JPH0147777B2 - - Google Patents
Info
- Publication number
- JPH0147777B2 JPH0147777B2 JP6026581A JP6026581A JPH0147777B2 JP H0147777 B2 JPH0147777 B2 JP H0147777B2 JP 6026581 A JP6026581 A JP 6026581A JP 6026581 A JP6026581 A JP 6026581A JP H0147777 B2 JPH0147777 B2 JP H0147777B2
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- compound
- image
- gelatin
- vinyl
- 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
- -1 Silver halide Chemical class 0.000 claims description 137
- 229910052709 silver Inorganic materials 0.000 claims description 68
- 239000004332 silver Substances 0.000 claims description 68
- 229920002554 vinyl polymer Polymers 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 30
- 238000011161 development Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000004001 thioalkyl group Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 47
- 150000001875 compounds Chemical class 0.000 description 43
- 108010010803 Gelatin Proteins 0.000 description 42
- 229920000159 gelatin Polymers 0.000 description 42
- 239000008273 gelatin Substances 0.000 description 42
- 235000019322 gelatine Nutrition 0.000 description 42
- 235000011852 gelatine desserts Nutrition 0.000 description 42
- 239000000839 emulsion Substances 0.000 description 39
- 239000000975 dye Substances 0.000 description 37
- 238000006116 polymerization reaction Methods 0.000 description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 230000035945 sensitivity Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 206010070834 Sensitisation Diseases 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000981 basic dye Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 230000008313 sensitization Effects 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000004571 lime Substances 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
- 239000003960 organic solvent Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 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 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- KSCQDDRPFHTIRL-UHFFFAOYSA-N auramine O Chemical compound [H+].[Cl-].C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 KSCQDDRPFHTIRL-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- IWWWBRIIGAXLCJ-BGABXYSRSA-N chembl1185241 Chemical compound C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC IWWWBRIIGAXLCJ-BGABXYSRSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- DJDYMAHXZBQZKH-UHFFFAOYSA-M sodium;1-amino-4-(cyclohexylamino)-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S([O-])(=O)=O)C=C1NC1CCCCC1 DJDYMAHXZBQZKH-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- YLVACWCCJCZITJ-UHFFFAOYSA-N 1,4-dioxane-2,3-diol Chemical compound OC1OCCOC1O YLVACWCCJCZITJ-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- SAVMNSHHXUMFRQ-UHFFFAOYSA-N 1-[bis(ethenylsulfonyl)methoxy-ethenylsulfonylmethyl]sulfonylethene Chemical compound C=CS(=O)(=O)C(S(=O)(=O)C=C)OC(S(=O)(=O)C=C)S(=O)(=O)C=C SAVMNSHHXUMFRQ-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical group OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-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
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WHJDYNKUABBTRF-UHFFFAOYSA-N C(C=C)(=O)OCCN(C(=O)OCC)CCCN(C(=O)OCC)CCOC(C=C)=O Chemical compound C(C=C)(=O)OCCN(C(=O)OCC)CCCN(C(=O)OCC)CCOC(C=C)=O WHJDYNKUABBTRF-UHFFFAOYSA-N 0.000 description 1
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
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- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000008130 triterpenoid saponins Chemical class 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical group OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/0285—Silver salts, e.g. a latent silver salt image
Description
本発明は重合物による画像の形成方法に関す
る。特にハロゲン化銀写真乳剤と還元剤の作用に
よつて写真的潜像に対応する部分に選択的に高分
子化合物を生成させる方法に関する。
光の作用によつてビニール化合物を重合させ高
分子化合物を生成させて像を形成する方法は種々
提案されている。ハロゲン化銀を触媒として用い
て光重合を直接起させることも提案されている
（英国特許第86631号明細書、S.レビノス
（Levinos）他フオトグラフイツク・サイエン
ス・アンド・エンジニアリング（Phoographic
Science ＆ Engineering）第６巻第222〜226
頁（1962））。この反応では、ハロゲン化銀の光分
解によつて生じた生成物が直接重合の触媒となる
ものと考えられており、通常の現像によつてハロ
ゲン化銀粒子を還元する場合程の高感度は得られ
ていない。又、露光されたハロゲン化銀乳剤粒子
を通常の現像液によつて現像した後、生じた銀画
像、あるいは未反応のハロゲン化銀を触媒として
利用してビニール化合物の重合を行わせ高分子化
合物を画像状に生成させることも提案されている
（ベルギー特許第642477号明細書等）。この反応は
現像操作と重合操作を分離して行わねばならない
欠点がある。露光されたハロゲン化銀をビニール
化合物の存在下で還元性の化合物で現像し、その
過程で生じる酸化生成物或いはその中間生成物に
よつてビニール化合物の重合を起させることは、
すでにベンゼン環上でお互にオルト又はパラの位
置に２個以上の水酸基又はアミノ基又はアルキ
ル、又はアリールで置換されたアミノ基を有する
様な所謂ベンゼノイド化合物を還元剤としてこの
様な反応を行わせる事が提案されている（米国特
許第3019104号明細書、G.オスター・ネイチユア
（Oster.Nature）第180巻第1275頁（1957））。し
かし、このベンゼノイド化合物による反応の実例
では、ハロゲン化銀の銀像の光学濃度の上昇を認
めたのみであり、高分子の生長を直接裏付けする
様な粘度上昇、あるいは反応熱の発生の確認ある
いは生成分子の単離は行われていない。
更にまた他の研究者達は追試に成功しなかつた
とも報告している（S.レビノス（Levinos）and
F.W.H.ミユラー・フオトグラフイツク・サイエ
ンス（Mueller、Photographic Science）＆エン
ジニアリング（Engineering）第６巻第222頁
（1962））。
次いで露光されたハロゲン化銀の存在下でレゾ
ルシン、ナフトール、ピラゾロン、ヒドラジン化
合物を重合開始剤として用いたビニール化合物を
重合させせることが特公昭45−11149号、同50−
10488号、同45−30338号、同46−21723号、同47
−18585号、同46−6581号、同47−14667号、同47
−14668号、同47−14669号、同477−12638号、同
47−20741号、同49−1569号、同49−1570号、同
49−48769号及び同49−10697号で提案されてい
る。これらの発明ではビニール化合物の重合体は
生じるものの感度の点ではいまだ充分とはいえな
かつた。
又重合開始剤としてハイドロキノン等を用いる
発明が特開昭55−149939号で開示されているが、
これはハロゲン化銀が還元されなかつた部分、す
なわち非露光部分で重合反応がおこり、ハロゲン
化銀像に対してポジの像ができる。これも感度の
点ではいまだ充分とはいえない。
本発明の目的は、露光されたたハロゲン化銀の
存在下でビニール化合物を重合させる感度の高い
方法を提供することである。本発明のもう１つの
目的は、ハロゲン化銀像に対してネガのポリマー
像を得ることのできる高感度のハロゲン化銀感光
材料を提供することである。
本発明者らは下記に述べるフエノール化合物を
使用してビニール化合物の存在下でハロゲン化銀
を還元すると上記ビニール化合物の重合をひき起
し得る事を発見した。しかもハロゲン化銀として
ハロゲン化銀写真乳剤を用いると、反応はハロゲ
ン化銀微結晶が現像核を保有して居る場合により
速やかに起り、従つて適当な反応条件と反応時間
を選べば現像核を有するハロゲン化銀粒子の存在
する部分のみにおいて、選択的に重合を起す事が
出来る。
本発明は上記の事実を利用することに依つて達
成される。即ち本発明は写真的な潜像を有するハ
ロゲン化銀写真乳剤層にフエノール化合物の少く
とも一つを重合し得るビニール化合物の存在下
で、作用させる事に依り、潜像が存在する部分に
おいて選択的に、上記ビニール化合物の重合をひ
き起こさせる事に依つて達成される。
本発明に用いられるフエノール化合物は下記一
般式〔〕または〔〕で示される。
一般式
式中R1、R2、R3、R4は各々水素、ハロゲン原
子、アルキル基、置換アルキル基、アリール基、
置換アリール基、アルコキシ基、チオアルキル基
又はシアノ基を表わし、R1、R2、R3、R4の内少
くとも１つはハロゲン原子を表わす。
アルキル基および置換アルキル基の例としては
メチル基、ブチル基、メトキシエチル基、ハロメ
チル基、ベンジル基がある。
アリール基、置換アリール基の例としてはフエ
ニル基、トリル基がある。
前記のR1、R2、R3、R4が表わすハロゲン原子
のうち、塩素、臭素、ヨウ素が好ましく、R1、
R2、R3、R4全部水素原子以外のものである場合
が好ましい。
本発明に用いられる化合物としては例えば次の
ような化合物がある。
写真的な潜像とは電磁波又は粒子線の作用に依
つてハロゲン化銀写真乳剤に生じた、通常そのま
までは目に見えない像状の変化であり、現像する
事に依つて可視像とするものである。通常の陰画
を生ずる乳剤では、電磁波又は粒子線で照射され
たハロゲン化銀粒子に現像核が生ずる事に依つて
潜像が生じ、直接陽画乳剤では最初全粒子に存在
していた現像液が照射に依つて消失するために、
潜像が生ずるジエームス（James）andハギンス
（Huggins.）著“フアンダメンタルス・オブ・ホ
トグラフイツク・セオリー（Fundameentals of
Photographic Theory）”第二版Morgam ＆
Morgam.社、1960年発行、３章及び４章参照）。
本発明に用いられるハロゲン化銀写真乳剤は、
電磁波又は粒子線の作用に依つて照射された部分
に現像核を生ずるように即ち、現像に依つて陰画
を生ずる様な通常のハロゲン化銀写真乳剤も使用
できるし、画像状の光の照射を受けた部分よりも
それ以外の部分の方が多数のハロゲン銀粒子に現
像核が存在する様ないわゆる直接陽画乳剤も使用
できる。
本発明において、陰画を生ずるようなハロゲン
化銀写真乳剤としては、通常の現像処理に対して
用いられるハロゲン化銀写真乳剤が好都合に使用
されうる。即ち塩化銀、臭化銀、塩臭化銀、沃臭
化銀、塩沃臭化銀写真乳剤が使用可能である。本
発明に使用される写真乳剤には、通常の写真乳剤
に対して行われる様な化学増感、光学増感を適用
する事が出来る。即ち、化学増感としては、硫黄
増感、貴金属増感、還元増感を行う事が出来る。
（例えばP.グラフキテス・シミー・フオトグラフ
イツク（Glafkides Chimi Photo−graphique）
第２版フオトシネマ・ホール・モンテル・パリ
（Photocinema Paul Montel Paris）1957年第
247〜301頁参照）。ザ・セオリー・オブ・ザ・フ
オトグラフイツクプロセス（The Theory of
the Photographic Process）第４版マクミラン
（Macmillan社）1977年発行の第５章参照。又、
光学増感には、シアニン色素、メロシアニン色素
等通常の写真法で用いられる光学増感色素（例え
ば菊地真一他科学写真便覧、中巻、丸善発行1959
年、15〜24頁参照）が有効である。又、本発明で
使用する乳剤は通常の写真法で利用される様な安
定剤を含んでいても良い。
本発明に使用出来る直接陽画ハロゲン化銀写真
乳剤は、ソラリゼーシヨン、ハーシエル効果、ク
ライデン効果、サバチエ効果を利用して作成する
ことができる。此等の効果の説明は例えばC.E.K.
ミース（Mees）著ザ・セオリー・オブ・ザ・フ
オトグラフイツク・プロセス（The Theory of
the Photographic Process）、第二版（マクミラ
ン（MACMILLAN）社、1954年発行）の第六章
及び第七章に述べられているソラリゼーシヨンを
利用して、直接陽画ハロゲン化銀乳剤を作るには
ソラリゼーシヨンを起し易いタイプのハロゲン化
銀写真乳剤を作り、画像露光なしで充分現像可能
となる様にあらかじめ全面に露光を与えるか化学
薬品を作用させておけば良い。此の様な乳剤の作
り方の例は、例えば英国特許第443245号明細書及
び同第462730号明細書等に見られる。
ハーシエル効果は全面露光を受けるか、化学薬
品に依つて全面的に現像可能性を有する様になつ
たハロゲン化銀に長波長の光を当てる事に依つて
ひき起こされるが、此の場合には、塩化銀を多く
含むハロゲン化銀乳が有利であり、又ハーシエル
効果を助長する為にピナクリプトールイエロー、
フエノサフラン等の減感色素を加える事も行われ
る。ハーシエル効果を利用した直接陽画乳剤の製
造方法は例えば英国特許第667206号明細書、米国
特許第2857273号明細書等に見られる。
クライデン効果を利用して直接陽画を得るに
は、高照度で短時間の画像露光を与えた後に、比
較的低照度で全面に露光することが必要であつ
て、この全面露光の後にはじめて、高照度の画像
露光を受けなかつた部分が現像可能性を持つよう
になる。
サバチエ効果は、ハロゲン化銀乳剤が画像状に
露光を受けた後、現像液に浸された状態で全面に
露光されるか、化学薬品の作用を受けるかするこ
とによつて、画像状の露光を受けなかつた部分に
現像可能性を生じることに依つて起る。クライデ
ン効果、サバチエ効果は、最初の露光に依つてハ
ロゲン化銀粒子粒子の表面よりも、粒子内部に現
像核を生ずる傾向が強い様なハロゲン化銀乳剤を
用いた場合に容易に実用的におこすことができ
る。
この様な内部現像核を生じ易い乳剤の製造方法
は例えば、米国特許第2592250号明細書、米国特
許第2497876号明細書、英国特許第1011062号明細
書、ドイツ特許第1207791号明細書等に記載され
ている。
コア・シエル乳剤を用いて陽画を作成すること
もできる。コア・シエル乳剤の製造法は米国特許
第3761276号明細書、米国特許第3206313号明細書
に記載されている。
上記写真乳剤は高分子物質の溶液中にハロゲン
化銀粒子の分散した系からなつており、その高分
子物質としてはゼラチンが広く用いられている
が、それ以外の親水性コロイドも用いることとが
できる。たとえばゼラチン誘導体、ゼラチンと他
の高分子とのグラフトポリマー、アルブミン、カ
ゼイン等の蛋白質；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、セルローズ硫
酸エステル類等の如きセルロース誘導体、アルギ
ン酸ソーダ、澱粉誘導体などの糖誘導体；ポリビ
ニルアルコール、ポリビニルアルコール部分アセ
タール、ポリ−Ｎ−ビニルピロリドン、ポリアク
リル酸、ポリメタクリル酸（またはポリ（メタ）
アクリル酸にグリシジル（メタ）アクリレートを
エステル結合させたもの。）、ポリアクリルアミ
ド、ポリビニルイミダゾール、ポリビニルピラゾ
ール等の単一あるいは共重合体の如き多種の合成
親水性高分子物質を用いることができる。
ゼラチンとしては石灰処理ゼラチンのほか、酸
処理ゼラチンを用いてもよく、ゼラチン加水分解
物、ゼラチン酸素分解物も用いることができる。
ゼラチン誘導体としては、ゼラチンにたとえば酸
ハライド、酸無水物、イソシアナート類、プロモ
酢酸、アルカンサルトン類、ビニルスルホンアミ
ド類、マレインイミド化合物類、ポリアルキレン
オキシド類、エポキシ化合物類等種々の化合物を
反応させて得られるものが用いられる。その具体
例は米国特許2614928号、同3132945号、同
3186846号、同3312553号、英国特許861414号、同
1033189号、同1005784号、特公昭42−26845号な
どに記載されている。
前記ゼラチン・グラフトポリマーとしては、ゼ
ラチンにアクリル酸、メタアクリ酸、それらのエ
ステル、アミドなどの誘導体、アクリロニトリ
ル、スチレンなどの如き、ビニル系モノマーの単
一（ホモ）または共重合体をグラフトさせたもの
を用いることができる。ことに、ゼラチンとある
程度相溶性のあるポリマーたとえばアクリル酸、
メタアクリル酸、アクリルアミド、メタアクリル
アミド、ヒドロキシアルキルメタアクリレート等
の重合体とのグラフトポリマーが好ましい。これ
らの例は米国特許2763625号、同2831767号、同
2956884号などに記載がある。代表的な合成親水
性高分子物質はたとえば西独特許出願（OLS）
2312708号、米国特許3620751号、同3879205号、
特公昭43−7561号に記載のものである。
本発明のフエノール化合物は通常は重合禁止剤
として単量体の保存性良化のため、またプラスチ
ツク、ゴム等の酸化防止剤として用いられ、本発
明の様に重合開始剤として用いられる例はない。
このように従来重合禁止剤として用いられてい
たフエノール化合物を本発明のように重合開始剤
として用いるのは画期的なことである。
前記フエノール化合物によるハロゲン化銀の還
元の結果ビニール化合物の重合の起る反応機構は
末だ明らかでない。しかし一般にラジカル重合を
行う化合物が利用でき、水溶液中で反応が進むこ
と、また酸素が重合反応を遅らせることから重合
はラジカル機構で進むものと考えられる。前記フ
エノール化合物とハロゲン化銀の反応で直接ラジ
カルが発生するか、あるいは更に系内の水、酸素
等との相互作用によつてラジカル発が発生するの
かは未だ明らかでない。照射されたハロゲン化銀
を前記フエノール化合物で還元してから、反応系
にビニール化合物を加えた場合には重合は認めら
れないので、ハロゲン化銀が還元されると同時に
その場所でビニール化合物の重合が起こるという
ことは明らかである。従つてハロゲン化銀と前記
フエノール化合物との中間生成物が反応に寄与し
ていると考えられる。
ハロゲン化銀の光感度を利用して高分子に依る
画像を形成する方法として、従来良く知られた現
像主薬の酸化生成物に依つてゼラチンに架橋を行
ういわゆるタンニング現像法では生成した画像は
ゼラチンに架橋が行われた物に限られて居る。し
かし本発明で得られる高分子の画像は、使用した
ビニール化合物に応じて種々の性質のものが得ら
れるので、染色性、耐薬品性等ゼラチンに架橋し
た物では得られない性質を得ることが出来るのが
特徴である。
更に本発明方法において亜硫酸イオンが系内に
存在すると、ビニール化合物の重合が促進され
る。
亜硫酸イオンは例えばアルカリ金属又はアンモ
ニウムの亜硫酸塩、重亜硫酸塩の如く亜硫酸イオ
ンを最初から有している化合物として、加えられ
ても良いし、アルカリ金属又はアンモニウムのピ
ロ亜硫酸塩、又は重亜硫酸塩とフオルムアルデヒ
ド又はグリオキザールの如きアルデヒドとの附加
物の如く、水溶液中で分解して亜硫酸イオンを発
生する物質として加えられても良い。亜硫酸イオ
ンの適当な添加量は、使用するフエノール化合
物、ビニルモノマーの種類および量、および系の
PH等で変化するが、反応系１当り0.002モル以
上、特に0.01モル以上が有効である。
亜硫酸塩を写真現像液に加える事は、周知の事
である。此の場合、亜硫酸塩は、ハイドロキノン
パラアミノフエノールの如き現像主薬の酸化生成
物と反応する事に依つて現像主薬の自動酸化を防
止し、又現像反応が不均一に起る事を防止すると
考えられて居る（例えばC.E.K.ミース（Mees）
著、ザ・セオリー・オブ・ザ・フオトグラフイツ
ク・プロセス（The Theory of the
Photographic Process）（第二版）マクミラン
（MACMILLAN）社発行、1954年（652頁参
照））。
本発明ではフエノール化合物のハロゲン化銀に
依る酸化の中間生成物が重合を開始するのである
から、亜硫酸塩の重合促進効果は、上の様な普通
現像液中での酸化生成物除去の作用とは根本的に
異つて居ることに注意せねばならない。
亜硫酸塩が酸化生成物を単に除去するのであれ
ば、重合はむしろ抑制されねばならないはずであ
る。又、亜硫酸塩は酸化還元反応の還元剤として
著名な化合物であり、ハロゲン化銀−亜硫酸イオ
ンの系による重合も考えられうるが、本発明で行
なつた実験では本発明で述べるようなフエノール
化合物の存在しない場合には、それによる重合は
ほとんど無視できた。
本発明における亜硫酸の作用機構は明らかでは
ないが、酸素に依る重合の阻害作用を防止して居
ると考えるのが妥当であろうと思われる。
本発明に於てビニール化合物は常温で液体又は
固体の附加重合性の化合物又はそれ等の混合物を
使用する。此の様な化合物としては、アクリルア
ミド、アクリルニトリル、Ｎ−ヒドロキシメチル
アクリルアミド、メタアクリルアミド、Ｎ−ｔ−
ブチルアクリルアミド、メタアクリル酸、アクリ
ル酸、アクリル酸カルシウム、アクリル酸アルミ
ニウム、アクリル酸ナトリウム、メタアクリルア
ミド、メタアクリル酸メチル、アクリル酸メチ
ル、アクリル酸エチル、２−アクリルアミド−２
−メチプロパンスルホン酸、ビニルピロリドン、
２−ビニルピリジン、４−ビニルピリン、２−メ
チル−Ｎ−ビニルイミダゾール、ビニルベンゼン
スルホン酸カリウム、ビニールカルバゾール等が
ある。本発明に於ては二つ以上のビニール基を有
する化合物が特に好都合であり、前記の様なビニ
ール基一個を有する化合物と併用するか、あるい
は此の様な複数個のビニール基を有する化合物単
独で使用する。此の様な化合物の例としてはＮ・
N′−メチレンビスアクリルアミド、エチレング
リコールジメタアクリレート、ジエチレングリコ
ールジメタアクリレート、トリエチレングリコー
ルジメタアクリレート、ポリエチレングリコール
ジメタアクリレート、ジビニルエーテル、ジビニ
ルベンゼンビスフエノール−Ａ−ジメタアクリレ
ート、トリメチロールプロパントリアクリレー
ト、ペンタエリスリトールテトラアクリレート、
ビスオキシエチレン化ビスフエノール−Ａ−ジア
クリレートあるいはウレタン基を含有する不飽和
単量体例えばジ−（2′−メタクリロキシエチル）−
２，４−トリレンジウレタン、ジ−（2′−アクリ
ロキシエチル）トリメチレンジウレタンのような
ジオールモノ（メタ）アリレートとジイソシアネ
ートとの反応生成物等がある。
本発明に於て水溶性のビニール化合物を用いて
も良く、また非水溶性のビニール化合物を乳液と
してまたは適当な溶媒に溶解して添加する事によ
り重合を行わせることも出来る。乳化は常法に従
つて界面活性剤及び／又は高分子化合物の存在下
で適当な撹拌装置によつて行うことが出来る。
本反応は一般にアルカリ性で良く進行するが最
も適当なPHはハロゲン化銀、フエノール化合物、
ビニール化合物及び媒体高分子化合物の種類、濃
度及び反応温度により異り、PH約８以上で反応は
可能であり、９以上が特に都合が良い。
写真乳剤を支持体に塗布して使用する場合は、
この感光材料を電磁線或いは粒子線で照射した後
アルカリ性水溶液中に浸漬して反応を進行させる
事が出来る。還元剤或いはビニール化合物はこの
アルカリ性水溶液中に含有させても良く、また感
光材料に含有させても良い。
反応の停止は系を酸性、例えばPHを５以下にす
る事に依つて容易に行われるが、冷却、洗滌に依
る反応物の除去、写真用定着液に依るハロゲン化
銀の溶解、又は重合禁止剤の系への添加に依つて
も停止する事ができる。
ビニール化合物単量体を最初から感光材料に加
えておく場合には、使用されるビニール化合物の
重量は、あらかじめ加えられた高分子化合物の1/
３０ないし30倍、特に1/4ないし４倍が好都合であ
る。又使用されるハロゲン化銀はあらかじめ用い
られる高分子化合物の1/1000ないし２倍の重量、
特に4/1000ないし1/2倍の重量が好都合である。
又、本願のフエノール化合物をあらかじめ感材に
加えておく場合は、使用するハロゲン化銀１モル
に対して1/10ないし20モルが好都合である。フエ
ノール化合物は水または有機溶剤に溶かすか、ま
たは水もしく有機溶剤に適当な界面活性剤を加え
て溶かし、感材の調製時に加えてもよい。
ビニール化合物を処理液中に添加する場合は通
常濃度がなるべく高い方が好都合であり、液中へ
の添加量は使用されるビニール化合物の処理液中
での溶解度にむしろ制限される。還元剤として用
いられるフエノール化合物を処理液中に添加する
場合には、用いる化合物によつて最適濃度は多少
異るが、濃度は１あたり1/1000モルないし５モ
ルが適当であり、特に1/500モルないし１モルが
好都合である。
またフエノール化合物を添加する際水溶液ある
いは有機溶剤溶液として加えても良く、さらに界
面活性剤を加えて可溶化しても良い。
本発明の感光材料は無機または有機の硬膜剤を
含有することができる。例えばクロム塩（クロム
明ばん、酢酸クロムなど）、アルデヒド類（ホル
ムアルデヒド、グリオキサール、グルタールアル
デヒドなど）、Ｎ−メチロール化合物（ジメチロ
ール尿素、メチロールジメチルダントインなど）、
ジオキサン誘導体（２，３−ジヒドロキシジオキ
サンなど）、活性ビニル化合物（１，３，５−ト
リアクリロイル−ヘキサヒドロ−ｓ−トリアジ
ン、ビス（ビニルスルホニル）メチルエーテルな
ど）、活性ハロゲン化合物（２，４−ジクロル−
６−ヒドロキシ−ｓ−トリアジンなど）、ムコハ
ロゲン酸類（ムコクロル酸、ムコフエノキシクロ
ル酸など）、イソオキサゾール類、ジアルデヒド
でん粉、２−クロル−６−ヒドロキシトリアジニ
ル化ゼラチンなどを、単独または組合せで用にる
ことができる。その具体例は、米国特許1870354
号、同2080019号、同2726162号、同2870013号、
同2983611号、同2992109号、同3047394号、同
3057723号、同3103437号、同3321313号、同
3325287号、同3362827号、同3539644号、同
3543292号、英国特許676628号、同825544号、同
1270578号、ドイツ特許872153号、同1090427号、
特公昭34−7133号、同46−1872号などに記載があ
る。
本発明に用いられる感光材料には塗布助剤、帯
電防止、スベリ性改良、乳化分散、および接着防
止など種々の目的で種々の公知の界面活性剤を含
んでもよい。
たとえばサポニン（ステロイド系）、アルキレ
ンオキサイド誘導体（例えばポリエチレングリコ
ール、ポリエチレングリコール／ポリプロピレン
グリコール縮合物、ポリエチレングリコールアル
キルまたはアルキルアリールエーテル、ポリエチ
レングリコールエステル類、ポリエチレングリコ
ールソルビタンエステル類、ポリアルキレングリ
コールアルキルアミンまたはアミド類、シリコー
ンのポリエチレンオキサイド付加物類）、グリシ
ドール誘導体（たとえばアルケニルコハク酸ポリ
グリセリド、アルキルフエノールポリグリセリ
ド）、多価アルコールの脂肪酸エステル類、糖の
アルキルエステル類、同じくウレタン類またはエ
ーテル類などの非イオン性界面活性剤：トリテル
ペノイド系サポニン、アルキルカルボン酸塩、ア
ルキルスルフオン酸塩、アルキルベンゼンスルフ
オン酸塩、アルキルナフタレンスルフオン酸塩、
アルキル硫酸エステル類、アルキルリン酸エステ
ル類、Ｎ−アシル−Ｎ−アルキルタウリン類、ス
ルホコハク酸エステル類、スルホアルキルポリオ
キシエチレンアルキルフエノールエーテル類、ポ
リオキシエチレンアルキルリン酸エステル類など
のような、カルボキシ基、スルホ基、ホスホ基、
硫酸エステル基、燐酸エステル基等の酸性基を含
むアニオン界面活性剤：アミノ酸類、アミノアル
キルスルホン酸類、アミノアルキル硫酸または燐
酸エステル類、アルキルベタイン類、アミンイミ
ド類、アミンオキシド類などの両性界面活性剤：
アルキルアミン塩類、脂肪族あるいは芳香族第４
級アンモニウム塩類、ピリジニウム、イミダゾリ
ウムなどの複素環第４級アンモニウム塩類、およ
び脂肪族または複素環を含むホスホニウムまたは
スルホニウム塩類などのカチオン界面活性剤を用
いることができる。
これらの界面活性剤の具体例は米国特許
2240472号、同2831766号、同3158484号、同
3210191号、同3294540号、同3507660号、英国特
許1012495号、同1022878号、同1179290号、同
1198450号、特開昭50−117414号、米国特許
2739891号、同2823123号、同3068101号、同
3415649号、同3666478号、同3756828号、英国特
許1397218号、米国特許3133816号、同3441413号、
同3475174号、同3545974号、同3726683号、同
3843368号、ベルギー特許731126号、英国特許
1138514号、同1159825号、同1374780号、特公昭
40−378号、同40−379号、同43−13822号、米国
特許2271623号、同2288226号、同2944900号、同
3253919号、同3671247号、同3772021号、同
3589906号、同3666478号、同3754924号、西独特
許出願OLS1961638号、特開昭50−59025号など
に記載のものである。
本発明を用いて作られる写真感光材料において
ハロゲン化銀写真乳剤層その他の層は写真感光材
料に通常用いられているプラスチツクフイルム、
紙、布などの可撓性支持体またはガラス、陶器、
金属などの剛性の支持体に塗布される。可撓性支
持体として有用なものは、硝酸セルロース、酢酸
セルロース、酢酸酪酸セルロース、ポリスチレ
ン、ポリ塩化ビニル、ポリエチレンテレフタレー
ト、ポリカーボネート等の半合成または合成高分
子から成るフイルム、バライタ層またはα−オレ
フインポリマー（例えばポリエチレン、ポリプロ
ピレン、エチレン／ブテン共重合体）等を塗布ま
たはラミネートした紙等である。支持体は染料や
顔料を用いて着色されてもよい。遮光の目的で黒
色にしてもよい。これらの支持体の表面は一般
に、写真乳剤等との接着をよくするために下塗処
理される。支持体表面は下塗処理の前または後
に、コロナ放電、紫外線照射、火焔処理等を施し
てもよい。
本発明に於ては写真画像を得るために使用でき
る電磁波又は粒子線としては、通常の写真乳剤が
感光するあらゆる電磁波又は粒子線が利用可能で
ある。即ち可視光線、紫外線、1.3μ以下の赤外
線、Ｘ線、ガンマ線及び電子線、アルフア線の如
き粒子線が適用できる。特に通常の方法すなわ
ち、タングステン電灯、螢光灯、水銀灯、キセノ
ン、アーク灯、炭素アーク灯、キセノンフラツシ
ユ灯、ハロゲンランプ、発光ダイオード、陰極線
管フライングスポツト、グローチユーブなどの放
電管、アルゴンレーザー等のレーザー光など公知
の多種の光源をいずれでも用いることができる。
螢光時間は1/1000秒から50秒の露光時間はもちろ
ん、1/1000秒より短い露光、たとえばキセノン閃
光灯や陰極線管やレーザー光を用いた1/104〜1/1
０6頻の露光を用いることもできるし、50秒より長
い露光を用いることもできる。必要に応じて色フ
イルターで露光に用いられる光の分光組成を調節
することができる。
本発明の方法を画像の記録に利用する場合は、
ビニール化合物とその重合体との間の溶解度、光
散乱、粘着性、染着性等の物理的及び化学的性質
の差を種々に利用する事が可能である。溶解性の
差を利用する事に依り、照射と反応を行つた後に
未重合部分を溶解し去る事によつて、照射を受け
た部分にのみ高分子物質に依る像が残留する様に
して画像を形成する事ができる。
この場合には最初に加えた高分子化合物は未反
応の単量体と共に溶解し去られる方が好都合であ
る。その為に最初から系内に含まれている高分子
化合物は、所謂二次元の線状で架橋が殆んど行わ
れていないか、あるいは、容易に主鎖ないし架橋
が切断される様な高分子化合物であつて、一方反
応により生成する高分子化合物は架橋の行われた
所謂三次元の重合体であるのが好都合である。此
の為には、前述したビニール基を複数個持つた化
合物を単独又はビニール基一個を持つ化合物との
併用で使用するのが好都合である。しかし、生成
した高分子物質が二次元の可溶性高分子物質であ
つても、あらかじめ添加してあつた高分子化合物
との相互作用の結果、反応に依つて高分子物質が
生じた部分とそうでない部分の間に著しく溶解性
に差の生じる場合も多いので（例えばポリアクリ
ル酸とゼラチンの場合）、複数個のビニール基を
持つた単量体を使用する事は不可欠の条件ではな
い。
本発明方法を用いて作成した高分子物質よりな
る画像は種々の印刷方法にも利用する事ができ
る。
又、本発明は、色素画像の形成方法にも利用す
る事ができる。この方法においては、ビニール単
量体として電離又は水素陽イオンの付加によつて
電荷を持つ事ができる様な基を有する単量体を使
用し、電離又は水素陽イオンの付加に依つて電荷
を持つ事ができる重合体を形成させ、その画像を
反対の電荷を有する色素によつて、選択的に染色
する。又、この様にしてできた色素画像は種々の
方法で別の支持体に転写する事も可能である。
この場合に利用できる電離又は水素陽イオンの
附加に依つて電荷を持つ事のできる付加重合性の
ビニル化合物としては、生成した高分子化合物に
負の電荷を持たせるもの例えばアクリル酸、メタ
アクリル酸、イタコン酸、マレイン酸の如きカル
ボキシル基を持つたビニール化合物、アクリル酸
アンモニウム、アクリル酸ナトリウム、アクリル
酸カリウム、アクリル酸カルシウム、アクリル酸
マグネシウム、アクリル酸亜鉛、アクリル酸カド
ミウム、メタアクリル酸ナトリウム、メタアクリ
ル酸カルシウム、メタアクリル酸マグネシウム、
メタアクリル酸亜鉛、メタアクリル酸カドミウ
ム、イタコン酸ナトリウム、マレイン酸ナトリウ
ムの如きカルボキシル基の金属塩又はアンモニウ
ム塩をもつビニール化合物、ビニールスルホン
酸、Ｐ−ビニールベンゼンスルホン酸の如きスル
ホン酸基を有するビニール化合物、及びビニルス
ルホン酸アンモニウム、ビニールスルホン酸ナト
リウム、ビニールスルホン酸カリウム、Ｐ−ビニ
ールベンゼンスルホン酸カリウムの如きスルホン
酸の金属塩又はアンモニウム塩をもつビニール化
合物があり、生成した高分子に正の電荷を持たせ
るもの例えば２−ビニールピリジン、４−ビニー
ルピリジン、５−ビニール−２−メチルピリジ
ン、Ｎ，Ｎ−ジメチルアミノエチルアクリレー
ト、Ｎ，Ｎ−ジメチルアミノエチルメタアクリレ
ート、Ｎ，Ｎ−ジエチルアミノエチルアクリレー
ト、Ｎ，Ｎ−ジエチルアミノエチルメタアクリレ
ートの如き塩基性窒素原子を有するビニール化合
物及びそれらの塩基に塩化メチル、臭化エチル、
ジメチル硫酸、ジエチル硫酸、Ｐ−トルエンスル
ホン酸メチル等を作用させて作つた四級塩の窒素
を持つビニール化合物があり、此等の化合物の合
成法は良く知られており市販品も入手出来る。此
等の化合物は単独で使用して良いし二つ以上を混
合しても用いられる。又、電荷を持たない水溶性
の付加重合性のビニール化合物と併用しても良
い。併用し得るビニール化合物としては、アクリ
ルアミド、Ｎ−ヒドロキシメチルアクリルアミ
ド、メタアクリルアミド、メタアクリル酸メチ
ル、ビニルピロリドン、Ｎ，Ｎ−メチレンビスア
クリルアミド、トリエチレングリコールジメタア
クリレート、ポリエチレングリコールジメタアク
リレート等がある。電荷を持たないビニール化合
物を併用する場合には、電荷を持たない化合物の
み重合して、生成した高分子に電離性の基が実質
的に含まれなくなる様なことがない様に反応性と
ビニール化合物の使用量を比率の関係に注意しな
ければならない。
この場合に利用できる電離して電荷を持つ事の
できる染料としては通常の酸性染料と塩基性染料
が一般に使用できる。負の電荷を有する高分子化
合物を与える様なビニール化合物を使用した場合
には塩基性染料を、正の電荷を有する高分子化合
物を与える様なビニール化合物を使用した場合に
は、酸性染料を使用する。即ち塩基性染料は染料
分子が正の電荷を有しているので負の電荷を有す
る高分子化合物に特に良く染着し、一方酸性染料
は染料分子の負の電荷を有しているので正の電荷
を有する高分子化合物に特に良く染着するので、
画像状に生成した高分子化合物に対応して色素画
像が得られるのである。
写真乳剤の結合剤としてゼラチンを用いた場合
には、ゼラチンが両性電解質であるので、ゼラチ
ンの等電点を考慮に入れて染色しなければならな
い。即ち使用するゼラチンの等電点より高いPHで
はゼラチンは負の電荷を持ち、低いPHでは正の電
荷を持つている。従つて負の電荷を有する様な高
分子化合物が生成する場合にはゼラチンの等電点
より低いPHで、塩基性染料で染色すれば、ゼラチ
ンに染めつくことなく高分子画像のみを染色する
事ができる。又、最初、等電点より高いPHで一様
に染色しておいて、ゼラチンの等電点より低いPH
の洗液で洗滌すると高分子の画像のない部分が洗
い出されて、高分子画像の部分のみが着色した状
態にする事ができる。正の電荷を有する高分子画
像を酸性染料で染色する場合には同様にゼラチン
の等電点より高いPHの条件で染色すれば良い。も
ちろんPHが高すぎたり低すぎたりすると、染料の
溶解度が下つたり、電荷をもつべき高分子の電離
が妨害されたりするので、最も適当なPHの範囲は
使用されるビニール化合物、染料の種類及びゼラ
チン等の結合剤の種類によつて変化するが、通常
の石灰処理による等電点が約4.9のゼラチンを使
用した場合には負の電荷を有する高分子化合物を
塩基性染料で染色する場合にはPH2.5〜4.5、正の
電荷を有する高分子化合物を酸性染料で染色する
場合にはPH5.0〜8.0が適当である。使用し得る染
料の例としては酸性染料では、C.I.アシツド・イ
エロー（Acid yellow）７（C.I.56205）、C.I.アシ
ツド・イエロー（Acid yellow）23（C.I.19140）、
C.I.アシツド・レツド（Acid Red）１（C.
I.18050）、C.I.アシツド・レツド（Acid Red）52
（C.I.45100）、C.I.アシツド・ブルー（Acid Blue）
９（C.I.42090）、C.I.アシツド・ブルー（Acid
Blue）45、C.I.アシツド・ブルー（Acid Blue）
62（C.I.62045）、C.I.アシツド・ヴアイオレツト
（Acid Violet）７（C.I.18055）等、塩基性染料と
してはC.I.ベイシツク・イエロー（Basic yellw）
１（C.I.49005）、C.I.ベイシツク・イエロー
（Basic yellow）２（C.I.41000）、C.I.ベイシツ
ク・レツド（Basic Red）１（C.I.45160）、C.I.ベ
イシツク・レツド（Basic Red）２（C.I.50240）、
C.I.ベイシツク・ブルー（Basic Blue）25（C.
I.52025）、C.I.ベイシツク・ヴアイオレツト
（Basic Violet）３（C.I.42555）、C.I.ベイシツ
ク・ヴアイオレツト（Basic Violet）10（C.
I.45170）等がある。ここであげた染料の番号は
カラーインデツクス（第二版）によるものであ
り、此等の染料は種種の商品名で市販されてい
る。
この方法を実施するには電磁波又は粒子線によ
る照射を行つてから、還元重合反応を行わせ、次
に染色を行う必要がある。
照射と還元、重合を行つた後に未重合のビニー
ル単量体のみを洗い流すと、重合物の画像を残す
事ができる。重合物は単量体より一般に溶解しに
くいし、使用されたハロゲン化銀写真乳剤の結合
剤として最初から加えられた高分子化合物がゼラ
チンの如く水に溶解してしまわない残つて居る場
合には、重合物がゼラチン層中で殆んど拡散でき
ない為に、重合した部分のみが残つて画像を形成
する。ビニール基を２個以上有する単量体を混合
して使用すると、重合物の非溶解性、非拡散性を
更に強める事ができる。
重合を行わせた後に前記の如く染色すれば、高
分子画像と結びついた色素画像が得られる。この
色素画像は、定着操作によつてハロゲン銀を除去
し、更に酸化剤及び銀塩の溶剤を作用させて銀画
像を溶解し去ると鮮明な画像として利用する事が
できる。非常に重合開始効率の良い還元剤を使用
した場合には、ごく微量の還元銀しか生じない状
態で既に充分重合反応が起るので、銀画像を酸化
除去する必要が全くあるいはほとんどない場合も
ある。
更に生じた色素画像を他の支持体に転写するこ
ともできる。転写を行うには、上記の如くして生
成した色素画像を有する層を、メタノール、水、
酸、塩基、塩の水溶液の如き色素の溶媒で湿らし
ておいて、転写すべき支持体と密接に接触させる
ことによつて行なわれる。転写される支持体とし
ては、普通の紙、親水性ポリマー層又はゼラチン
層を塗布した紙、親水性ポリマー層又はゼラチン
層を塗布したフイルム等が用いられる。ゼラチン
層を塗布した支持体に転写する場合には、従来の
ダイトランフアー法で用いられたのと同じ様に、
アルミニウム塩等で媒染処理されたものを使用す
ると好都合である。電荷を持つ事のできる高分子
の画像を一度作成すると、それを上記の如く染色
転写して、複数の複製を得る事ができる。一回の
染色で、数枚の転写像を得ることができ、又、一
つの高分子画像は多数回染色を繰り返す事ができ
るので、多数の複製を容易に作ることができる。
実施例 １
75モル％の塩化銀、24.5モル％の臭化銀および
0.5モル％の沃化銀からなるハロゲン化銀乳剤を
粒子形成時には石灰ゼラチンを用い、希釈ゼラチ
ンとして酸処理ゼラチンを用いて調製し、通常の
方法で硫黄増感、金増感した。ハロゲン化銀粒子
の平均粒子径は0.20μｍであつた。ポリエチレン
テレフタレートに支持体の両面に下塗りを行なつ
てから、一方の面にアチハレーシヨン層を塗布し
た後に、他方の面に上記のハロゲン化銀乳剤を増
感色素として550ｍμに感光極大を有するメロシ
アニン色素を加え、硬膜剤としてゼラチン100ｇ
当り約1.5ｇのムコクロール酸を加え更に適当な
安定剤、表面活性剤を加えたものを１m2当り0.2
ｇの銀と４ｇのゼラチンを含む様に塗布し、更に
乳剤層の上に約0.8μｍのゼラチンよりなる保護層
を塗布して塗膜試料を作製した。
この試料を段差0.15（△logE）の階段ウエツジ
に密着せしめ、200ルツクスの白色タングステン
光（2860K）で１秒間露光してから、赤色の安全
光の下で下記の現像液に40℃で２分間浸した。
２−アクリルアミド−２−メチルプロパンスルホ
ン酸 250ｇ
亜硫酸ナトリウム ７ｇ
無水炭酸ナトリウム ５ｇ
フエノール化合物（第１表記載） 0.09モル
水酸化ナトリウムでPHを10.2に調整して、水を加
えて １
水洗後、下記の定着液で定着した。
チオ硫酸ナトリウム（無水） 150ｇ
メタ重亜硫酸カリウム 15ｇ
水を加えて １
充分定着、水洗した試料を赤色塩基性染料ロー
ダミン6G.C.P.（Rhodamine6G.C.P.C.I.Basic
Red1）の0.1％水溶液に５分間漬け室温で放置し
た。更に水洗すると余分の染料が流れ落ち画像状
の重合体の上に赤色染料が付着して赤色画像を生
じた。この赤色画像よりフアーマー減力液で還元
銀を酸化して除去し鮮明な赤色画像を得た。
この赤色画像の緑色光に対する光学濃度を測定
し、濃度を2.0にするのに必要な露光量の逆数を
感度と定義し、試料２の感度を100とした時の相
対感度を第１表に示した。
本発明内のフエノール化合物を還元剤として含
むサンプルNo.１からNo.６はいずれも重合画像を生
じ。
本発明外のフエノール化合物であるハイドロキ
ノンを含むサンプルNo.７カテコールを含むサンプ
ルNo.８およびフエノール化合物を含まないNo.９は
重合画像を生じなかつた。
The present invention relates to a method for forming images using polymers. In particular, the present invention relates to a method of selectively producing a polymer compound in a portion corresponding to a photographic latent image by the action of a silver halide photographic emulsion and a reducing agent. Various methods have been proposed for forming images by polymerizing vinyl compounds to produce polymeric compounds through the action of light. Direct photopolymerization using silver halide as a catalyst has also been proposed (UK Patent No. 86631, S. Levinos et al., Photographic Science and Engineering).
Science & Engineering) Volume 6 No. 222-226
(1962)). In this reaction, the products generated by photolysis of silver halide are thought to act as direct catalysts for polymerization, and the sensitivity is not as high as that of reducing silver halide grains by normal development. Not obtained. Furthermore, after the exposed silver halide emulsion grains are developed with an ordinary developer, a vinyl compound is polymerized using the resulting silver image or unreacted silver halide as a catalyst to form a polymer compound. It has also been proposed to generate images in the form of images (Belgium Patent No. 642477, etc.). This reaction has the disadvantage that the development operation and the polymerization operation must be carried out separately. Developing exposed silver halide with a reducing compound in the presence of a vinyl compound and causing polymerization of the vinyl compound by the oxidation product or its intermediate product produced in the process is as follows:
Such a reaction is carried out using a so-called benzenoid compound, which already has two or more hydroxyl groups, amino groups, alkyl, or aryl-substituted amino groups at mutually ortho or para positions on the benzene ring, as a reducing agent. (U.S. Pat. No. 3,019,104, G. Oster. Nature, Vol. 180, p. 1275 (1957)). However, in this example of a reaction using a benzenoid compound, only an increase in the optical density of the silver halide image was observed, and an increase in viscosity that directly supported the growth of the polymer, or the generation of reaction heat was confirmed. No isolation of product molecules was performed. Furthermore, other researchers have reported that they were not successful in follow-up testing (S. Levinos and
FWH Mueller, Photographic Science & Engineering, Vol. 6, p. 222 (1962)). Then, in the presence of exposed silver halide, a vinyl compound is polymerized using a resorcinol, naphthol, pyrazolone, or hydrazine compound as a polymerization initiator, as described in Japanese Patent Publication Nos. 11149-1970 and 50-50.
No. 10488, No. 45-30338, No. 46-21723, No. 47
−18585, No. 46-6581, No. 47-14667, No. 47
-14668, 47-14669, 477-12638, 47-14669, 477-12638,
No. 47-20741, No. 49-1569, No. 49-1570, No.
No. 49-48769 and No. 49-10697. Although these inventions produced polymers of vinyl compounds, the sensitivity was still not sufficient. Furthermore, an invention using hydroquinone or the like as a polymerization initiator is disclosed in JP-A-55-149939,
This is because a polymerization reaction occurs in the areas where the silver halide has not been reduced, that is, in the non-exposed areas, and a positive image is formed with respect to the silver halide image. This is still not sufficient in terms of sensitivity. It is an object of the present invention to provide a sensitive method for polymerizing vinyl compounds in the presence of exposed silver halide. Another object of the present invention is to provide a highly sensitive silver halide photosensitive material capable of obtaining a negative polymer image for a silver halide image. The inventors have discovered that reduction of silver halide in the presence of a vinyl compound using the phenolic compounds described below can cause polymerization of the vinyl compound. Moreover, when a silver halide photographic emulsion is used as the silver halide, the reaction occurs more quickly when the silver halide microcrystals contain development nuclei, and therefore, if appropriate reaction conditions and reaction time are selected, the development nuclei can be removed. Polymerization can occur selectively only in the areas where the silver halide grains containing the silver halide grains are present. The present invention is achieved by taking advantage of the above facts. That is, in the present invention, at least one phenol compound is applied to a silver halide photographic emulsion layer having a photographic latent image in the presence of a polymerizable vinyl compound, thereby selectively forming a latent image in the area where the latent image is present. Generally, this is achieved by causing polymerization of the vinyl compound. The phenol compound used in the present invention is represented by the following general formula [] or []. general formula In the formula, R 1 , R 2 , R 3 , and R 4 are each hydrogen, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group,
It represents a substituted aryl group, alkoxy group, thioalkyl group or cyano group, and at least one of R 1 , R 2 , R 3 and R 4 represents a halogen atom. Examples of alkyl groups and substituted alkyl groups include methyl, butyl, methoxyethyl, halomethyl, and benzyl groups. Examples of the aryl group and substituted aryl group include phenyl group and tolyl group. Among the halogen atoms represented by R 1 , R 2 , R 3 , and R 4 , chlorine, bromine, and iodine are preferred ;
It is preferable that R 2 , R 3 , and R 4 are all other than hydrogen atoms. Examples of the compounds used in the present invention include the following compounds. A photographic latent image is an image-like change that occurs in a silver halide photographic emulsion due to the action of electromagnetic waves or particle beams and is normally invisible to the naked eye, but becomes a visible image by developing it. It is something. In ordinary negative emulsions, a latent image is produced by the formation of development nuclei in silver halide grains that are irradiated with electromagnetic waves or particle beams, whereas in direct positive emulsions, the developing solution that was initially present on all grains is irradiated. to disappear depending on
``Fundamentals of Photographic Theory'' by James and Huggins.
Photographic Theory)” 2nd edition Morgam &
Published by Morgam., 1960, see Chapters 3 and 4). The silver halide photographic emulsion used in the present invention is
Ordinary silver halide photographic emulsions that produce development nuclei in the irradiated areas by the action of electromagnetic waves or particle beams, that is, produce negative images upon development, can also be used. It is also possible to use a so-called direct positive emulsion in which more development nuclei are present in the halogen silver grains in the other areas than in the exposed areas. In the present invention, as the silver halide photographic emulsion that produces a negative image, silver halide photographic emulsions used for ordinary development processing can be conveniently used. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide photographic emulsions can be used. The photographic emulsion used in the present invention can be subjected to chemical sensitization and optical sensitization as applied to ordinary photographic emulsions. That is, as chemical sensitization, sulfur sensitization, noble metal sensitization, and reduction sensitization can be performed.
(e.g. P. Glafkides Chimi Photo−graphique)
2nd edition Photocinema Paul Montel Paris (1957)
(See pages 247-301). The Theory of the Photographic Process
See Chapter 5 of the Photographic Process, 4th edition, Macmillan, 1977. or,
For optical sensitization, optical sensitizing dyes used in ordinary photography such as cyanine dyes and merocyanine dyes (for example, Shinichi Kikuchi et al. Scientific Photography Handbook, Volume 2, Maruzen Publishing 1959)
2013, pp. 15-24) are valid. The emulsion used in the present invention may also contain stabilizers such as those used in conventional photography. Direct positive silver halide photographic emulsions that can be used in the present invention can be prepared by utilizing solarization, Herschel effect, Kleiden effect, and Sabatier effect. An explanation of these effects is, for example, CEK
The Theory of the Photographic Process by Mees
To make direct positive silver halide emulsions, use solarization as described in Chapters 6 and 7 of The Photographic Process, Second Edition (MACMILLAN, 1954). It is sufficient to prepare a type of silver halide photographic emulsion that is easy to develop, and to expose the entire surface of the emulsion to light in advance or to make it work with chemicals so that it can be sufficiently developed without image exposure. Examples of how to prepare such emulsions can be found, for example, in British Patent Nos. 443,245 and 462,730. The Hersiel effect is caused by exposing silver halide to long-wavelength light that has been exposed to light or made fully developable by chemicals; , silver halide milk containing a large amount of silver chloride is advantageous, and to promote the Herschel effect, pinacryptol yellow,
Desensitizing dyes such as phenosaffron are also added. Methods for producing direct positive emulsions using the Herschel effect are found in, for example, British Patent No. 667,206 and US Pat. No. 2,857,273. To obtain a direct positive using the Kleiden effect, it is necessary to give a short image exposure at high illuminance, followed by a full-face exposure at relatively low light; only after this full-face exposure can the high Portions that have not received image exposure of illuminance become developable. The Sabatier effect is produced by exposing a silver halide emulsion to light in an imagewise manner, and then exposing the entire surface to light while immersed in a developer or by being exposed to chemical agents. This occurs by creating developability in areas that have not been exposed. The Kleiden effect and the Sabatier effect can easily occur practically when using a silver halide emulsion in which the initial exposure has a stronger tendency to form development nuclei inside the silver halide grains than on their surfaces. be able to. Methods for producing emulsions that are likely to generate such internal development nuclei are described, for example, in US Pat. has been done. Positives can also be made using core shell emulsions. Methods for making core-shell emulsions are described in US Pat. No. 3,761,276 and US Pat. No. 3,206,313. The above photographic emulsion consists of a system in which silver halide grains are dispersed in a solution of a polymeric substance, and gelatin is widely used as the polymeric substance, but other hydrophilic colloids may also be used. can. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid (or poly(meth)
An ester bond of glycidyl (meth)acrylate to acrylic acid. ), polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., a variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate and gelatin oxygen decomposition product may also be used.
As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent No. 2614928, U.S. Patent No. 3132945,
3186846, 3312553, British Patent No. 861414,
It is described in No. 1033189, No. 1005784, and Japanese Patent Publication No. 42-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferred. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. Typical synthetic hydrophilic polymer substances include West German patent applications (OLS)
No. 2312708, U.S. Patent No. 3620751, U.S. Patent No. 3879205,
This is described in Japanese Patent Publication No. 7561/1973. The phenol compound of the present invention is normally used as a polymerization inhibitor to improve the storage stability of monomers, and as an antioxidant for plastics, rubber, etc., but there is no example of it being used as a polymerization initiator as in the present invention. . As described above, it is revolutionary to use a phenol compound, which has been conventionally used as a polymerization inhibitor, as a polymerization initiator as in the present invention. The reaction mechanism by which polymerization of vinyl compounds occurs as a result of the reduction of silver halide by the phenolic compounds is still unclear. However, since compounds that undergo radical polymerization are generally available, the reaction proceeds in an aqueous solution, and oxygen delays the polymerization reaction, it is thought that polymerization proceeds by a radical mechanism. It is not yet clear whether radicals are generated directly by the reaction between the phenol compound and silver halide, or whether radicals are generated by further interaction with water, oxygen, etc. in the system. If the irradiated silver halide is reduced with the phenol compound and then the vinyl compound is added to the reaction system, no polymerization is observed, so the polymerization of the vinyl compound occurs at the same time as the silver halide is reduced. It is clear that this will occur. Therefore, it is considered that an intermediate product between silver halide and the phenol compound contributes to the reaction. In the so-called tanning development method, which cross-links gelatin using the oxidation product of a developing agent, which is a well-known method for forming images using polymers by utilizing the photosensitivity of silver halide, the resulting image is formed on gelatin. It is limited to products that have been crosslinked. However, the polymer images obtained in the present invention have various properties depending on the vinyl compound used, so it is possible to obtain properties such as dyeability and chemical resistance that cannot be obtained with gelatin crosslinked images. The feature is that it can be done. Furthermore, in the method of the present invention, the presence of sulfite ions in the system promotes polymerization of the vinyl compound. Sulfite ions may be added as compounds that already contain sulfite ions, such as alkali metal or ammonium sulfites or bisulfites, or may be added as alkali metal or ammonium pyrosulfites or bisulfites. It may also be added as a substance that decomposes in an aqueous solution to generate sulfite ions, such as an adjunct with an aldehyde such as formaldehyde or glyoxal. The appropriate amount of sulfite ion to be added depends on the phenol compound used, the type and amount of vinyl monomer, and the system.
Although it varies depending on the pH etc., 0.002 mol or more, particularly 0.01 mol or more per reaction system is effective. The addition of sulfites to photographic developers is well known. In this case, the sulfite is thought to prevent auto-oxidation of the developing agent by reacting with oxidation products of the developing agent such as hydroquinone para-aminophenol, and also prevent the development reaction from occurring non-uniformly. (e.g. CEK Mees)
Author, The Theory of the Photographic Process
Photographic Process (2nd edition) published by Macmillan, 1954 (see page 652)). In the present invention, since the intermediate product of the oxidation of the phenol compound by silver halide initiates polymerization, the polymerization promoting effect of the sulfite is due to the above-mentioned action of removing oxidation products in the ordinary developer. It must be noted that they are fundamentally different. If the sulfite simply scavenges oxidation products, polymerization should rather be inhibited. In addition, sulfite is a well-known compound as a reducing agent in redox reactions, and polymerization using a silver halide-sulfite ion system may be considered, but in the experiments conducted in the present invention, phenolic compounds as described in the present invention were not used. In the absence of , the resulting polymerization was almost negligible. Although the mechanism of action of sulfite in the present invention is not clear, it seems reasonable to assume that it prevents the polymerization inhibition effect caused by oxygen. In the present invention, the vinyl compound used is a liquid or solid addition-polymerizable compound at room temperature, or a mixture thereof. Such compounds include acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylamide, N-t-
Butylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, aluminum acrylate, sodium acrylate, methacrylamide, methyl methacrylate, methyl acrylate, ethyl acrylate, 2-acrylamide-2
-Methipropanesulfonic acid, vinylpyrrolidone,
Examples include 2-vinylpyridine, 4-vinylpyrine, 2-methyl-N-vinylimidazole, potassium vinylbenzenesulfonate, and vinylcarbazole. Compounds having two or more vinyl groups are particularly advantageous in the present invention, and can be used in combination with a compound having one vinyl group as described above, or alone as a compound having a plurality of vinyl groups such as this. Use with. An example of such a compound is N.
N'-methylene bisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, divinylbenzene bisphenol-A-dimethacrylate, trimethylolpropane triacrylate , pentaerythritol tetraacrylate,
Bisoxyethylated bisphenol-A-diacrylate or unsaturated monomers containing urethane groups such as di-(2'-methacryloxyethyl)-
These include reaction products of diol mono(meth)arylates and diisocyanates, such as 2,4-tolylene diurethane and di-(2'-acryloxyethyl)trimethylene diurethane. In the present invention, a water-soluble vinyl compound may be used, or a water-insoluble vinyl compound may be added as an emulsion or dissolved in an appropriate solvent to carry out polymerization. Emulsification can be carried out according to a conventional method in the presence of a surfactant and/or a polymer compound using a suitable stirring device. This reaction generally proceeds well under alkaline conditions, but the most suitable pH is silver halide, phenol compounds,
The reaction is possible at a pH of about 8 or higher, and a pH of 9 or higher is particularly convenient, depending on the type and concentration of the vinyl compound and medium polymer compound, and the reaction temperature. When applying a photographic emulsion to a support,
This photosensitive material can be irradiated with electromagnetic radiation or particle beams and then immersed in an alkaline aqueous solution to allow the reaction to proceed. The reducing agent or vinyl compound may be contained in this alkaline aqueous solution, or may be contained in the photosensitive material. The reaction can be easily stopped by making the system acidic, for example, by reducing the pH to 5 or less, but it is also possible to remove the reactants by cooling and washing, dissolve the silver halide with a photographic fixer, or inhibit polymerization. It can also be stopped by adding agents to the system. When vinyl compound monomers are added to the photosensitive material from the beginning, the weight of the vinyl compound used is 1/1/2 of the polymer compound added in advance.
30 to 30 times, especially 1/4 to 4 times is advantageous. In addition, the silver halide used is 1/1000 to twice the weight of the polymer compound used in advance,
Particularly advantageous is a weight of 4/1000 to 1/2.
Further, when the phenol compound of the present invention is added to the sensitive material in advance, it is convenient to add it in an amount of 1/10 to 20 moles per mole of silver halide used. The phenol compound may be dissolved in water or an organic solvent, or dissolved in water or an organic solvent with the addition of a suitable surfactant, and may be added at the time of preparing the sensitive material. When adding a vinyl compound to a processing solution, it is usually advantageous to have a concentration as high as possible, and the amount added to the solution is rather limited by the solubility of the vinyl compound used in the processing solution. When adding a phenol compound used as a reducing agent to the processing solution, the optimum concentration differs somewhat depending on the compound used, but the appropriate concentration is 1/1000 mol to 5 mol, especially 1/1. 500 mol to 1 mol is advantageous. Further, when adding the phenol compound, it may be added as an aqueous solution or an organic solvent solution, and a surfactant may be further added to solubilize it. The light-sensitive material of the present invention may contain an inorganic or organic hardening agent. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl dantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, etc.), active halogen compounds (2,4-dichloro −
6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc., alone. Or it can be used in combination. A specific example is US Patent No. 1870354
No. 2080019, No. 2726162, No. 2870013,
Same No. 2983611, No. 2992109, No. 3047394, Same No.
No. 3057723, No. 3103437, No. 3321313, No.
No. 3325287, No. 3362827, No. 3539644, No. 3325287, No. 3362827, No. 3539644, No.
3543292, British Patent No. 676628, British Patent No. 825544, British Patent No.
1270578, German Patent No. 872153, German Patent No. 1090427,
It is described in Tokuko No. 34-7133, No. 46-1872, etc. The photosensitive material used in the present invention may contain various known surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, and prevention of adhesion. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) , polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and non-ionic materials such as urethanes or ethers. Surfactants: triterpenoid saponins, alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates,
Carboxyl esters such as alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl phosphates, etc. group, sulfo group, phospho group,
Anionic surfactants containing acidic groups such as sulfate ester groups and phosphate ester groups: Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine imides, and amine oxides. :
Alkylamine salts, aliphatic or aromatic quaternary
Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Specific examples of these surfactants are listed in the U.S. patent.
No. 2240472, No. 2831766, No. 3158484, No.
No. 3210191, No. 3294540, No. 3507660, British Patent No. 1012495, No. 1022878, No. 1179290, British Patent No.
No. 1198450, Japanese Unexamined Patent Publication No. 117414, US patent
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, British Patent No. 1397218, US Patent No. 3133816, No. 3441413,
Same No. 3475174, No. 3545974, No. 3726683, Same No.
No. 3843368, Belgian Patent No. 731126, British Patent
No. 1138514, No. 1159825, No. 1374780, Tokko Akira
40-378, 40-379, 43-13822, U.S. Patent No. 2271623, 2288226, 2944900, U.S. Pat.
No. 3253919, No. 3671247, No. 3772021, No.
3589906, 3666478, 3754924, West German patent application OLS 1961638, Japanese Patent Application Laid-Open No. 50-59025, etc. In the photographic light-sensitive material produced using the present invention, the silver halide photographic emulsion layer and other layers may be made of plastic film ordinarily used in photographic light-sensitive materials.
Flexible supports such as paper, cloth or glass, ceramics,
Applied to a rigid support such as metal. Useful as flexible supports are films, baryta layers or alpha-olefin polymers of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. In the present invention, any electromagnetic waves or particle beams to which ordinary photographic emulsions are sensitive can be used as the electromagnetic waves or particle beams that can be used to obtain photographic images. That is, particle beams such as visible light, ultraviolet light, infrared rays of 1.3μ or less, X-rays, gamma rays, electron beams, and alpha rays can be applied. In particular, conventional methods include tungsten lamps, fluorescent lamps, mercury lamps, xenon, arc lamps, carbon arc lamps, xenon flash lamps, halogen lamps, light emitting diodes, cathode ray tubes, flying spots, discharge tubes such as glow tubes, argon lasers, etc. Any of various known light sources such as laser light can be used.
Fluorescence time is not only exposure time of 1/1000 second to 50 seconds, but also exposure time shorter than 1/1000 second, such as 1/10 4 to 1/1 using xenon flash lamp, cathode ray tube, or laser light.
0.6 frequent exposures can be used, or exposures longer than 50 seconds can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. When using the method of the present invention to record images,
Differences in physical and chemical properties such as solubility, light scattering, adhesiveness, dyeability, etc. between vinyl compounds and their polymers can be utilized in various ways. By taking advantage of the difference in solubility, by dissolving the unpolymerized portion after irradiation and reaction, an image created by the polymer substance remains only in the irradiated area. can be formed. In this case, it is more convenient for the initially added polymer compound to be dissolved away together with unreacted monomers. Therefore, the polymer compound contained in the system from the beginning is either so-called two-dimensional linear with almost no crosslinking, or it is so high that the main chain or crosslinks are easily severed. It is convenient that the molecular compound and the polymer compound produced by the one-sided reaction are so-called three-dimensional crosslinked polymers. For this purpose, it is convenient to use the aforementioned compound having a plurality of vinyl groups alone or in combination with a compound having one vinyl group. However, even if the generated polymeric substance is a two-dimensional soluble polymeric substance, as a result of interaction with the polymeric compound added in advance, some parts of the polymeric substance are generated by reaction and others are not. The use of monomers with multiple vinyl groups is not an essential condition, since there are often significant differences in solubility between the moieties (eg, in the case of polyacrylic acid and gelatin). Images made of polymeric substances created using the method of the present invention can also be used in various printing methods. Further, the present invention can also be used in a method of forming a dye image. In this method, a monomer having a group that can be charged by ionization or the addition of hydrogen cations is used as the vinyl monomer, and the vinyl monomer can be charged by ionization or addition of hydrogen cations. The image is selectively dyed with a dye of opposite charge. The dye image thus produced can also be transferred to another support by various methods. Addition-polymerizable vinyl compounds that can be charged by ionization or addition of hydrogen cations that can be used in this case include those that give the produced polymer compound a negative charge, such as acrylic acid and methacrylic acid. , itaconic acid, vinyl compounds with carboxyl groups such as maleic acid, ammonium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate, zinc acrylate, cadmium acrylate, sodium methacrylate, methacrylate. Calcium acrylate, Magnesium methacrylate,
Vinyl compounds having metal salts or ammonium salts of carboxyl groups such as zinc methacrylate, cadmium methacrylate, sodium itaconate, and sodium maleate; vinyl compounds having sulfonic acid groups such as vinyl sulfonic acid and P-vinylbenzenesulfonic acid; There are vinyl compounds with metal salts or ammonium salts of sulfonic acid such as ammonium vinylsulfonate, sodium vinylsulfonate, potassium vinylsulfonate, potassium P-vinylbenzenesulfonate, and the resulting polymer has a positive charge. For example, 2-vinylpyridine, 4-vinylpyridine, 5-vinyl-2-methylpyridine, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate , N,N-diethylaminoethyl methacrylate, and their bases include methyl chloride, ethyl bromide,
There are nitrogen-containing vinyl compounds that are quaternary salts made by reacting dimethyl sulfate, diethyl sulfate, methyl p-toluenesulfonate, etc. The methods for synthesizing these compounds are well known, and commercially available products are also available. These compounds may be used alone or in combination of two or more. Further, it may be used in combination with a water-soluble addition-polymerizable vinyl compound that does not have an electric charge. Vinyl compounds that can be used in combination include acrylamide, N-hydroxymethylacrylamide, methacrylamide, methyl methacrylate, vinylpyrrolidone, N,N-methylenebisacrylamide, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, etc. . When using an uncharged vinyl compound in combination, make sure that the reactivity and the vinyl do not polymerize only the uncharged compound and the resulting polymer does not substantially contain ionizable groups. Pay attention to the relationship between the amount of the compound used and the ratio. In this case, ordinary acidic dyes and basic dyes can be used as dyes that can be ionized and have a charge. When using a vinyl compound that gives a polymer compound with a negative charge, use a basic dye; when using a vinyl compound that gives a polymer compound with a positive charge, use an acidic dye. do. In other words, basic dyes have a positive charge on their dye molecules, so they dye particularly well on negatively charged polymer compounds, whereas acidic dyes have a negative charge on their dye molecules, so they dye particularly well on polymeric compounds that have a negative charge. Because it dyes particularly well on charged polymer compounds,
A dye image is obtained corresponding to the image-formed polymer compound. When gelatin is used as a binder in a photographic emulsion, the isoelectric point of gelatin must be taken into consideration when dyeing, since gelatin is an ampholyte. That is, gelatin has a negative charge at a pH higher than the isoelectric point of the gelatin used, and has a positive charge at a lower pH. Therefore, when a polymer compound with a negative charge is generated, if it is dyed with a basic dye at a pH lower than the isoelectric point of gelatin, it is possible to dye only the polymer image without staining the gelatin. Can be done. Also, first, dye uniformly at a pH higher than the isoelectric point, and then dye at a pH lower than the isoelectric point of gelatin.
When washed with the washing liquid, the parts without the polymer image are washed out, and only the part with the polymer image can be colored. When staining a positively charged polymer image with an acidic dye, the dyeing may be performed under conditions of a pH higher than the isoelectric point of gelatin. Of course, if the pH is too high or low, the solubility of the dye will decrease and the ionization of polymers that should have an electric charge will be hindered, so the most appropriate pH range depends on the vinyl compound used and the type of dye. It varies depending on the type of binder such as gelatin, but when gelatin with an isoelectric point of about 4.9 after normal lime treatment is used, it is difficult to dye a negatively charged polymer compound with a basic dye. PH2.5 to 4.5 is suitable for dyeing, and PH5.0 to 8.0 is suitable for dyeing positively charged polymer compounds with acidic dyes. Examples of dyes that can be used include acid dyes such as CI Acid Yellow 7 (CI56205), CI Acid Yellow 23 (CI19140),
CI Acid Red 1 (C.
I.18050), CI Acid Red 52
(CI45100), CI Acid Blue
9 (CI42090), CI Acid Blue (Acid
Blue) 45, CI Acid Blue
62 (CI62045), CI Acid Violet 7 (CI18055), etc., and CI Basic Yelw as a basic dye.
1 (CI49005), CI Basic Yellow 2 (CI41000), CI Basic Red 1 (CI45160), CI Basic Red 2 (CI50240),
CI Basic Blue 25 (C.
I.52025), CI Basic Violet 3 (CI42555), CI Basic Violet 10 (C.
I.45170) etc. The dye numbers listed here are from the Color Index (2nd edition), and these dyes are commercially available under various trade names. To carry out this method, it is necessary to perform irradiation with electromagnetic waves or particle beams, perform a reduction polymerization reaction, and then perform dyeing. If only the unpolymerized vinyl monomer is washed away after irradiation, reduction, and polymerization, it is possible to leave an image of the polymerized product. Polymers are generally more difficult to dissolve than monomers, and if the polymer compound added from the beginning as a binder for the silver halide photographic emulsion used remains, such as gelatin, which does not dissolve in water. Since the polymer hardly diffuses in the gelatin layer, only the polymerized portion remains to form an image. When monomers having two or more vinyl groups are used in combination, the non-solubility and non-diffusibility of the polymer can be further strengthened. If dyeing is performed as described above after polymerization, a dye image combined with a polymer image can be obtained. This dye image can be used as a clear image by removing the silver halide through a fixing operation and further dissolving the silver image by the action of an oxidizing agent and a silver salt solvent. If a reducing agent with very high polymerization initiation efficiency is used, the polymerization reaction will already occur sufficiently with only a very small amount of reduced silver produced, so there may be no or almost no need to oxidize and remove the silver image. . Additionally, the resulting dye image can be transferred to other supports. To perform the transfer, the layer with the dye image produced as described above is mixed with methanol, water,
This is accomplished by moistening the dye with a solvent, such as an aqueous solution of an acid, base, or salt, and bringing it into intimate contact with the support to be transferred. The support to be transferred may be ordinary paper, paper coated with a hydrophilic polymer layer or gelatin layer, film coated with a hydrophilic polymer layer or gelatin layer, or the like. When transferring a gelatin layer to a coated support, the same method as used in the conventional dye transfer method is used.
It is convenient to use a mordant treated with aluminum salt or the like. Once an image of a polymer capable of carrying a charge is created, it can be dyed and transferred as described above to obtain multiple copies. Several transfer images can be obtained by one dyeing process, and one polymer image can be dyed many times, making it easy to make many copies. Example 1 75 mol% silver chloride, 24.5 mol% silver bromide and
A silver halide emulsion containing 0.5 mol % silver iodide was prepared using lime gelatin for grain formation and acid-treated gelatin as diluted gelatin, and sulfur-sensitized and gold-sensitized using conventional methods. The average grain size of the silver halide grains was 0.20 μm. After undercoating polyethylene terephthalate on both sides of the support, and applying an achihalation layer on one side, a merocyanine dye having a maximum sensitivity at 550 mμ was applied to the other side using the above silver halide emulsion as a sensitizing dye. In addition, 100g of gelatin as a hardening agent.
Approximately 1.5g of mucochloric acid is added to the mixture, and appropriate stabilizers and surfactants are added to the solution at a rate of 0.2g per m2 .
A coating film sample was prepared by coating the emulsion layer so as to contain 1 g of silver and 4 g of gelatin, and further coating a protective layer of about 0.8 μm of gelatin on the emulsion layer. This sample was placed in close contact with a step wedge with a step difference of 0.15 (△logE), exposed to 200 lux white tungsten light (2860K) for 1 second, and then exposed to the following developer under red safety light at 40°C for 2 minutes. Soaked. 2-Acrylamide-2-methylpropanesulfonic acid 250g Sodium sulfite 7g Anhydrous sodium carbonate 5g Phenol compound (listed in Table 1) Adjust the pH to 10.2 with 0.09M sodium hydroxide, add water 1. After washing with water, proceed as follows. It was fixed with a fixer. Sodium thiosulfate (anhydrous) 150g Potassium metabisulfite 15g Add water 1 Thoroughly fix and wash the sample with red basic dye Rhodamine 6G.CP (Rhodamine6G.CPCIBasic)
It was immersed in a 0.1% aqueous solution of Red1) for 5 minutes and left at room temperature. Further washing with water caused the excess dye to run off and the red dye was deposited on the image-shaped polymer, producing a red image. From this red image, the reduced silver was oxidized and removed using a Farmar reducing solution to obtain a clear red image. The optical density of this red image with respect to green light is measured, and the reciprocal of the exposure amount required to make the density 2.0 is defined as sensitivity. Table 1 shows the relative sensitivity when the sensitivity of sample 2 is set as 100. Ta. Samples No. 1 to No. 6 containing the phenol compound of the present invention as a reducing agent all produced polymerized images. Sample No. 8 containing hydroquinone, which is a phenolic compound outside the present invention; Sample No. 8 containing catechol; and Sample No. 9 containing no phenolic compound did not produce a polymerized image.
【表】
実施例 ２
フエノール化合物を溶液にして感材調製時に添
加した以外は実施例１と同様にして試料を調製し
た。添加したフエノール化合物の量はハロゲン化
銀と当モルで、塗布銀量は0.2ｇ／m2であつた。
この試料を実施例１の現像液からフエノール化合
物を除いた以外は実施例１と同様に処理して感度
を測定した。試料11の感度を100とした時の相対
感度を第２表に示した。[Table] Example 2 A sample was prepared in the same manner as in Example 1, except that the phenol compound was made into a solution and added at the time of preparing the sensitive material. The amount of the phenol compound added was equimolar to the silver halide, and the amount of coated silver was 0.2 g/m 2 .
This sample was processed in the same manner as in Example 1 except that the phenol compound was removed from the developer in Example 1, and the sensitivity was measured. Table 2 shows the relative sensitivity when the sensitivity of sample 11 is set as 100.
【表】
本発明フエノール化合物を含むサンプルNo.10か
らNo.14はいずれも重合画像を生じた。フエノール
化合物を含まないNo.15は重合画像を生じなかつ
た。
実施例 ３
１m2当りアクリル酸ナトリウムを2.5ｇ、ゼラ
チンを2.5ｇ、銀を0.2ｇ含む以外は実施例１と同
様にして塗膜試料を作製した。この試料を実施例
１と同様に露光し下記の現像液に40℃で２分間浸
した。
亜硫酸ナトリウム ７ｇ
無水炭酸ナトリウム ５ｇ
フエノール化合物（第３表記載） 0.09モル
水酸化ナトリウムでPHを10.2に調整して水を加え
て １
実施例１と同様に処理し、感度を測定した。サ
ンプルNo.17の感度を10として相対感度を第３表に
記載した。[Table] Samples No. 10 to No. 14 containing the phenol compound of the present invention all produced polymerized images. No. 15 containing no phenol compound did not produce a polymerized image. Example 3 A coating sample was prepared in the same manner as in Example 1 except that 2.5 g of sodium acrylate, 2.5 g of gelatin, and 0.2 g of silver were contained per m 2 . This sample was exposed in the same manner as in Example 1 and immersed in the following developer at 40°C for 2 minutes. Sodium sulfite 7g Anhydrous sodium carbonate 5g Phenol compound (listed in Table 3) 0.09 mol The pH was adjusted to 10.2 with sodium hydroxide and water was added. 1 The same procedure as in Example 1 was carried out, and the sensitivity was measured. Relative sensitivities are listed in Table 3, setting the sensitivity of sample No. 17 to 10.
【表】
本発明のフエノール化合物を含むサンプルNo.16
からNo.18はいずれも重合画像を生じた。フエノー
ル化合物を含まないNo.19は重合画像を生じなかつ
た。
実施例 ４
１m2当り２−アクリルアミド−２−メチルプロ
パンスルホン酸ナトリウムを2.5ｇ、ゼラチンを
2.5ｇ、銀を0.2ｇ、0.002モルのフエノール化合物
を含む以外は実施例１と同様にして塗膜試料を作
製した。この試料を実施例１と同様にして露光
し、下記の現像液に40℃で２分間浸した。
亜硫酸ナトリウム ７ｇ
無水炭酸ナトリウム ５
水酸化ナトリウムでPHを10.2に調整して水を加え
て １
以下実施例１と同様に処理し、感度を測定し
た。
サンプルNo.21の感度を100として相対感度を第
４表に示した。[Table] Sample No. 16 containing the phenol compound of the present invention
and No. 18 all produced polymerized images. No. 19 containing no phenol compound did not produce a polymerized image. Example 4 2.5 g of sodium 2 -acrylamido-2-methylpropanesulfonate and gelatin per 1 m 2
A coating sample was prepared in the same manner as in Example 1 except that it contained 2.5 g of silver, 0.2 g of silver, and 0.002 mol of a phenol compound. This sample was exposed in the same manner as in Example 1 and immersed in the following developer at 40° C. for 2 minutes. Sodium sulfite 7g Anhydrous sodium carbonate 5 The pH was adjusted to 10.2 with sodium hydroxide and water was added. 1 The following treatment was carried out in the same manner as in Example 1, and the sensitivity was measured. Relative sensitivities are shown in Table 4, setting the sensitivity of sample No. 21 as 100.
【表】
本発明のフエノール化合物を含むサンプルNo.20
からNo.22は重合画像を生じたが、フエノール化合
物を含を含まないサンプルNo.23は重合画像を生じ
なかつた。[Table] Sample No. 20 containing the phenol compound of the present invention
Sample No. 22 produced a polymerized image, but sample No. 23, which did not contain a phenol compound, did not produce a polymerized image.
Claims (1)
とも１つの存在下で現像核を有するハロゲン化銀
を下記一般式〔〕また〔〕で示されるフエノ
ール化合物を用いて還元し、現像核を有するハロ
ゲン化銀において選択的にビニル化合物を重合さ
せることを特徴とする画像形成方法。 一般式 式中、R1、R2、R3、R4は各々水素、ハロゲン
原子、アルキル基、置換アルキル基、アリール
基、置換アリール基、アルコキシ基、チオアルキ
ル基又はシアノ基を表わし、R1、R2、R3、R4の
内少くとも１つはハロゲン原子を表わす。[Claims] 1. Silver halide having development nuclei is reduced using a phenol compound represented by the following general formula [] or [] in the presence of at least one addition-polymerizable vinyl compound, and development is performed. An image forming method characterized by selectively polymerizing a vinyl compound in silver halide having a nucleus. general formula In the formula, R 1 , R 2 , R 3 , and R 4 each represent hydrogen, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a thioalkyl group, or a cyano group, and R 1 , R At least one of 2 , R 3 and R 4 represents a halogen atom.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6026581A JPS57176033A (en) | 1981-04-21 | 1981-04-21 | Formation of picture using polymer |
| DE19823214537 DE3214537A1 (en) | 1981-04-21 | 1982-04-20 | Process for producing polymeric images |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6026581A JPS57176033A (en) | 1981-04-21 | 1981-04-21 | Formation of picture using polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57176033A JPS57176033A (en) | 1982-10-29 |
| JPH0147777B2 true JPH0147777B2 (en) | 1989-10-16 |
Family
ID=13137140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6026581A Granted JPS57176033A (en) | 1981-04-21 | 1981-04-21 | Formation of picture using polymer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS57176033A (en) |
| DE (1) | DE3214537A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0619570B2 (en) | 1986-02-07 | 1994-03-16 | 富士写真フイルム株式会社 | Photosensitive material |
| US4719280A (en) * | 1986-09-29 | 1988-01-12 | E. I. Du Pont De Nemours And Company | Anisotropic melt polyesters with improved glass transition temperature |
| US5158847A (en) * | 1989-10-19 | 1992-10-27 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member comprising an azo pigment as a charge generating material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE731640A (en) * | 1968-04-19 | 1969-10-01 | ||
| JPS4910697B1 (en) * | 1968-12-10 | 1974-03-12 | ||
| DE3206030A1 (en) * | 1981-02-19 | 1982-09-09 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | Process for formation of polymeric images and printing plates |
-
1981
- 1981-04-21 JP JP6026581A patent/JPS57176033A/en active Granted
-
1982
- 1982-04-20 DE DE19823214537 patent/DE3214537A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57176033A (en) | 1982-10-29 |
| DE3214537C2 (en) | 1992-12-03 |
| DE3214537A1 (en) | 1982-11-11 |
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