JPS6123547B2 - - Google Patents
Info
- Publication number
- JPS6123547B2 JPS6123547B2 JP8078582A JP8078582A JPS6123547B2 JP S6123547 B2 JPS6123547 B2 JP S6123547B2 JP 8078582 A JP8078582 A JP 8078582A JP 8078582 A JP8078582 A JP 8078582A JP S6123547 B2 JPS6123547 B2 JP S6123547B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- gelatin
- printing
- silver
- fine powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000007639 printing Methods 0.000 claims description 60
- 229910052709 silver Inorganic materials 0.000 claims description 31
- 239000004332 silver Substances 0.000 claims description 31
- -1 silver halide Chemical class 0.000 claims description 30
- 239000000839 emulsion Substances 0.000 claims description 27
- 108010010803 Gelatin Proteins 0.000 claims description 26
- 229920000159 gelatin Polymers 0.000 claims description 26
- 239000008273 gelatin Substances 0.000 claims description 26
- 235000019322 gelatine Nutrition 0.000 claims description 26
- 235000011852 gelatine desserts Nutrition 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000011161 development Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 description 65
- 239000007788 liquid Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical class N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 3
- AJKLCDRWGVLVSH-UHFFFAOYSA-N 4,4-bis(hydroxymethyl)-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(CO)(CO)CN1C1=CC=CC=C1 AJKLCDRWGVLVSH-UHFFFAOYSA-N 0.000 description 2
- ZZEYCGJAYIHIAZ-UHFFFAOYSA-N 4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)CN1C1=CC=CC=C1 ZZEYCGJAYIHIAZ-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- KQGGODSZBZTAQX-UHFFFAOYSA-N 1-(2-chlorophenyl)-4-ethyl-4-methylpyrazolidin-3-one Chemical compound N1C(=O)C(CC)(C)CN1C1=CC=CC=C1Cl KQGGODSZBZTAQX-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- SJSJAWHHGDPBOC-UHFFFAOYSA-N 4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=CC=C1 SJSJAWHHGDPBOC-UHFFFAOYSA-N 0.000 description 1
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 1
- QTXSDPJOPCWEME-UHFFFAOYSA-N 4-amino-2-sulfanylbenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(S)=C1 QTXSDPJOPCWEME-UHFFFAOYSA-N 0.000 description 1
- BEUWBSAVSYYTEI-UHFFFAOYSA-N 5,5-dimethylpyrazolidin-3-one Chemical compound CC1(C)CC(=O)NN1 BEUWBSAVSYYTEI-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- KGIWBAWUVJNZQH-UHFFFAOYSA-N n-(3-heptyl-5-sulfanylidene-1h-1,2,4-triazol-4-yl)acetamide Chemical compound CCCCCCCC1=NNC(=S)N1NC(C)=O KGIWBAWUVJNZQH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011101 paper laminate Substances 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
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin 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
- G03F7/06—Silver salts
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
本発明は、銀錯塩拡散転写法を応用する平版印
刷材料に関する。
平版印刷版は、油脂性のインキを受理する親油
性の画線部分と、インキを受理しない撥油性の非
画線部分とからなり、一般に該非画線部は水を受
付ける親水性部分から構成されている。
通常の平版印刷では、従つて、水とインキの両
方を版面に供給し、画線部は着色性のインキを、
非画線部は水を選択的に受入れ、該画線上のイン
キを例えば紙などの基質に転写させることによつ
てなされている。
したがつて、良い印刷物を得るためには、画線
部と背景非画線部の表面の親油および親水性の差
が十分に大きくて、水およびインキを適用したと
きに、画線部は十分量のインキを受付け非画線部
は全くインキを受け付けないことが必要である。
銀錯塩拡散転写法（DTR法）によつて作られ
た平版印刷版に伴われる欠点は、例えば機械的摩
耗に対する抵抗性が不十分で、インキ像を担持す
る疎水性部域が欠落したり、或いは徐々にそのイ
ンキ受容性を失わしめるため、耐刷力を低下する
ことである。更に親水性部域が徐々に疎水性にな
り、従つて非画線部域または地部域がインキで汚
れるようになる。更に疎水性像部域における均一
脂性インキ受理性に欠陥を生じ、これが上記像部
域にインキ受理性の変動を生ぜしめ、従つて印刷
される部域が均一量のインキを受け入れられない
ようになる。
DTR法を応用し、形成された金属銀模様をイ
ンキ受理性として利用する印刷版が既に知られ
（例えば、米国特許第3220837号、同第3721559
号、特公昭48−16725、同昭48−30562、特開昭46
−4432、同昭53−21602等）、いくつかは現実化さ
れているけれども、上記の欠点を依然として有し
ている。
その他の平版印刷版でもそうであるように、
DTR法を応用した平版印刷版においても、版材
の構成・処理液の構成あるいは印刷条件等により
耐刷力を増強せしめることが要求され、これまで
に多くの試みが提案されてきた。
支持体上に順に下塗層、ハロゲン化銀乳剤層、
物理現像核層を設けた平版印刷版は、特公昭48−
30562、特開昭49−55402、同昭53−21602等に記
載されており、このものは、物理現像核粒子が埋
没することなく、少なくとも一部が表面に露出し
た構造から成り、転写現像された銀粒子は、酸化
処理を施こさなくても、直接インキ受理性とする
ことができる特徴を有しているものである。特に
そのような印刷版では、転写銀粒子が良好なイン
キ受理性を持つようにすることはもちろん、細線
部の転写銀もが印刷中にとれたりしないことが耐
刷力を決める重要な一要因である。
また、既述したように耐刷力は、非画像部域の
親水性低下によるインキ汚れによつても低下す
る、従つて、画像の飛びや地汚れがなく、長い印
刷に耐える平版印刷版でなければならないことは
当然である。そして、親油性と親水性の両方を同
時に、長い印刷の間、満足しうるレベルに維持す
ることは、一般に相反する性質だけに困難ではあ
るが、より耐刷力の改良された平版印刷版の開発
が望まれている。
ところで、一般的はDTR法を実施するに当つ
ては、現像主薬を材料中に混入する方法が広く知
られており、従つてこのような材料においては、
現像段階で使用される処理液は、現像主薬を実質
的に含まぬ所謂「アルカリ性活性化液」を使用す
ることができ、このアルカリ性活性化液は、空気
酸化による疲労が極めて小さいという利点を有し
ている。
現像主薬は、通常、ハロゲン化銀乳剤層および
それに隣接する水透過性層、例えば下塗層、保護
層等、あるいは受像層のいずれにも混入すること
ができ、その層は２つ以上の層であつてもよい。
しかし、現像主薬をゼラチン含有量に含む場合
には、ゼラチンの物性劣化に起因すると考えられ
る耐刷力の低下の問題がある。
本発明の目的は、アルカリ性活性化液での処理
に適した、耐刷力の改良された平版印刷版を提供
することである。
本発明の目的は、支持体上に順に、下塗層、ハ
ロゲン化銀乳剤層および物理現像核層を少なくと
も有する平版印刷版において、少なくとも１つの
ゼラチン含有量に現像主薬を含み、さらに少なく
とも前記下塗層には平均粒子２〜10μｍの微粉末
を含み、かつ該下塗層の微粉末の親水性コロイド
に対する含有割合は、全層中で最も高いものであ
ることを特徴とする平版印刷版とすることによつ
て達成された。
特開昭49−55402には、ハロゲン化銀乳剤層に
平均粒子２〜10μ微粉末を含むことによつて保水
性を向上し、インキ汚れを防止することが記載さ
れている。特開昭55−100554には、下塗層につい
て同様なことが記載されている。確かに、この微
粉末は、インキ汚れ防止に対して有効である。特
に、ハロゲン化銀乳剤層での微粉末は、印刷表面
での保水性に関して重要と考えられてきたもので
あり、多くの特許明細書に記載されている。しか
し、本発明の重要な特徴は、微粉末を最下層であ
る下塗層で主体的に使用すべきであるということ
である。
これは、下塗層、乳剤層などの少なくとも１つ
のゼラチン含有量に現像主薬を含むことによつ
て、物性が劣化し、微粉末の乳剤層表面での分散
状態あるいは微粉末に保持性に対して微妙な影響
を与えているものと考えられる。微粉末は乳剤層
の表面状態を変化させ、いわゆる砂目立て効果に
より印刷層表面の保水性を向上するものである
が、その表面状態は、乳剤層での微粉末の適用条
件によつて実に微妙な影響を受けるものであるこ
とが経験上知られている。しかし、微粉末をゼラ
チン下塗層に高含有割合で含有せしめた方が乳剤
層表面状態をより保水性の良いものにすると共に
現像主薬を含むゼラチン含有層の機械的抵抗力を
も強め、より耐刷力の改良された平版印刷版とな
ることは予想外のことであつた。即ち、下塗層の
微粉末は、印刷層表面のより良好な保水性向上だ
けでなく、転写銀の印刷中における飛びを防止
し、さらに最下層にあつて、現像主薬を含むゼラ
チン含有層の機械的抵抗力を強める効果が総合さ
れて耐刷力の優れた平版印刷版を得ることができ
たものと考えられる。
本発明のより改良された態様は、ゼラチン含有
層のすべてをそのゼラチンの等電点未満のPH値と
する平版印刷版である。ホルマリンを含む下塗層
さらにはハロゲン化銀乳剤層を塗設した後、40℃
で３日間の加温により硬化することは公知であ
る。一般的には、そのような短期間でも上記平版
印刷版に必要な硬化レベルを得ることはできる。
しかし、ゼラチン含有量のすべてをそのゼラチン
の等電点未満のPH値にした本発明のより改良され
た態様において、上記加温の日数を長くすること
によつて必要な硬化レベルとした場合に、少なく
とも１つのゼラチン含有層のPH値を等電点以上に
した場合に比べて、より好ましい結果を与えるこ
とができる。
本発明に用いられる現像主薬は、ジヒドロキシ
ベンゼン化合物、１−フエニル−３−ピラゾリド
ン化合物から選択される少なくとも１つであるこ
とが好ましい。
Ｐ−ジヒドロキシベンゼン化合物と１−フエニ
ル−３−ピラゾリドン化合物を組合わせて用いる
ことが好ましく、いずれか一方はゼラチン非含有
層に含まれることも、あるいは２層以上のゼラチ
ン含有層に含むこともできる。
ハイドロキノン、メチルハイドロキノン、クロ
ルハイドロキノン等のＰ−ジヒドロキシベンゼン
化合物は１平方メートル当り約0.3〜約３グラム
の範囲で用いることができる。１−フエニル−３
−ピラゾリドン化合物は、１平方メートル当り約
0.01〜約１グラムの範囲で用いることができる。
好ましく用いることができる１−フエニル−３−
ピラゾリドンは、１−フエニル−３−ピラゾリド
ン、１−フエニル−４−メチル−３−ピラゾリド
ン、１−フエニル４・４−ジヒドロキシメチル−
３−ピラゾリドン、１−フエニル−４−ヒドロキ
シメチル−４−メチル−３−ピラゾリドン、１−
フエニル−４・４−ジメチル−３−ピラゾリド
ン、１−（２−クロロフエニル）−４−メチル−４
−エチル−３−ピラゾリドン、１−フエニル−
５・５−ジメチル−３−ピラゾリドンなどを包含
する。
本発明に用いられるハロゲン化銀乳剤は、塩化
銀、臭化銀、塩臭化銀およびそれらと沃化銀から
なるハロゲン化銀のいずれでも使用することがで
き、特に好ましくは塩化銀が約50モル％以上のハ
ロゲン化銀である、ハロゲン化銀粒子の大きさ、
晶癖、分布などは制限されるものではなく、また
ハロゲン化銀乳剤の製法も通常の写真分野で知ら
れている任意の方法が採用しうる。ハロゲン化銀
乳剤は、よく知られている化学増感法で増感する
ことができ、青、緑、赤のスペクトル増感するこ
とができる。その他、カブリ防止剤、安定剤、錯
化剤、硬膜剤、なども適宜添加しうる。ハロゲン
化銀乳剤の結合剤はゼラチンの一部を他の天然お
よび／または合成親水性コロイド、例えばアルブ
ミン、カゼイン、ポリビニルアルコール、アルギ
ン酸ナトリウム、カルボキシメチルセルロースの
ナトリウム塩などで置換されていてもよい。
硝酸銀として表わしたハロゲン化銀に対する親
水性コロイドの重量比は、一般に３〜0.2、好ま
しくは1.5〜0.3である。支持体上に存在させるハ
ロゲン化銀の量は約0.2〜約５ｇ/m2、好ましくは
0.5〜３ｇ/m2の硝酸銀に等しくなるように被覆す
る。
ゼラチン下塗層は、ゼラチン単独でもよいが例
えば特開昭55−100554に記載の如き親水性コロイ
ドやアルギン酸ナトリウム、繊維素誘導体、ポリ
ビニルアルコール、ポリビニルピロリドンなどの
親水性コロイドを組合せて用いることができる。
ゼラチンの等電点未満のPH値に調整する酸とし
ては、硫酸、クエン酸などの無機および有機の任
意の酸を用いることができる。ゼラチン層の硬化
剤としては、ホルマリン、ムコクロル酸グルター
ルアルデヒド、グリオキザール、特開昭54−
130930に記載の如き初期縮合物、活性ハロゲン
型、エチレンイミン型、ビニルスルホン型、エポ
キシ型あるいはクロム塩のような公知のものが使
用できる。
平均粒径２〜10μｍの微粉末としては、シリ
カ、クレー、タルク、ジークライト、米でんぷん
などが挙げられ、特に好ましくは平均粒径４〜10
μｍのシリカ粒子である。
また、２μｍ以下の微粒子を組合わすこともで
きる。
平均粒径２〜10μｍの微粉末の使用量は、下塗
層には、親水性コロイド100重量に対して５〜40
重量部程度である。ハロゲン化銀乳剤に含む場合
には、親水性コロイド100重量部に対して１〜20
重量部程度であり、下塗層に用いた微粉末の割合
よりも少なく用いる。一般的には、親水性コイド
に対する割合として、1/2〜1/10を目安にするこ
とができる。
物理現像核としては、アンチモン、ビスマス、
カドミウム、コバルト、パラジウム、ニツケル、
銀、鉛、亜鉛などの金属およびそれらの硬化物な
ど公知のものが使用しうる。受像層には、親水性
コロイドを含んでいなくてもよく、ゼラチン、カ
ルボキシメチルセルロース、アラビアゴム、アル
ギン酸ナトリウム、ヒドロキシエチル澱粉、デキ
ストリン、ヒドロキシエチルセルロース、ポリス
チレンスルホン酸、ビニルイミダゾールとアクリ
ルアミドの共重合体、ポリビニルアルコール等の
親水性コロイドを含むこともできる。
受像層中には、吸湿性物質、例えばソルビトー
ル、グリセロールなどの湿潤剤を存在させてもよ
い。さらに受像層中には、硫酸バリウム、二酸化
チタン、チヤイナクレーおよび銀などのスカミン
グ防止のための顔料、ハイドロキノンの如き現像
主薬およびホルムアルデヒドの如き硬化剤も含有
しうる。
支持体は、例えば紙、フイルム、例えば酢酸セ
ルロースフイルム、ポリビニルアセタールフイル
ム、ポリスチレンフイルム、ポリプロピレンフイ
ルム、ポリエチレンテレフタレートフイルム、あ
るいはポリエステル、ポリプロピレンまたはポリ
スチレンフイルム等をポリエチレンフイルムで被
覆した複合フイルム、金属、金属化紙または金
属／紙積層体の支持体であることができる。片面
または両面をα−オレフイン重合体、例えばポリ
エチレンで被覆した紙支持体も有効である。これ
ら支持体には、ハレーシヨン防止染料または顔料
を混入していてもよい。
本発明で使用するDTR処理液にはアルカリ性
物質、例えば水酸化ナトリウム、水酸化カリウ
ム、水酸化リチウム、第三燐酸ナトリウム等の保
恒剤としての亜硫酸塩、ハロゲン化銀溶剤、例え
ばチオ硫酸塩、チオシアン酸塩、環状イミド、チ
オサリチル酸、アミン等、粘稠剤、例えばヒドロ
キシエチルセルロース、カルボキシメチルセルロ
ース、かぶり防止剤、例えば臭化カリウム、１−
フエニル−５−メルカプトテトラゾール、特開昭
47−26201に記載の化合物、現像変性剤、例えば
ポリオキシアルキレン化合物、オニウム化合物等
を含むことができる。必要に応じて、現像主薬を
含んでいてもよい。
本発明の平版印刷板は、例えば特公昭48−
29723、米国特許第3721559号明細書に記載されて
いる如き化合物でインキ受理性に変換ないしは増
強しうる。印刷方法あるいは使用する不感脂化
液、給湿液などは普通によく知られた方法による
ことができる。
以下に本発明を実施例により説明するが、勿
論、これだけに限定されるものではない。
実施例 １
135ｇ/m2の両面ポリエチレン被覆紙の片面に平
均粒子サイズ５μのシリカ粒子を含有するマツト
化層を設け、反対側の面をコロナ放電加工後、カ
ーボンブラツク１−フエニル−３−ピラゾリドン
0.2ｇ/m2を含むハレーシヨン防止層（ゼラチン
3.5ｇ/m2）を設け、その上に平均粒子サイズが７
μのシリカ粒子および１−フエニル−３−ピラゾ
リドン0.1ｇ/m2を含有するオルソ増感された高感
度塩化銀乳剤（ゼラチン1.0ｇ/m2）を硝酸銀とし
て1.2ｇ/m2で塗布した。
このハレーシヨン防止層および乳剤層はPH4.2
に調整され、硬化剤としてホルマリンを含んでい
る。乾燥後40℃で10日間加湿した後、この乳剤層
の上に下記の方法により調製した硫化パラジウム
ゾルを５ｍ／分の速度で塗布した（比較Ａ）
硫化パラジウムゾルの調製
The present invention relates to a lithographic printing material to which a silver complex diffusion transfer method is applied. A lithographic printing plate consists of an oleophilic image area that accepts oil-based ink and an oil-repellent non-image area that does not accept ink, and the non-image area generally consists of a hydrophilic area that accepts water. ing. In normal planographic printing, both water and ink are supplied to the plate surface, and colored ink is applied to the printing area.
The non-image areas are created by selectively accepting water and transferring the ink on the image to a substrate such as paper. Therefore, in order to obtain good printed matter, the difference in lipophilicity and hydrophilicity between the surface of the printed area and the background non-printed area must be sufficiently large so that when water and ink are applied, the printed area is It is necessary that a sufficient amount of ink be received and that the non-image areas receive no ink at all. Disadvantages associated with lithographic printing plates made by the silver complex diffusion transfer method (DTR method) include, for example, insufficient resistance to mechanical abrasion, lack of hydrophobic areas that carry the ink image, and Alternatively, it gradually loses its ink receptivity, resulting in a decrease in printing durability. Furthermore, the hydrophilic areas gradually become hydrophobic, so that the non-imaged areas or areas become smeared with ink. Furthermore, the uniform greasy ink receptivity in the hydrophobic image areas is compromised, which causes variations in the ink receptivity in said image areas, so that the areas to be printed do not receive a uniform amount of ink. Become. Printing plates that apply the DTR method and use the formed metallic silver pattern as ink receptivity are already known (for example, U.S. Pat. No. 3,220,837, U.S. Pat. No. 3,721,559).
No., 1972-16725, 30562, 1972, 1973
-4432, 1983-21602, etc.), although some of them have been realized, they still have the above-mentioned drawbacks. As with other lithographic printing plates,
Even in lithographic printing plates to which the DTR method is applied, it is required to increase the printing durability by changing the composition of the plate material, the composition of the processing liquid, printing conditions, etc., and many attempts have been proposed so far. A subbing layer, a silver halide emulsion layer, and a silver halide emulsion layer are formed on the support in this order.
A lithographic printing plate with a physical development nucleus layer was published in 1973.
30562, JP-A No. 49-55402, JP-A No. 53-21602, etc., this product has a structure in which the physical development nuclear particles are not buried and at least a portion is exposed on the surface, and is transfer-developed. The silver particles have a characteristic that they can be made directly ink receptive without being subjected to oxidation treatment. Particularly in such printing plates, one of the important factors that determines printing durability is not only to ensure that the transferred silver particles have good ink receptivity, but also to ensure that the transferred silver in the fine line areas does not come off during printing. It is. In addition, as mentioned above, printing durability also decreases due to ink stains due to decreased hydrophilicity in non-image areas.Therefore, it is possible to use a lithographic printing plate that can withstand long printing without image skipping or background smearing. Of course it has to be done. Although it is generally difficult to maintain both lipophilicity and hydrophilicity at a satisfactory level during long printing periods due to their contradictory properties, it is difficult to maintain both lipophilicity and hydrophilicity at a satisfactory level during long printing periods. Development is desired. By the way, when carrying out the DTR method, it is generally known that a developing agent is mixed into the material, and therefore, for such materials,
The processing solution used in the development stage can be a so-called "alkaline activating solution" that does not substantially contain a developing agent, and this alkaline activating solution has the advantage of extremely little fatigue caused by air oxidation. are doing. The developing agent can usually be incorporated into either the silver halide emulsion layer and the adjacent water-permeable layer, such as a subbing layer, a protective layer, etc., or an image-receiving layer, and the layer is composed of two or more layers. It may be. However, when a developing agent is included in the gelatin content, there is a problem of a decrease in printing durability, which is thought to be caused by deterioration of the physical properties of gelatin. An object of the present invention is to provide a lithographic printing plate with improved printing durability that is suitable for treatment with an alkaline activating liquid. The object of the present invention is to provide a lithographic printing plate having at least a subbing layer, a silver halide emulsion layer and a physical development nucleus layer on a support, in which at least one gelatin content contains a developing agent, and further comprises a developing agent in the gelatin content of at least one of the subbing layers, a silver halide emulsion layer and a physical development nucleus layer. A lithographic printing plate characterized in that the coating layer contains fine powder with an average particle size of 2 to 10 μm, and the content ratio of the fine powder to hydrophilic colloid in the undercoat layer is the highest among all the layers. was achieved by. JP-A-49-55402 describes that water retention is improved and ink stains are prevented by including fine powder with an average grain size of 2 to 10 μm in a silver halide emulsion layer. JP-A-55-100554 describes a similar matter regarding the undercoat layer. Indeed, this fine powder is effective in preventing ink stains. In particular, fine powder in the silver halide emulsion layer has been considered important in terms of water retention on the printing surface and is described in many patent specifications. However, an important feature of the present invention is that the fine powder should be used predominantly in the bottom layer, the subbing layer. This is because the inclusion of a developing agent in at least one gelatin content in the undercoat layer, emulsion layer, etc. deteriorates the physical properties and affects the dispersion state of the fine powder on the surface of the emulsion layer or the retention of the fine powder. It is thought that this has a subtle influence. The fine powder changes the surface condition of the emulsion layer and improves the water retention properties of the surface of the printing layer through the so-called graining effect, but the surface condition is very delicate depending on the application conditions of the fine powder in the emulsion layer. It is known from experience that the effects of However, it is better to include fine powder in a high proportion in the gelatin undercoat layer, as this will make the surface condition of the emulsion layer better in water retention, as well as strengthen the mechanical resistance of the gelatin-containing layer containing the developing agent. It was unexpected that a lithographic printing plate with improved printing durability could be obtained. In other words, the fine powder in the undercoat layer not only improves water retention on the surface of the printing layer, but also prevents transfer silver from flying off during printing, and further improves the gelatin-containing layer containing the developing agent, which is the lowest layer. It is thought that the combination of the effects of increasing mechanical resistance made it possible to obtain a lithographic printing plate with excellent printing durability. A more improved embodiment of the invention is a lithographic printing plate in which all of the gelatin-containing layers have a PH value below the isoelectric point of the gelatin. After coating the formalin-containing undercoat layer and silver halide emulsion layer,
It is known that the material is cured by heating for 3 days. Generally, it is possible to obtain the required level of curing for the lithographic printing plate in such a short period of time.
However, in an improved embodiment of the present invention in which all of the gelatin content has a PH value below the isoelectric point of the gelatin, the required hardening level is achieved by increasing the number of days of heating. , more preferable results can be provided than when the PH value of at least one gelatin-containing layer is set to be equal to or higher than the isoelectric point. The developing agent used in the present invention is preferably at least one selected from dihydroxybenzene compounds and 1-phenyl-3-pyrazolidone compounds. It is preferable to use a combination of a P-dihydroxybenzene compound and a 1-phenyl-3-pyrazolidone compound, and either one can be included in a gelatin-free layer or in two or more gelatin-containing layers. . P-dihydroxybenzene compounds such as hydroquinone, methylhydroquinone, chlorohydroquinone, etc. can be used in amounts ranging from about 0.3 to about 3 grams per square meter. 1-phenyl-3
- Pyrazolidone compounds are approximately
A range of 0.01 to about 1 gram can be used.
1-phenyl-3- which can be preferably used
Pyrazolidone is 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone, 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone, 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-(2-chlorophenyl)-4-methyl-4
-ethyl-3-pyrazolidone, 1-phenyl-
Includes 5,5-dimethyl-3-pyrazolidone and the like. The silver halide emulsion used in the present invention can be any of silver chloride, silver bromide, silver chlorobromide, and silver halides consisting of silver iodide and silver chloride. silver halide grain size, which is more than mol% silver halide;
There are no restrictions on crystal habit, distribution, etc., and any method known in the ordinary photographic field may be used for producing the silver halide emulsion. Silver halide emulsions can be sensitized by well-known chemical sensitization methods and can be spectrally sensitized in blue, green, and red. In addition, antifoggants, stabilizers, complexing agents, hardening agents, and the like may be added as appropriate. The binder of the silver halide emulsion may include replacing a portion of the gelatin with other natural and/or synthetic hydrophilic colloids, such as albumin, casein, polyvinyl alcohol, sodium alginate, sodium salt of carboxymethyl cellulose, and the like. The weight ratio of hydrophilic colloid to silver halide, expressed as silver nitrate, is generally from 3 to 0.2, preferably from 1.5 to 0.3. The amount of silver halide present on the support is from about 0.2 to about 5 g/m 2 , preferably
Coating equal to 0.5-3 g/m 2 silver nitrate. The gelatin undercoat layer may be made of gelatin alone, or may be used in combination with hydrophilic colloids such as those described in JP-A-55-100554, sodium alginate, cellulose derivatives, polyvinyl alcohol, and polyvinylpyrrolidone. . As the acid for adjusting the pH value below the isoelectric point of gelatin, any inorganic or organic acid such as sulfuric acid or citric acid can be used. Hardening agents for the gelatin layer include formalin, mucochloric acid glutaraldehyde, glyoxal, and JP-A-54-
130930, known ones such as active halogen type, ethyleneimine type, vinyl sulfone type, epoxy type, or chromium salt can be used. Examples of the fine powder having an average particle size of 2 to 10 μm include silica, clay, talc, ziecrite, and rice starch, and particularly preferably one having an average particle size of 4 to 10 μm.
They are micrometer silica particles. Further, fine particles of 2 μm or less can also be combined. The amount of fine powder with an average particle size of 2 to 10 μm used in the undercoat layer is 5 to 40 μm per 100 weight of hydrophilic colloid.
It is about parts by weight. When included in a silver halide emulsion, 1 to 20 parts by weight per 100 parts by weight of hydrophilic colloid.
It is about parts by weight, and is used in a smaller amount than the proportion of fine powder used in the undercoat layer. Generally, the ratio to the hydrophilic coid can be set at 1/2 to 1/10. Physical development nuclei include antimony, bismuth,
cadmium, cobalt, palladium, nickel,
Known metals such as silver, lead, zinc, and cured products thereof can be used. The image-receiving layer does not need to contain hydrophilic colloids, and may include gelatin, carboxymethylcellulose, gum arabic, sodium alginate, hydroxyethyl starch, dextrin, hydroxyethylcellulose, polystyrene sulfonic acid, a copolymer of vinylimidazole and acrylamide, Hydrophilic colloids such as polyvinyl alcohol may also be included. Hygroscopic substances such as humectants such as sorbitol, glycerol, etc. may be present in the image-receiving layer. Furthermore, the image-receiving layer may also contain pigments for preventing scumming such as barium sulfate, titanium dioxide, china clay and silver, a developing agent such as hydroquinone, and a hardening agent such as formaldehyde. The support may be, for example, paper, film, such as cellulose acetate film, polyvinyl acetal film, polystyrene film, polypropylene film, polyethylene terephthalate film, or a composite film in which polyester, polypropylene, or polystyrene film is coated with polyethylene film, metal, or metallized paper. Or it can be a support for a metal/paper laminate. Paper supports coated on one or both sides with an alpha-olefin polymer, such as polyethylene, are also useful. These supports may also contain antihalation dyes or pigments. The DTR processing solution used in the present invention includes alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sulfites as preservatives such as sodium triphosphate, silver halide solvents such as thiosulfates, Thiocyanates, cyclic imides, thiosalicylic acid, amines, etc., thickening agents such as hydroxyethyl cellulose, carboxymethyl cellulose, antifoggants such as potassium bromide, 1-
Phenyl-5-mercaptotetrazole, JP-A-Sho
47-26201, a development modifier such as a polyoxyalkylene compound, an onium compound, and the like. A developing agent may be included if necessary. The lithographic printing plate of the present invention is, for example,
29723, and U.S. Pat. No. 3,721,559. The printing method, the desensitizing liquid, the dampening liquid, etc. used can be any commonly known method. The present invention will be explained below with reference to examples, but of course it is not limited thereto. Example 1 A matting layer containing silica particles with an average particle size of 5 μm was provided on one side of a 135 g/m 2 double-sided polyethylene coated paper, and the opposite side was coated with carbon black 1-phenyl-3-pyrazolidone after corona discharge machining.
Antihalation layer (gelatin) containing 0.2g/ m2
3.5g/m 2 ), with an average particle size of 7.
An ortho-sensitized high-sensitivity silver chloride emulsion (gelatin 1.0 g/m 2 ) containing μ silica particles and 0.1 g/m 2 of 1-phenyl-3-pyrazolidone was coated at 1.2 g/m 2 as silver nitrate. This antihalation layer and emulsion layer have a pH of 4.2
and contains formalin as a hardening agent. After drying and humidifying at 40°C for 10 days, palladium sulfide sol prepared by the following method was applied onto this emulsion layer at a speed of 5 m/min (Comparison A) Preparation of palladium sulfide sol
【表】
Ｂ液〓
〓水 1
Ａ液とＢ液を撹拌しながら混合し、30分後に純
水製造用に作られたイオン交換樹脂の入つたカラ
ムの中を通して精造し、Ｃ液を加えて塗液とし
た。（PH４に調整）[Table] B liquid〓
〓Water 1
Liquids A and B were mixed with stirring, and after 30 minutes, they were purified by passing through a column containing an ion exchange resin made for pure water production, and liquid C was added to prepare a coating liquid. (adjusted to PH4)
【表】
比較Ａの印刷版に於いて、ハレーシヨン防止層
（下塗層）および乳剤層のゼラチンに対するシリ
カ粒子の含有量（重量％）を第１表に示すように
用いる以外は、全く同様にして印刷版Ｂ〜Ｆを製
造した。
このようにして得られた平版印刷版の原版に像
反転機構を有する凸版用カメラで像露光を行な
い、下記の銀錯塩拡散転写現像液により80℃で１
分間現像処理を行なつた。
転写現像液
水 750 ml
水酸化カリウム 20 ｇ
無水亜硫酸ナトリウム 60 ｇ
臭化カリウム 0.5 ｇ
２−メルカプト安息香酸 １ ｇ
３−メルカプト−４−アセトアミド−５
−ｎ−ヘプチル−１・２・４
−トリアゾール 0.15ｇ
２−メチル−２−アミノ−１−プロパノール
10 ｇ
水を加えて１とする。
現像処理後、該原版を２本の絞りローラー間を
通し、余分の現像液を除去し、直ちに下記組成を
有する中和液で25℃、20秒間処理し、絞りローラ
で余分の液を除去し、室温で乾燥した。
中和液
水 600ml
クエン酸 10ｇ
クエン酸ナトリウム 35ｇ
コロイダルシリカ（20％液） ５ml
エチレングリコール ５ml
水を加えて１とする。
以上の操作により作製した平版印刷をオフセツ
ト印刷機に装着し、下記不感脂化液液を版面にく
まなく与え、下記給湿液を用いて印刷を行なつ
た。
不感脂化液
水 600ml
イソプロピルアルコール 400ml
エチレングリコール 50ｇ
３−メルカプト−４−アセトアミド−５
−ｎ−ヘプチル−１・２・４
−トリアゾール １ｇ
給湿液
Ｏ−リン酸 10ｇ
硝酸ニツケル ５ｇ
亜硫酸ナトリウム ５ｇ
エチレングリコール 100ｇ
コロイダルシリカ（20％液） 28ｇ
水を加えて２とする。
印刷機は、エー・ビー・デイツク350CD（Ａ・
Ｂ・Diek社製オフセツト印刷機の商標）を使用
し、転写銀の飛びあるいは地汚れが生じて印刷が
不可となつたときの印刷枚数で次の基準によりそ
れぞれ評価した。
○ 10000枚以上
△ 7000〜10000枚
× 7000枚以下[Table] The printing plate of Comparative A was prepared in exactly the same manner except that the content (wt%) of silica particles relative to gelatin in the antihalation layer (undercoat layer) and emulsion layer was used as shown in Table 1. Printing plates B to F were produced. The lithographic printing plate master thus obtained was subjected to image exposure using a letterpress camera having an image reversal mechanism, and the following silver complex salt diffusion transfer developer was used at 80°C for 1 hour.
A minute development process was performed. Transfer developer water 750 ml Potassium hydroxide 20 g Anhydrous sodium sulfite 60 g Potassium bromide 0.5 g 2-mercaptobenzoic acid 1 g 3-Mercapto-4-acetamido-5-n-heptyl-1,2,4-triazole 0.15 g 2-methyl-2-amino-1-propanol
Add 10 g water to make 1. After the development process, the original plate was passed between two squeezing rollers to remove excess developer, and immediately treated with a neutralizing solution having the following composition at 25°C for 20 seconds, and the excess liquid was removed using squeezing rollers. , dried at room temperature. Neutralized liquid water 600ml Citric acid 10g Sodium citrate 35g Colloidal silica (20% liquid) 5ml Ethylene glycol 5ml Add water to make 1. The lithographic printing plate prepared by the above operations was mounted on an offset printing machine, the following desensitizing liquid was applied all over the plate surface, and printing was carried out using the following dampening liquid. Desensitized liquid water 600ml Isopropyl alcohol 400ml Ethylene glycol 50g 3-mercapto-4-acetamide-5-n-heptyl-1,2,4-triazole 1g Humidifying liquid O-phosphoric acid 10g Nickel nitrate 5g Sodium sulfite 5g Ethylene glycol 100g Colloidal silica (20% liquid) 28g Add water to make 2. The printing machine is AB Deitsku 350CD (A.
Using an offset printing machine manufactured by B. Diek Co., Ltd. (trademark), the number of sheets printed was evaluated according to the following criteria based on the number of sheets printed when printing became impossible due to transfer silver flying or background smearing. ○ 10,000 sheets or more △ 7,000 to 10,000 sheets × 7,000 sheets or less
【表】
第１表の結果は、シリカ粒子を乳剤層よりも下
塗層の方がゼラチンに対する含有割合として高く
することが必要であることを示している。
実施例 ２
実施例１の比較印刷版Ａの下塗層に更にハイド
ロキノン0.2ｇ/m2を含有して比較印刷版Ｇとし
た。比較Ｇの印刷版の下塗層および乳剤層のシリ
カ粒子を実施例１の印刷版Ｂ〜Ｆと同様にして含
有させて印刷版Ｈ〜Ｌを得た。以後実施例１に準
じて試験した結果、本発明の印刷版ＫおよびＬ
は、比較印刷版Ｇ〜Ｊに比べてより耐刷力が優れ
ていることが確認された。
また、本発明の印刷版ＫおよびＬの下塗層と乳
剤層のPH値をゼラチンの等電点5.0よりも大きい
5.4に調整し、乳剤層塗布後の加温を40℃で５日
間とする以外は同様にして印刷版ＭおよびＮを作
製した。これら印刷版Ｇ〜Ｎを38℃、相対湿度80
％の条件下で１ケ月間保存後実施例１に従つて試
験した。比較印刷版Ｇ〜Ｊは5000枚以下で汚れが
発生したのに対し、本発明の印刷版ＭおよびＮは
約7500枚まで汚れが発生せず、印刷版ＫおよびＬ
は約9000枚までの印刷が可能であつた。
実施例 ３
実施例１を繰返した。但し、１−フエニル−３
−ピラゾリドンを１−フエニル−４・４−ジヒド
ロキシメチル−３−ピラゾリドンまたは１−フエ
ニル−４−メチル−３−ピラゾリドンに、またハ
イドロキノンをメチルハイドロキノンに変更し
た。実施例１と同様の結果が得られた。
実施例 ４
実施例１の転写現像液を下記のものに変更する
以外は同様に試験したところ、同様な結果を得
た。
水酸化カリウム 15ｇ
リン酸三ナトリウム 10ｇ
無水亜硫酸ナトリウム 60ｇ
２−メルカプト−４−アミノ安息香酸15ミリモル
２−メチル−２−アミノ−１−
プロパノール 10ｇ
２−エチルアミノエタノール 10ｇ
水を加えて１とする。
また、実施例１の転写現像液の２−メルカプト
安息香酸をチオ硫酸ナトリウム（15ｇ/）に変
えても同様な結果が得られた。
実施例 ５
実施例１を繰り返した。
但し、転写現像液を下記のものに変更する以外
は全く同様に行なつたところ、実施例１と同様な
結果を得た。
水 750 ml
水酸化カリウム 20 ｇ
無水亜硫酸ナトリウ 60 ｇ
ハイドロキノン 10 ｇ
１−フエニル−３−ピラゾリドン １ ｇ
チオ硫酸ナトリウム 15 ｇ
３−メルカプト−４−アセトアミド−５
−ｎ−ヘプチル−１・２・４
−トリアゾール 0.15ｇ
水を加えて１とする。[Table] The results in Table 1 indicate that it is necessary to make the content of silica particles higher in the undercoat layer than in the emulsion layer relative to gelatin. Example 2 Comparative printing plate G was prepared by further containing 0.2 g/m 2 of hydroquinone in the undercoat layer of comparative printing plate A of Example 1. Silica particles in the undercoat layer and emulsion layer of the printing plate of Comparative G were incorporated in the same manner as in the printing plates B to F of Example 1 to obtain printing plates H to L. Thereafter, as a result of testing according to Example 1, printing plates K and L of the present invention
It was confirmed that the printing durability was better than that of comparative printing plates G to J. In addition, the PH value of the undercoat layer and emulsion layer of the printing plates K and L of the present invention is set to be higher than the isoelectric point of gelatin, which is 5.0.
Printing plates M and N were produced in the same manner except that the temperature was adjusted to 5.4 and the heating after coating the emulsion layer was held at 40°C for 5 days. These printing plates G to N were heated at 38℃ and relative humidity 80℃.
After storage for one month under conditions of Comparative printing plates G to J showed stains after 5,000 sheets or less, whereas printing plates M and N of the present invention did not stain until about 7,500 sheets, and printing plates K and L
It was possible to print up to approximately 9,000 sheets. Example 3 Example 1 was repeated. However, 1-phenyl-3
-Pyrazolidone was changed to 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone or 1-phenyl-4-methyl-3-pyrazolidone, and hydroquinone was changed to methylhydroquinone. Results similar to those in Example 1 were obtained. Example 4 A test was conducted in the same manner as in Example 1 except that the transfer developer was changed to the one below, and similar results were obtained. Potassium hydroxide 15g Trisodium phosphate 10g Anhydrous sodium sulfite 60g 2-mercapto-4-aminobenzoic acid 15 mmol 2-methyl-2-amino-1-propanol 10g 2-ethylaminoethanol 10g Add water to make 1. Furthermore, similar results were obtained when 2-mercaptobenzoic acid in the transfer developer of Example 1 was replaced with sodium thiosulfate (15 g/). Example 5 Example 1 was repeated. However, when the same procedure was carried out except that the transfer developer was changed to the one shown below, the same results as in Example 1 were obtained. Water 750 ml Potassium hydroxide 20 g Anhydrous sodium sulfite 60 g Hydroquinone 10 g 1-phenyl-3-pyrazolidone 1 g Sodium thiosulfate 15 g 3-mercapto-4-acetamide-5 -n-heptyl-1,2,4 - Triazole 0.15g Add water to make 1.
Claims (1)
層および物理現像核層を少なくとも有する平版印
刷版において、少なくとも１つのゼラチン含有層
に現像主薬を含み、さらに前記下塗層には平均粒
径２〜10μｍの微粉末を含みかつ該下塗層の微粉
末の親水性コロイドに対する含有割合は、全層中
で最も高いものであることを特徴とする平版印刷
版。1. A lithographic printing plate having at least an undercoat layer, a silver halide emulsion layer, and a physical development nucleus layer on a support, in which at least one gelatin-containing layer contains a developing agent, and the undercoat layer further contains an average grain particle. 1. A lithographic printing plate comprising fine powder having a diameter of 2 to 10 μm, wherein the content ratio of the fine powder to hydrophilic colloid in the undercoat layer is the highest among all the layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8078582A JPS58196548A (en) | 1982-05-13 | 1982-05-13 | Lithographic printing plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8078582A JPS58196548A (en) | 1982-05-13 | 1982-05-13 | Lithographic printing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58196548A JPS58196548A (en) | 1983-11-16 |
| JPS6123547B2 true JPS6123547B2 (en) | 1986-06-06 |
Family
ID=13728095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8078582A Granted JPS58196548A (en) | 1982-05-13 | 1982-05-13 | Lithographic printing plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58196548A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6396345U (en) * | 1986-12-15 | 1988-06-22 | ||
| JPS63129748U (en) * | 1987-02-18 | 1988-08-24 | ||
| JPS63129745U (en) * | 1987-02-17 | 1988-08-24 | ||
| JPS63152938U (en) * | 1987-03-28 | 1988-10-06 | ||
| JPS63162145U (en) * | 1987-04-10 | 1988-10-24 | ||
| JPS63201246U (en) * | 1987-06-17 | 1988-12-26 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60244954A (en) * | 1984-05-21 | 1985-12-04 | Konishiroku Photo Ind Co Ltd | Silver salt lithographic material |
| JPS63226658A (en) * | 1987-03-16 | 1988-09-21 | Mitsubishi Paper Mills Ltd | Planographic printing material for back exposure |
| JP2549784B2 (en) * | 1991-10-14 | 1996-10-30 | 三菱製紙株式会社 | Lithographic printing plate |
| JP2549781B2 (en) * | 1991-09-19 | 1996-10-30 | 三菱製紙株式会社 | Lithographic printing plate |
| DE4480342T1 (en) * | 1993-12-28 | 1996-01-11 | Mitsubishi Paper Mills Ltd | Process for the treatment of photosensitive materials and device therefor |
-
1982
- 1982-05-13 JP JP8078582A patent/JPS58196548A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6396345U (en) * | 1986-12-15 | 1988-06-22 | ||
| JPS63129745U (en) * | 1987-02-17 | 1988-08-24 | ||
| JPS63129748U (en) * | 1987-02-18 | 1988-08-24 | ||
| JPS63152938U (en) * | 1987-03-28 | 1988-10-06 | ||
| JPS63162145U (en) * | 1987-04-10 | 1988-10-24 | ||
| JPS63201246U (en) * | 1987-06-17 | 1988-12-26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58196548A (en) | 1983-11-16 |
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