001-02-19 | 2006-07-04 | Jsr Corporation | Radiation-sensitive composition capable of having refractive index distribution |
| US7125647B2 (en) | 2001-03-13 | 2006-10-24 | Jsr Corporation | Radiation-sensitive composition changing in refractive index and utilization thereof |
| US7205085B2 (en) | 2001-08-01 | 2007-04-17 | Jsr Corporation | Composition having permitivity being radiation-sensitively changeable and method for forming permitivity pattern |
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