JPH07120016B2 - Image forming method - Google Patents
Image forming methodInfo
- Publication number
- JPH07120016B2 JPH07120016B2 JP61089511A JP8951186A JPH07120016B2 JP H07120016 B2 JPH07120016 B2 JP H07120016B2 JP 61089511 A JP61089511 A JP 61089511A JP 8951186 A JP8951186 A JP 8951186A JP H07120016 B2 JPH07120016 B2 JP H07120016B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- layer
- compound
- light
- emulsion
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 67
- 239000000126 substance Substances 0.000 claims description 43
- -1 silver halide Chemical class 0.000 claims description 41
- 229910052709 silver Inorganic materials 0.000 claims description 32
- 239000004332 silver Substances 0.000 claims description 32
- 238000011161 development Methods 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 1
- 239000000975 dye Substances 0.000 description 130
- 239000010410 layer Substances 0.000 description 92
- 150000001875 compounds Chemical class 0.000 description 70
- 239000000839 emulsion Substances 0.000 description 64
- 239000000463 material Substances 0.000 description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- 239000002585 base Substances 0.000 description 38
- 238000010438 heat treatment Methods 0.000 description 34
- 108010010803 Gelatin Proteins 0.000 description 25
- 229920000159 gelatin Polymers 0.000 description 25
- 239000008273 gelatin Substances 0.000 description 25
- 235000019322 gelatine Nutrition 0.000 description 25
- 235000011852 gelatine desserts Nutrition 0.000 description 25
- 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 25
- 239000000243 solution Substances 0.000 description 25
- 239000003638 chemical reducing agent Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 20
- 239000002243 precursor Substances 0.000 description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000012546 transfer Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 239000011241 protective layer Substances 0.000 description 10
- 238000011160 research Methods 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 206010070834 Sensitisation Diseases 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000008313 sensitization Effects 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001235 sensitizing effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000011033 desalting Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical compound [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000009918 complex formation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical group C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001409 amidines Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 150000002357 guanidines Chemical class 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 125000005647 linker group Chemical group 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
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VQIQPNAYDOXKST-UHFFFAOYSA-M sodium;4-(2-ethylhexoxy)-4-oxobutanoate Chemical compound [Na+].CCCCC(CC)COC(=O)CCC([O-])=O VQIQPNAYDOXKST-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- HXMRAWVFMYZQMG-UHFFFAOYSA-N 1,1,3-triethylthiourea Chemical compound CCNC(=S)N(CC)CC HXMRAWVFMYZQMG-UHFFFAOYSA-N 0.000 description 1
- FUOSTELFLYZQCW-UHFFFAOYSA-N 1,2-oxazol-3-one Chemical group OC=1C=CON=1 FUOSTELFLYZQCW-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical class C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- VYNUATGQEAAPAQ-UHFFFAOYSA-N 2-sulfonylacetic acid Chemical compound OC(=O)C=S(=O)=O VYNUATGQEAAPAQ-UHFFFAOYSA-N 0.000 description 1
- OOKDVIRNOUPNFD-UHFFFAOYSA-N 3-(4-acetamidophenyl)prop-2-ynoic acid Chemical compound CC(=O)NC1=CC=C(C#CC(O)=O)C=C1 OOKDVIRNOUPNFD-UHFFFAOYSA-N 0.000 description 1
- UEGFKFNFTYLWMM-UHFFFAOYSA-N 3-azaniumylbutan-2-ylazanium;dichloride Chemical compound Cl.Cl.CC(N)C(C)N UEGFKFNFTYLWMM-UHFFFAOYSA-N 0.000 description 1
- UAEYLNOMJREEAO-UHFFFAOYSA-N 3-phenylprop-2-ynoic acid;silver Chemical compound [Ag].OC(=O)C#CC1=CC=CC=C1 UAEYLNOMJREEAO-UHFFFAOYSA-N 0.000 description 1
- LROUPBJRCFXQIH-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-2-one Chemical compound N1=C(C)C=CN2NC(=O)N=C21 LROUPBJRCFXQIH-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical class NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003819 basic metal compounds Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- BOCHMRRKXXKQIJ-UHFFFAOYSA-N carbamimidoylazanium;pyridine-2-carboxylate Chemical compound NC(N)=N.OC(=O)C1=CC=CC=N1 BOCHMRRKXXKQIJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SAIGUZYNPDJAHY-UHFFFAOYSA-N ethane;2-ethenylsulfonylacetamide Chemical compound CC.NC(=O)CS(=O)(=O)C=C SAIGUZYNPDJAHY-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/40—Development by heat ; Photo-thermographic processes
- G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
- G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は熱現像により色素画像を形成する方法に関する
ものである。The present invention relates to a method of forming a dye image by heat development.
（先行技術とその問題点） 熱現像で色画像（カラー画像）を得る方法については、
既に多くの方法が提案されている。(Prior art and its problems) Regarding the method of obtaining a color image (color image) by heat development,
Many methods have already been proposed.
現像薬の酸化体とカプラーとの結合により色画像を形成
する方法については、米国特許第3,531,286号、米国特
許第3,761,270号、ベルギー特許第802,519号、リサーチ
・ディスクロージャー1975年９月号31頁〜32頁、米国特
許第4,021,240号等に提案されている。For the method of forming a color image by combining an oxidant of a developing agent and a coupler, U.S. Pat. No. 3,531,286, U.S. Pat.No. 3,761,270, Belgian Pat.No. 802,519, Research Disclosure, September 1975, pages 31-32 Page, U.S. Pat. No. 4,021,240 and the like.
また、感光銀色素漂白法によりポジの色画像を形成する
方法については、例えば、リサーチ・ディスクロージャ
ー1976年４月号30頁〜32頁（RD−14433）、同1976年12
月号14頁〜15頁（RD−15227）、米国特許第4,235,957号
等に記載されている。For the method of forming a positive color image by the light-sensitive silver dye bleaching method, see, for example, Research Disclosure, April 1976, pp. 30-32 (RD-14433), 12: 1976.
Monthly pages 14 to 15 (RD-15227), U.S. Pat. No. 4,235,957 and the like.
しかし、上記の方法では形成された色素像と銀像とが混
在しているため、鮮明な色素像が得られないという問題
があった。However, the above method has a problem that a clear dye image cannot be obtained because the formed dye image and silver image are mixed.
この欠点を改良するため種々の方法が提案されている。
例えば加熱により画像状に可動性の色素を放出させ、こ
の可動性の色素を水などの溶媒によって媒染剤を有する
色素固定材料に転写する方法、高沸点有機溶剤により色
素固定材料に転写する方法、色素固定材料に内蔵させた
親水性熱溶剤により色素固定材料に転写する方法、可動
性の色素が熱拡散性または昇華性であり、支持体等の色
素受容材料に転写する方法などが挙げられる（米国特許
第4,463,079号、同第4,474,867号、同第4,478,927号，
同第4,507,380号、同第4,500,626号、同第4,483,914
号；特開昭58−149046号、同58−149047号、同59−1524
40号、同59−154445号、同59−165054号、同59−180548
号、同59−168439号、同59−174832号、同59−174833
号、同59−174834号、同59−174835号、同59−218443
号、特願昭60−79709号など）。Various methods have been proposed to remedy this drawback.
For example, a method of releasing a movable dye imagewise by heating and transferring the movable dye to a dye fixing material having a mordant with a solvent such as water, a method of transferring to a dye fixing material with a high boiling organic solvent, a dye Examples include a method of transferring to a dye fixing material by a hydrophilic thermal solvent incorporated in the fixing material, and a method of transferring to a dye receiving material such as a support where the movable dye is heat diffusible or sublimable (US Patents 4,463,079, 4,474,867, 4,478,927,
No. 4,507,380, No. 4,500,626, No. 4,483,914
JP; A 58-149046, JP 58-149047, and JP 59-1524.
40, 59-154445, 59-165054, 59-180548
No. 59, No. 168439, No. 59-174832, No. 59-174833
No. 59-174834, 59-174835, 59-218443.
No. 60/79709).
上記の画像形成方法では、可動性色素を感光要素から色
素固定要素へ転写した後、色素固定要素を感光要素から
引き剥すが、この際感光要素の塗布膜と色素固定要素の
塗布膜が一体化して容易に剥離できなかったり、あるい
は無理に剥離すると塗布膜がはがれて剥離面に損傷や汚
れが生じたりして、満足すべき鮮明な画像が得られない
という問題があった。In the above image forming method, the movable dye is transferred from the light-sensitive element to the dye-fixing element, and then the dye-fixing element is peeled off from the light-sensitive element. At this time, the coating film of the light-sensitive element and the coating film of the dye-fixing element are integrated. There is a problem in that a satisfactory clear image cannot be obtained because the coating film is peeled off to cause damage or stains on the peeled surface when the film is forcibly peeled off.
かかる問題を解決するために、特開昭61−20944号には
剥離面に弗素系界面活性剤を存在させる方法が記述され
ている。しかし、ここに具体的に挙げられている化合物
は、充分な転写濃度を得るために転写の際の加熱温度を
上げたり、加熱時間を延長したりしたときの剥離性に関
しては未だ満足できるものではなく、更に微量の水並び
に塩基及び／又は塩基プレカーサーの存在下に感光要素
と色素固定要素の組合せを加熱して現像と転写を同時に
行う方法における剥離性を改良するには不十分な性能し
か持たなかった。In order to solve such a problem, JP-A-61-20944 describes a method in which a fluorine-containing surfactant is present on the release surface. However, the compounds specifically listed here are still not satisfactory in terms of releasability when the heating temperature during transfer is increased or the heating time is extended to obtain a sufficient transfer density. In addition, it has insufficient performance to improve the releasability in the method of simultaneously performing development and transfer by heating the combination of the light-sensitive element and the dye-fixing element in the presence of a trace amount of water and a base and / or a base precursor. There wasn't.
（発明の目的） 従って、本発明の目的は、熱現像と色素の転写後の感光
要素と色素固定要素の剥離性が改良された画像形成方法
を提供することである。OBJECTS OF THE INVENTION Accordingly, it is an object of the present invention to provide an image forming method in which the releasability of a light-sensitive element and a dye fixing element after heat development and transfer of a dye is improved.
（発明の構成） 本発明の目的は、感光層中に少なくとも感光性ハロゲン
化銀、バインダーおよび熱現像により拡散性の色素を生
成または放出する色素供与性物質を含有する感光要素を
源露光後または像露光と同時に加熱し、生成または放出
された拡散性色素を色素固定要素の色素固定層へ転写し
次いで感光要素と色素固定要素を剥離する画像形成方法
において、前記色素固定要素の少なくとも最上層に下記
一般式（Ｉ）で表される界面活性剤を含有することを特
徴とする画像形成方法によって達成された。(Constitution of the Invention) An object of the present invention is to provide a light-sensitive element containing at least a light-sensitive silver halide, a binder, and a dye-donor substance capable of forming or releasing a diffusible dye by heat development in a light-sensitive layer after source exposure or In the image forming method, in which the diffusible dye formed or released is transferred to the dye fixing layer of the dye fixing element by heating at the same time as the imagewise exposure, and then the light-sensitive element and the dye fixing element are peeled off, at least the uppermost layer of the dye fixing element. It is achieved by an image forming method characterized by containing a surfactant represented by the following general formula (I).
式中、Rf，Rf′は炭素数５〜16のパーフルオロアルキル
基もしくはω位に水素原子１コを有するパーフルオロア
ルキル基またはパーフルオロアルケニル基を表わす。
R1，R2は水素原子、アルキル基、アルケニル基、アラル
キル基を表わし、R1とR2の炭素数の総和は５〜22であ
る。 In the formula, R f and R f ′ represent a perfluoroalkyl group having 5 to 16 carbon atoms or a perfluoroalkyl group having 1 hydrogen atom at the ω-position or a perfluoroalkenyl group.
R 1 and R 2 represent a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group, and the total number of carbon atoms of R 1 and R 2 is 5 to 22.
A,A′は −CO−または を表わす。（ここで、n,n′は１〜５の整数を表わし、
Ｒ′は水素原子または低級アルキル基を表わす。）a,b,
c,dは各々０又は１を表わすが、ａとｂおよびａとｃが
同時に０になることはない。Ｚはスルホン酸又はその
塩、カルボン酸又はその塩、リン酸又はその塩、−OSO3
M（ここでＭは水素原子又はアルカリ金属を表わす）、
CH2CH2OmH（ここでｍは１〜10の整数を表わす）、
オニウム塩またはベタイン基を表わす。A, A ′ is -CO- or Represents (Here, n and n'represent an integer of 1 to 5,
R'represents a hydrogen atom or a lower alkyl group. ) A, b,
Each of c and d represents 0 or 1, but a and b and a and c cannot be 0 at the same time. Z is sulfonic acid or a salt thereof, carboxylic acid or a salt thereof, phosphoric acid or a salt thereof, -OSO 3
M (where M represents a hydrogen atom or an alkali metal),
CH 2 CH 2 O m H (where m represents an integer of 1 to 10),
Represents an onium salt or betaine group.
一般式（Ｉ）について更に詳細に説明する。The general formula (I) will be described in more detail.
一般式（Ｉ）のRf，Rf′は各々炭素数５〜16のパーフル
オロアルキル基もしくはω−位に水素原子１個を有する
パーフルオロアルキル基またはパーフルオロアルケニル
基を表わす。この基は直鎖でも分岐でもよい。一般式
（Ｉ）でｂ＝ｄ＝１の場合、RfとRf′は同一でも互いに
異なっていてもよい。RfとRf′の具体例としては、C6F
13−，C8F17−，H(CF2CH2)4−，C6H11−，C9F17−，C10
F21−等が挙げられる。R f and R f ′ in the general formula (I) each represent a perfluoroalkyl group having 5 to 16 carbon atoms or a perfluoroalkyl group having one hydrogen atom at the ω-position or a perfluoroalkenyl group. This group may be linear or branched. When b = d = 1 in the general formula (I), R f and R f ′ may be the same or different from each other. A specific example of R f and R f ′ is C 6 F
13 -, C 8 F 17 - , H (CF 2 CH 2) 4 -, C 6 H 11 -, C 9 F 17 -, C 10
F 21- and the like.
一般式（Ｉ）のR1，R2は各々水素原子、アルキル基、ア
ルケニル基、アラルキル基を表わす。但し、R1とR2の炭
素数の総和は５〜22である。Rf，Rf′の炭素数又はR1と
R2の炭素数の総和が５より少ないと本発明で意図した剥
離性改良の効果は得られない。炭素数が上記各々の上限
を越えると有機溶媒（メタノールなど）に対する溶解性
が低下して、親水性コロイド層中へ安定に添加すること
が困難になる。本発明の効果は特にR1とR2の炭素数の総
和が７〜22、更には８〜22の範囲で顕著である。R1，R2
の例としては、CH3−，C2H5−，C5H11，C8H17−，C12H
25−，C14H29−，C16H33，C18H37−， C8H15−，C12H23−，C18H35−などが挙げられる。R 1 and R 2 in the general formula (I) each represent a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group. However, the total number of carbon atoms of R 1 and R 2 is 5 to 22. Carbon number of R f , R f ′ or R 1 and
If the total carbon number of R 2 is less than 5, the effect of improving the peeling property intended by the present invention cannot be obtained. When the number of carbon atoms exceeds the above upper limits, the solubility in an organic solvent (such as methanol) decreases, and it becomes difficult to stably add it to the hydrophilic colloid layer. The effect of the present invention is particularly remarkable when the total number of carbon atoms of R 1 and R 2 is 7 to 22, more preferably 8 to 22. R 1 , R 2
For example, CH 3 −, C 2 H 5 −, C 5 H 11 , C 8 H 17 −, C 12 H
25- , C 14 H 29- , C 16 H 33 , C 18 H 37- , C 8 H 15 -, C 12 H 23 -, C 18 H 35 - , and the like.
一般式（Ｉ）のA,A′は −CONHCH2 n， （ここでn,n′は１〜５の整数を表わし、Ｒ′は水素原
子または低級アルキル基を表わす。）より具体的には などがあり、この中でも が好ましい。A and A ′ in the general formula (I) are -CONHCH 2 n , (Here, n and n'represent an integer of 1 to 5, and R'represents a hydrogen atom or a lower alkyl group.) More specifically Etc. Among these, Is preferred.
一般式（Ｉ）においてＺはスルホン酸又はその塩、カル
ボン酸又はその塩、リン酸又はその塩、−OSO3M（ここ
でＭは水素原子又はアルカリ金属を表わす）、CH2CH2
OmH（ここでｍは１〜10の整数を表わす）、オニウム
塩またはベタイン基を表わす。より具体的には、−SO3N
a，−COONa,−PO4Na，−OSO3Na，CH2CH2O4， などがある。In the general formula (I), Z is sulfonic acid or a salt thereof, carboxylic acid or a salt thereof, phosphoric acid or a salt thereof, -OSO 3 M (where M represents a hydrogen atom or an alkali metal), CH 2 CH 2
O m H (where m represents an integer of 1 to 10), an onium salt or a betaine group. More specifically, --SO 3 N
a, −COONa, −PO 4 Na, −OSO 3 Na, CH 2 CH 2 O 4 , and so on.
本発明では、特に下記一般式（II）の化合物が好ましく
使用される。In the present invention, the compound represented by the following general formula (II) is preferably used.
ここで、Rf,A,Z,R1は前記と同様の意味を持つ。但しR1
の炭素数は５〜22、特に７〜22である。 Here, R f , A, Z and R 1 have the same meanings as described above. However, R 1
Has 5 to 22, especially 7 to 22 carbon atoms.
以下に本発明に使用される一般式（Ｉ）の化合物の具体
例を示すが、本発明はこれらに限定されるものではな
い。Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.
化合物 本発明に使用する一般式（Ｉ）で示されるこれらの化合
物は例えば米国特許4,547,459号、特開昭51−32322号、
同56−19042号等に記載の方法により合成することがで
きる。Compound These compounds represented by the general formula (I) used in the present invention are described in, for example, US Pat. No. 4,547,459, JP-A-51-32322,
It can be synthesized by the method described in No. 56-19042 or the like.
次に、本発明に使用する化合物の具体的合成例を示す。Next, specific synthesis examples of the compound used in the present invention will be shown.
合成例１ （ａ）Ｎ−ｎ−テトラデシルパーフルオロオクタンスル
ホンアミドの合成： ｎ−テトラデシルアミン（ニッサンアミンMB）46.95g
（0.22モル）、トリエチルアミン22.26g（0.22モル）、
トルエン65mlを３ツ口フラスコに入れ溶解後、C8F17SO2
F110.47g（0.22モル）を40℃以下で滴下した。同温度で
１時間、更に70℃で３時間かくはんを続けた。反応後に
酢酸エチル800mlを加え、温水（50℃）600mlで３回抽出
洗浄した。酢酸エチル相を分取し、溶媒を減圧留去後、
アセトンより再結晶し、Ｎ−ｎ−テトラデシルパーフル
オロオクタンスルホンアミドを得た。収量61.2g（40
％）、m.p.94〜95℃。Synthesis Example 1 (a) Synthesis of Nn-tetradecylperfluorooctanesulfonamide: 46.95 g of n-tetradecylamine (Nissanamine MB)
(0.22 mol), 22.26 g (0.22 mol) of triethylamine,
65 ml of toluene was placed in a 3-necked flask and dissolved, and then C 8 F 17 SO 2 was added.
F110.47 g (0.22 mol) was added dropwise at 40 ° C or lower. Stirring was continued for 1 hour at the same temperature and for 3 hours at 70 ° C. After the reaction, 800 ml of ethyl acetate was added, and the mixture was extracted and washed 3 times with 600 ml of warm water (50 ° C). The ethyl acetate phase was separated, the solvent was distilled off under reduced pressure,
Recrystallization from acetone gave Nn-tetradecyl perfluorooctane sulfonamide. Yield 61.2g (40
%), Mp 94-95 ° C.
（ｂ）化合物（３）の合成： 上記（ａ）で得られたＮ−ｎ−テトラデシルパーフルオ
ロオクタンスルホンアミド20.87g（0.03モル）、トルエ
ン21mlを３ツ口フラスコに入れ溶解後、NaOH1.56g（0.0
39モル）を加え強力にかきまぜながら50℃でブタンサル
トン5.31g（0.039モル）を滴下した。同温度で10分間、
更に70〜75℃で３時間かきまぜた。反応液にエタノール
200mlを加え、加熱溶解し不溶物を別後、液をアセ
トン400ml中に注入し、沈澱させた。沈澱を取、乾燥
して化合物（３）を得た。収量21.5g（84％）。(B) Synthesis of compound (3): 20.87 g (0.03 mol) of Nn-tetradecylperfluorooctanesulfonamide obtained in (a) above and 21 ml of toluene were placed in a three-necked flask and dissolved, and then NaOH 1. 56g (0.0
(39 mol) was added thereto, and 5.31 g (0.039 mol) of butanesultone was added dropwise at 50 ° C with strong stirring. 10 minutes at the same temperature,
Further, the mixture was stirred at 70 to 75 ° C for 3 hours. Ethanol in the reaction solution
After adding 200 ml and heating to dissolve and separating insoluble matter, the solution was poured into 400 ml of acetone for precipitation. The precipitate was taken and dried to obtain the compound (3). Yield 21.5g (84%).
合成例２ 化合物（19）の合成： 合成例１の（ａ）で得られたＮ−ｎ−テトラデシルパー
フルオロオクタンスルホンアミド20.87g（0.03モル）、
NaOH0.31gを３ツ口フラスコに入れ90〜95℃でかくはん
しながらエチレンオキシドを吹込み反応させた。エチレ
ンオキシドの付加モル数は重量増加とNMRより確認し
た。反応後に飽和NaCl水と酢酸エチルとで４回抽出洗浄
した。酢酸エチル相を分取し、脱色、溶媒留去し、目的
物を得た。収量24.0g（92％）。Synthesis Example 2 Synthesis of compound (19): 20.87 g (0.03 mol) of Nn-tetradecyl perfluorooctane sulfonamide obtained in (a) of Synthesis Example 1;
0.31 g of NaOH was placed in a three-necked flask and ethylene oxide was blown into the reaction while stirring at 90 to 95 ° C. The number of moles of ethylene oxide added was confirmed by weight increase and NMR. After the reaction, the mixture was extracted and washed 4 times with saturated aqueous NaCl and ethyl acetate. The ethyl acetate phase was separated, decolorized and the solvent was distilled off to obtain the desired product. Yield 24.0 g (92%).
合成例３ 化合物（２）の合成： 合成例２で得られた化合物（19）23.2g（0.26モル）、
トルエン7mlを３ツ口フラスコに入れ溶解後、NaOH1.35g
（0.034モル）を加え強力にかきまぜながら50℃でブタ
ンサルトン4.62g（0.034モル）を滴下した。滴下終了
後、同温度で10分間、更に70〜75℃で３時間かきまぜ
た。反応液にメタノール／トルエン（＝24ml/30ml）の
混合液を加え、加熱溶解した。不溶物を別後、液を
アセトニトリル／アセトン混合液（150ml/50ml）中に注
入し沈澱させた。沈澱を取、乾燥し、目的物を得た。
収量14.0g（52％）。Synthesis Example 3 Synthesis of Compound (2): 23.2 g (0.26 mol) of the compound (19) obtained in Synthesis Example 2,
Toluene (7 ml) was placed in a three-necked flask and dissolved.
(0.034 mol) was added and, while stirring vigorously, 4.62 g (0.034 mol) of butanesaltone was added dropwise at 50 ° C. After the completion of dropping, the mixture was stirred at the same temperature for 10 minutes and further at 70 to 75 ° C for 3 hours. A mixed solution of methanol / toluene (= 24 ml / 30 ml) was added to the reaction solution, and the mixture was heated and dissolved. After removing the insoluble matter, the solution was poured into an acetonitrile / acetone mixed solution (150 ml / 50 ml) to cause precipitation. The precipitate was removed and dried to obtain the desired product.
Yield 14.0 g (52%).
本発明の化合物は、製造能率や画像の品質等を考慮し
て、色素固定要素の少なくとも最上層に含有させる。The compound of the present invention is contained in at least the uppermost layer of the dye fixing element in consideration of production efficiency, image quality and the like.
本発明の化合物の添加量は広い範囲にわたって変化させ
ることができるが、好ましくは支持体１平方メートル当
たり0.001g〜1.0g、特に0.01g〜0.5g、更には0.03g〜0.
3gの範囲で使用する。The addition amount of the compound of the present invention can be varied over a wide range, but preferably 0.001 g to 1.0 g, particularly 0.01 g to 0.5 g, and further 0.03 g to 0.
Use in the range of 3g.
本発明の化合物を使用することにより、感光要素と色素
固定要素の剥離性は顕著に改良される。特に微量の水と
塩基及び／又は塩基プレカーサーの存在下感光要素と色
素固定要素の組み合わせを加熱して現像と色素の転写を
同時に行う方法において、本発明の化合物による剥離性
の改良は著しい。また、本発明の化合物は、これを添加
した写真要素、特に感光要素の保存安定性を悪化させな
いという特性を有する。更に、本発明の化合物を使用す
ることにより、感光要素や色素固定要素の滑り性が改良
され、また感光要素や色素固定要素を重ね合わせて保存
したときに接着しにくくなるという効果を得ることがで
きる。By using the compound of the present invention, the releasability between the light-sensitive element and the dye-fixing element is remarkably improved. In particular, in the method of simultaneously developing and transferring a dye by heating a combination of a light-sensitive element and a dye-fixing element in the presence of a trace amount of water and a base and / or a base precursor, the releasability of the compound of the present invention is remarkably improved. Further, the compound of the present invention has a characteristic that the storage stability of a photographic element to which the compound is added, particularly a light-sensitive element, is not deteriorated. Furthermore, by using the compound of the present invention, it is possible to improve the slipperiness of the light-sensitive element and the dye-fixing element, and obtain the effect that the light-sensitive element and the dye-fixing element are less likely to adhere to each other when stored overlaid. it can.
本発明においては、熱現像と色素の転写の工程は、それ
ぞれ独立であってもよいし、同時であってもよい。ま
た、一工程のなかで現像にひきつずき転写が行なわれる
という意味で連続であってもよい。In the present invention, the steps of heat development and dye transfer may be independent or simultaneous. Further, it may be continuous in the sense that the scratch transfer is performed for the development in one step.
例えば、（１）感光要素に画像露光し、加熱したあと、
色素固定要素を重ねて、必要に応じて加熱して可動性色
素を色素固定要素に転写する方法、（２）感光要素を画
像露光し、色素固定要素を重ねて加熱する方法がある。
上記（１）、（２）の方法は実質的に水が存在しない状
態で実施することもできるし、微量の水の存在下で行う
こともできる。For example, (1) after imagewise exposing the photosensitive element and heating,
There are a method of stacking dye-fixing elements and heating as required to transfer the movable dye to the dye-fixing element, and a method of (2) image-exposing the photosensitive element and stacking and heating the dye-fixing elements.
The above methods (1) and (2) can be carried out in the substantially absence of water, or can be carried out in the presence of a trace amount of water.
熱現像工程での加熱温度は、約50℃〜約250℃で現像可
能であるが、特に約80℃〜約180℃が有用である。微量
の水の存在下で加熱する場合は加熱温度の上限は沸点以
下である。転写工程を熱現像工程終了後に行う場合、転
写工程での加熱温度は、熱現像工程における温度から室
温の範囲で転写可能であるが、特に50℃以上で熱現像工
程における温度よりも約10℃低い温度までがより好まし
い。The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. When heating in the presence of a trace amount of water, the upper limit of the heating temperature is the boiling point or lower. When the transfer step is carried out after the completion of the heat development step, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but especially at 50 ° C or higher, about 10 ° C higher than the temperature in the heat development step. Up to a lower temperature is more preferable.
本発明において好ましい画像形成方法は、画像露光後ま
たは画像露光と同時に微量の水ならびに塩基及び／又は
塩基プレカーサーの存在下で加熱し、現像と同時に録画
像に対応又は逆対応する部分において生成した拡散性色
素を色素固定層に移すものである。この方法によれば、
拡散性色素の生成ないし放出反応が極めて速く進行し、
拡散性色素の色素固定層への移動も速やかに進行するの
で、高濃度の色画像が短時間で得られる。In the present invention, a preferable image forming method is that after or at the same time as the image exposure, heating is performed in the presence of a small amount of water and a base and / or a base precursor, and at the same time as the development, the diffusion generated in the portion corresponding to or opposite to the recorded image. The sex dye is transferred to the dye fixing layer. According to this method
The generation or release reaction of the diffusible dye proceeds extremely quickly,
The migration of the diffusible dye to the dye-fixing layer also progresses rapidly, so that a high-density color image can be obtained in a short time.
この態様で使用する水の量は、感光要素及び色素固定要
素の全塗布膜の重量の少なくとも0.1倍、好ましくは0.1
倍以上で該全塗布膜の最大膨潤体積に相当する溶媒の重
量以下（特に全塗布膜の最大膨潤体積に相当する溶媒の
重量から全塗布膜の重量を差引いた量以下）という少量
でよい。The amount of water used in this embodiment is at least 0.1 times the weight of the total coating film of the light-sensitive element and the dye-fixing element, preferably 0.1.
It may be as small as or more than twice the weight of the solvent corresponding to the maximum swelling volume of the entire coated film (particularly less than or equal to the weight of the solvent corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film).
膨潤時の膜の状態は不安定であり、条件によっては局所
的ににじみを生ずるおそれがありこれを避けるには感光
要素と色素固定要素の全塗布膜厚の最大膨潤時の体積に
相当する水の量以下が好ましい。具体的には感光要素と
色素固定要素の合計の面積１平方メートル当り1g〜50
g、特に2g〜35g、更には3g〜25gの範囲が好ましい。The state of the film at the time of swelling is unstable, and local bleeding may occur depending on the conditions. Or less is preferable. Specifically, the total area of the light-sensitive element and the dye-fixing element is 1 g to 50 per square meter.
The range of g, particularly 2 g to 35 g, and further 3 g to 25 g is preferable.
この態様において用いる塩基及び／又は塩基プレカーサ
ーは感光要素にも色素固定要素にも内蔵できる。また水
に溶解させて供給することもできる。塩基及び塩基プレ
カーサーとしては以下に述べるものを挙げることができ
る。The base and / or base precursor used in this embodiment can be incorporated in both the light-sensitive element and the dye-fixing element. It can also be dissolved in water and supplied. Examples of the base and the base precursor include those described below.
本発明に用いられる塩基としては、アルカリ金属、アル
カリ土類金属、アンモニウム、４級アルキルアンモニウ
ム等の水酸化物、炭酸塩、重炭酸塩、ホウ酸塩、第２お
よび第３リン酸塩、キノリン酸塩、メタホウ酸塩等の無
機塩基；脂肪族アミン類（トリアルキルアミン類、ヒド
ロキシルアミン類、脂肪族ポリアミン類）、芳香族アミ
ン類（Ｎ−アルキル置換芳香族アミン類、Ｎ−ヒドロキ
シルアルキル置換芳香族アミン類およびビス〔ｐ−（ジ
アルキルアミノ）フェニル〕メタン類）、複素環状アミ
ン類、アミジン類、環状アミジン類、グアニジン類、環
状グアニジン類等の有機塩基およびそれらの炭酸塩、重
炭酸塩、ホウ酸塩、第２および第３リン酸塩等が挙げら
れ、また米国特許第2,410,644号にはベタインヨウ化テ
トラメチルアンモニウム、ジアミノブタンジヒドロクロ
ライドが、米国特許3,506,444号にはウレア、６−アミ
ノカプロン酸のようなアミノ酸を含む有機化合物が記載
され有用である。本発明においてpKaの値が８以上のも
のが特に有用である。Examples of the base used in the present invention include alkali metal, alkaline earth metal, ammonium, quaternary alkylammonium hydroxide, carbonate, bicarbonate, borate, secondary and tertiary phosphates, and quinoline. Salts, inorganic bases such as metaborates; aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines), aromatic amines (N-alkyl substituted aromatic amines, N-hydroxylalkyl substituted) Aromatic amines and bis [p- (dialkylamino) phenyl] methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines and other organic bases, and their carbonates and bicarbonates , Borate, secondary and tertiary phosphates, and the like, and US Pat. No. 2,410,644 discloses betaine iodide tetramethylammonium. , Diaminobutane dihydrochloride is, U.S. Patent No. 3,506,444 urea is useful is described organic compound containing amino acids such as 6-aminocaproic acid. In the present invention, a pKa value of 8 or more is particularly useful.
本発明に用いられる塩基プレカーサーとは、熱分解、電
解または錯形成反応等により塩基を放出あるいは生成す
るものである。The base precursor used in the present invention is one that releases or produces a base by thermal decomposition, electrolysis or complex formation reaction.
塩基プレカーサーとしてはまず加熱により脱炭酸して分
解する有機酸と塩基の塩、ロッセン転位、ベックマン転
位などにより分解してアミンを放出する化合物など加熱
によりなんらかの反応を引き起して塩基を放出するもの
が挙げられる。As a base precursor, a salt of an organic acid and a base that is decarboxylated by heating to decompose, a compound that decomposes to release an amine by Rossen rearrangement, Beckmann rearrangement, etc. that causes some reaction by heating and releases a base. Is mentioned.
有機酸と塩基の塩に用いられる塩基として、前記した無
機塩基または有機塩基などが挙げられる。また、有機酸
としては、例えばトリクロロ酢酸、トリフロロ酢酸、プ
ロピオール酸、シアノ酢酸、スルホニル酢酸、アセト酢
酸など、米国特許第4,088,496号に記載の２−カルボキ
シカルボキサミドなどが挙げられる。Examples of the base used for the salt of an organic acid and a base include the above-mentioned inorganic bases and organic bases. Examples of the organic acid include trichloroacetic acid, trifluoroacetic acid, propiolic acid, cyanoacetic acid, sulfonylacetic acid and acetoacetic acid, and 2-carboxycarboxamide described in US Pat. No. 4,088,496.
有機酸と塩基の塩以外に、例えばロッセン転位を利用し
た特開昭59−168440号記載のヒドロキサムカルバメート
類、ニトリルを生成する特開昭59−157637号記載のアル
ドキシムカルバメート類、などが有効であり、また、リ
サーチディスクロージャー誌1977年５月号15776号に記
載のアミンイミド類、特開昭50−22625号公報に記載さ
れているアルドンアミド類、等は高温で分解し塩基を生
成するもので好ましく用いられる。In addition to salts of organic acids and bases, for example, hydroxam carbamates described in JP-A-59-168440 utilizing the Rossen rearrangement, aldoxime carbamates described in JP-A-59-157637 that form nitriles, etc. are effective. In addition, the amine imides described in Research Disclosure, May 1977, No. 15776, the aldonamides described in JP-A No. 50-22625, etc. are preferable because they decompose to form a base at high temperature. Used.
電解により塩基を発生させる塩基プレカーサーとして次
のものを挙げることができる。The following can be mentioned as base precursors that generate a base by electrolysis.
例えば、電解酸化を用いる方法の代表として各種脂肪酸
塩の電解を挙げることができる。この反応によってアル
カリ金属やグアニジン類、アミジン類等の有機塩基の炭
酸塩を極めて効率良く得ることができる。For example, electrolysis of various fatty acid salts can be mentioned as a representative method using electrolytic oxidation. By this reaction, carbonates of organic bases such as alkali metals, guanidines and amidines can be obtained very efficiently.
また電解還元を用いる方法としてはニトロおよびニトロ
ソ化合物の還元によるアミン類の生成；ニトリル類の還
元によるアミン類の生成；ニトロ化合物、アゾ化合物、
アゾキシ化合物等の還元によるｐ−アミノフェノール
類、ｐ−フェニレンジアミン類、ヒドラジン類の生成等
を挙げることができる。ｐ−アミノフェノール類、ｐ−
フェニレンジアミン類、ヒドラジン類は塩基として用い
るだけでなく、それらを直接色画像形成物質として使用
することもできる。As a method using electrolytic reduction, amines are produced by reduction of nitro and nitroso compounds; amines are produced by reduction of nitriles; nitro compounds, azo compounds,
Examples include production of p-aminophenols, p-phenylenediamines, and hydrazines by reduction of azoxy compounds and the like. p-aminophenols, p-
The phenylenediamines and hydrazines can be used not only as bases but also directly as color image forming substances.
また、種々の無機塩共存下での水の電解によりアルカリ
成分を生成させることももちろん利用できる。Further, it is of course possible to use an alkaline component produced by electrolysis of water in the presence of various inorganic salts.
次に、錯形成反応を用いて塩基を生成させる塩基プレカ
ーサーとして、例えば特願昭60−169585号に記載されて
いる難溶性金属化合物およびこの難溶性金属化合物を構
成する金属イオンと錯形成反応しうる化合物（錯形成化
合物という）との組み合わせが挙げられる。例えば、難
溶性金属化合物としては、亜鉛、アルミニウム、カルシ
ウム、バリウムなどの炭酸塩、水酸化物、酸化物が挙げ
られる。また錯形成化合物については、例えばエー・イ
ー・マーテル、アール・エム・スミス（A.E.Martell,R.
M.Smith）共著、「クリティカル・スタビリティ・コン
スタンツ（Critical Stability Constants）」第４ない
し５巻、プレナム・プレス（Plenum Press）に詳述され
ている。具体的にはアミノカルボン酸類、イミノジ酢酸
類、ピリジルカルボン酸類、アミノリン酸類、カルボン
酸類（モノ、ジ、トリ、テトラカルボン酸類およびさら
にフォスフォノ、ヒドロキシ、オキソ、エステル、アミ
ド、アルコキシ、メルカプト、アルキルチオ、フォスフ
ィノなどの置換基をもつ化合物）、ヒドロキサム酸類、
ポリアクリレート類、ポリリン酸類などのアルカリ金
属、グアニジン類、アミジン類もしくは４級アンモニウ
ム塩等との塩が挙げられる。Next, as a base precursor for producing a base by using a complex formation reaction, for example, a complex formation reaction is performed with a sparingly soluble metal compound described in Japanese Patent Application No. 60-169585 and a metal ion constituting the sparingly soluble metal compound. And a compound capable of forming a complex (referred to as a complex forming compound). For example, the sparingly soluble metal compound includes carbonates, hydroxides and oxides of zinc, aluminum, calcium, barium and the like. Further, regarding the complex-forming compound, for example, AEMartell, R.M.
M. Smith), "Critical Stability Constants," Volumes 4-5, Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and further phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, phosphino Compounds having substituents such as), hydroxamic acids,
Examples thereof include salts with alkali metals such as polyacrylates and polyphosphoric acids, guanidines, amidines and quaternary ammonium salts.
この難溶性金属化合物と錯形成化合物は、感光要素と色
素固定要素に別々に添加するのが有利である。The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.
塩基および／または塩基プレカーサーは単独でも２種以
上組み合わせても使用することができる。The base and / or the base precursor may be used alone or in combination of two or more kinds.
本発明に用いられる塩基および／または塩基プレカーサ
ーの量は、広い範囲で用いることができる。通常は感光
要素と色素固定要素の合計の塗布膜を重量換算して50重
量％以下、特に１重量％〜40重量％の範囲が有用であ
る。The amount of the base and / or base precursor used in the present invention can be used within a wide range. Usually, it is useful that the total coating film of the light-sensitive element and the dye-fixing element is 50% by weight or less in terms of weight, particularly in the range of 1% by weight to 40% by weight.
本発明では特に、塩基プレカーサーとして、水に難溶性
の塩基性金属化合物とこの難溶性金属化合物を構成する
金属イオンと水を媒体として錯形成反応しうる化合物を
含有させ、加熱時にこれらの２つの化合物の反応により
系のpHを上昇させるのが好ましい。In the present invention, in particular, as a base precursor, a water-insoluble basic metal compound and a metal ion that constitutes this hardly-soluble metal compound and a compound capable of a complex forming reaction with water as a medium are contained, and these two It is preferred to raise the pH of the system by reacting the compound.
難溶性金属化合物と錯形成化合物は、現像処理までに反
応するのを防止するために、少なくとも別層に添加する
必要がある。例えば、感光要素と色素固定要素とが同一
支持体上に設けられているいわゆるモノシート材料で
は、上記両者の添加層を別層とし、更に間に１層以上の
層を介在させるのがよい。また、より好ましい形態は、
難溶性金属化合物と錯形成化合物をそれぞれ別の支持体
上に設けた層に含有させるものである。例えば、難溶性
金属化合物を感光要素に、錯形成化合物を感光要素とは
別の支持体を持つ色素固定要素に含有させるのが好まし
い。錯形成化合物は、共存させる水の中に溶解させて供
給してもよい。難溶性金属化合物は特開昭56−17483
号、同53−102733号などに記載の方法で調整された微粒
子分散物として含有させるのが望ましく、その平均粒子
サイズは50ミクロン以下、特に５ミクロン以下が好まし
い。難溶性金属化合物は、感光要素の感光層、中間層、
保護層などのどの層に添加してもよく、２層以上に分割
して添加してもよい。The sparingly soluble metal compound and the complex-forming compound must be added to at least another layer in order to prevent them from reacting before the development processing. For example, in a so-called monosheet material in which a light-sensitive element and a dye-fixing element are provided on the same support, it is preferable that the additive layers of the both are separate layers and that one or more layers are interposed therebetween. In addition, a more preferable form is
The sparingly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. For example, it is preferable that the poorly soluble metal compound is contained in the light-sensitive element and the complex-forming compound is contained in the dye-fixing element having a support different from that of the light-sensitive element. The complex-forming compound may be dissolved in water to be coexistent and supplied. The sparingly soluble metal compound is disclosed in JP-A-56-17483.
No. 53-102733, etc., and it is desirable to include it as a fine particle dispersion prepared by the method described in JP-A No. 53-102733. The average particle size thereof is preferably 50 microns or less, particularly preferably 5 microns or less. The sparingly soluble metal compound is a photosensitive layer of the photosensitive element, an intermediate layer,
It may be added to any layer such as a protective layer, or may be divided into two or more layers and added.
難溶性金属化合物または錯形成化合物を支持体上の層に
含有させる場合の添加量は、化合物種、難溶性金属化合
物の粒子サイズ、錯形成反応速度などに依存するが、各
々塗布膜を重量に換算して50重量パーセント以下で用い
るのが適当であり更に好ましくは0.01重量パーセントか
ら40重量パーセントの範囲が有用である。また、錯形成
化合物を水の中に溶解して供給する場合には、１リット
ル当たり0.005molから5mol、特に0.05molから2molの濃
度が好ましい。更に、本発明において反応系の錯形成化
合物の含有量は難溶性化合物の含有量に対してモル比で
1/100倍から100倍、特に1/10倍から20倍が好ましい。The amount of the sparingly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the compound species, the particle size of the sparingly soluble metal compound, the complex formation reaction rate, etc. It is suitable to use it in an amount of 50% by weight or less, more preferably 0.01% by weight to 40% by weight. When the complex-forming compound is dissolved in water and supplied, a concentration of 0.005 mol to 5 mol, particularly 0.05 mol to 2 mol per liter is preferable. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is a molar ratio with respect to the content of the sparingly soluble compound.
It is preferably 1/100 to 100 times, particularly preferably 1/10 to 20 times.
感光層または色素固定層に水を付与する方法としては、
例えば、特願昭59−268926号の101頁９行〜102頁４行に
記載の方法がある。As a method of applying water to the photosensitive layer or the dye fixing layer,
For example, there is a method described in Japanese Patent Application No. 59-268926, page 101, line 9 to page 102, line 4.
現像および／または転写工程における加熱手段として
は、熱板、アイロン、熱ローラーなどの特願昭59−2689
26号の102頁14行〜103頁11行に記載の手段がある。ま
た、感光要素及び／又は色素固定要素に、グラファイ
ト、カーボンブラック、金属等の導電性材料の層を重ね
て施しておき、この導電性層に電流を通じ、直接的に加
熱するようにしてもよい。As a heating means in the developing and / or transferring process, a heating plate, an iron, a heating roller, or the like is disclosed in Japanese Patent Application No. 59-2689.
There are means described in No. 26, page 102, line 14 to page 103, line 11. Further, a layer of a conductive material such as graphite, carbon black or metal may be superposed on the photosensitive element and / or the dye fixing element, and a current may be passed through the conductive layer to directly heat the conductive layer. .
感光要素と色素固定要素とを重ね合わせ、密着させる時
の圧力条件や圧力を加える方法は特願昭59−268926号の
103頁〜104頁に記載の方法が適用できる。The pressure condition and the method of applying pressure when the photosensitive element and the dye fixing element are superposed and brought into close contact are described in Japanese Patent Application No. 59-268926.
The method described on pages 103 to 104 can be applied.
本発明の写真要素の処理には種々の熱現像装置のいずれ
もが使用できる。例えば、特開昭59−75247号、同59−1
77547号、同59−181353号、同60−18951号、実願昭60−
116734号等に記載されている装置などが好ましく使用さ
れる。Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75247 and 59-1.
77547, 59-181353, 60-18951, Jpn.
The devices described in 116734 and the like are preferably used.
加熱現像と色素転写の終了後、感光要素と色素固定要素
は剥離されるが、本発明によってこの剥離は極めて容易
に実行できる。両要素の剥離は人手によってもよいし、
また特公昭42−5474号、同41−5676号、同45−1354号、
同53−29713号、特開昭60−135944号などで周知の機械
による手段をとってもよい。After the completion of heat development and dye transfer, the light-sensitive element and the dye-fixing element are peeled off, but this peeling can be carried out very easily by the present invention. Both elements may be peeled off manually,
In addition, Japanese Patent Publications No. 42-5474, No. 41-5676, No. 45-1354,
Means using a machine well known in JP-A-53-29713 and JP-A-60-135944 may be used.
本発明において、色素画像を形成するための具体的な方
法は、熱現像によって生成又は、放出した可動性色素を
転写させることである。そのために、本発明では支持体
上に少なくとも感光性ハロゲン化銀、色素供与性物質、
バインダーおよび必要に応じて有機銀塩や還元剤を有す
る感光要素と、感光要素から拡散してくる可動性色素を
受けとめることのできる色素固定要素を用いる。In the present invention, a specific method for forming a dye image is to transfer a movable dye generated or released by thermal development. Therefore, in the present invention, at least a photosensitive silver halide, a dye-donor substance,
A photosensitive element having a binder and optionally an organic silver salt or a reducing agent, and a dye fixing element capable of receiving a movable dye diffused from the photosensitive element are used.
本発明に用いられる感光要素と色素固定要素とは２つの
支持体上に別個に塗設される形態をとるのが好ましい。The light-sensitive element and the dye-fixing element used in the present invention are preferably applied separately on two supports.
イエロー、マゼンタ、シアンの３原色を用いて、色度図
内の広範囲の色を得るために、本発明に用いられる感光
要素は、少なくとも３層のそれぞれ異なるスペクトル領
域に感光性を持つハロゲン化銀乳剤層を有する必要があ
る。In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, the light-sensitive element used in the present invention is a silver halide having sensitivity in at least three different spectral regions. It is necessary to have an emulsion layer.
互いに異なるスペクトル領域に感光性を持つ少なくとも
３つの感光性ハロゲン化銀乳剤層の代表的な組み合わせ
としては、青感性乳剤層、緑感性乳剤層および赤感性乳
剤層の組み合わせ、緑感性乳剤層、赤感性乳剤層および
赤外光感光性乳剤層の組み合わせ、青感光性乳剤層、緑
感性乳剤層および赤外光感光性乳剤層の組み合わせ、青
感性乳剤層、赤感性乳剤層および赤外光感光性乳剤層の
組み合わせなどがある。なお、赤外光感光性乳剤層とは
700nm以上、特に740nm以上の光に対して感光性を持つ乳
剤層をいう。Typical combinations of at least three photosensitive silver halide emulsion layers having sensitivities in mutually different spectral regions include a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. Combination of sensitive emulsion layer and infrared-sensitive emulsion layer, combination of blue-sensitive emulsion layer, green-sensitive emulsion layer and infrared-sensitive emulsion layer, blue-sensitive emulsion layer, red-sensitive emulsion layer and infrared-sensitive emulsion There are combinations of emulsion layers. What is the infrared-sensitive emulsion layer?
It means an emulsion layer sensitive to light of 700 nm or more, especially 740 nm or more.
本発明に用いられる感光材料は、必要に応じて同一のス
ペクトル領域に感光性を持つ乳剤層を乳剤の感度によっ
て二層以上に分けて有していてもよい。The light-sensitive material used in the present invention may optionally have two or more emulsion layers having photosensitivity in the same spectral region depending on the sensitivity of the emulsion.
上記の各乳剤層に使用し得るハロゲン化銀は、塩化銀、
臭化銀、あるいは塩臭化銀、塩沃化銀、塩沃臭化銀のい
ずれでもよい。The silver halide that can be used in each of the above emulsion layers is silver chloride,
It may be any of silver bromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.
具体的には、米国特許4,500,626号第50欄、リサーチ・
ディスクロージャー誌1978年６月号９頁〜10頁（RD1702
9）、特願昭59−228551号、同60−225176号、同60−228
267号等に記載されているハロゲン化銀乳剤のいずれも
が使用できる。Specifically, U.S. Pat.No. 4,500,626, column 50, Research
Disclosure, June 1978, pages 9-10 (RD1702
9), Japanese Patent Application Nos. 59-228551, 60-225176, and 60-228.
Any of the silver halide emulsions described in No. 267 etc. can be used.
本発明で使用するハロゲン化銀乳剤は、主として潜像が
粒子表面に形成される表面潜像型であっても、粒子内部
に形成される内部潜像型であってもよい。また粒子内部
と粒子表層が異なる相を持ったいわゆるコアシェル乳剤
であってもよい。また、本発明では内部潜像型乳剤と造
核剤とを組合わせた直接反転乳剤を使用することもでき
る。The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. It may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can be used.
ハロゲン化銀乳剤は未後熟のまま使用してもよいが通常
は化学増感して使用する。通常型感光材料用乳剤で公知
の硫黄増感法、還元増感法貴金属増感法などを単独また
は組合わせて用いることができる。これらの化学増感を
含窒素複素還化合物の存在下で行うこともできる（特開
昭58−126526号、同58−215644号）。The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known emulsions for conventional light-sensitive materials can be used alone or in combination with known methods such as sulfur sensitization method, reduction sensitization method and noble metal sensitization method. These chemical sensitizations can also be carried out in the presence of nitrogen-containing complex-reducing compounds (JP-A-58-126526 and JP-A-58-215644).
本発明において使用される感光性ハロゲン化銀の塗設量
は、銀換算1mgないし10g/m2の範囲である。The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m 2 in terms of silver.
本発明においては、感光性ハロゲン化銀と共に、有機金
属塩を酸化剤として併用することもできる。この場合、
感光性ハロゲン化銀と有機金属塩とは接触状態もしくは
接近した距離にあることが必要である。In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. in this case,
It is necessary that the photosensitive silver halide and the organic metal salt are in contact with each other or in close proximity.
このような有機金属塩の中、有機銀塩は、特に好ましく
用いられる。Among such organic metal salts, organic silver salts are particularly preferably used.
上記の有機銀塩酸化剤を形成するのに使用し得る有機化
合物としては、特願昭59−228551号の37頁〜39頁、米国
特許4,500,626号第52欄〜第53欄等に記載の化合物があ
る。また特願昭60−113235号記載のフェニルプロピオー
ル酸銀などのアルキニル基を有するカルボン酸の銀塩
や、特願昭60−90089号記載のマセチレン銀も有用であ
る。有機銀塩は２種以上を併用してもよい。Examples of the organic compound that can be used to form the above organic silver salt oxidizing agent include compounds described in Japanese Patent Application No. 59-228551, pages 37 to 39, U.S. Patent 4,500,626, columns 52 to 53, etc. There is. Further, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolic acid described in Japanese Patent Application No. 60-113235, and silver macetylene described in Japanese Patent Application No. 60-90089 are also useful. Two or more kinds of organic silver salts may be used in combination.
以上の有機銀塩は、感光性ハロゲン化銀１モルあたり、
0.01ないし10モル、好ましくは0.01ないし１モルを併用
することができる。感光性ハロゲン化銀と有機銀塩の塗
布量合計は銀換算で50mgないし10g/m2が適当である。The above organic silver salts are
0.01 to 10 mol, preferably 0.01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m 2 in terms of silver.
本発明に用いられるハロゲン化銀は、メチン色素類その
他によって分光増感されてもよい。用いられる色素に
は、シアニン色素、メロシアニン色素、複合シアニン色
素、複合メロシアニン色素、ホロポーラーシアニン色
素、ヘミシアニン色素、スチリル色素およびヘミオキソ
ノール色素が包含される。The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
具体的には、特開昭59−180550号、同60−140335号、リ
サーチ・ディスクロージャー誌1978年６月号12〜13頁
（RD17029）等に記載の増感色素や、特開昭60−111239
号、特願昭60−172967号等に記載の熱脱色性の増感色素
が挙げられる。Specifically, the sensitizing dyes described in JP-A-59-180550 and JP-A-60-140335, Research Disclosure June 1978, pages 12 to 13 (RD17029), and JP-A-60-111239.
And heat-decolorizing sensitizing dyes described in Japanese Patent Application No. 60-172967.
これらの増感色素は単独に用いてもよいが、それらの組
合わせを用いてもよく、増感色素の組合わせは特に、強
色増感の目的でしばしば用いられる。These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.
増感色素とともに、それ自身分光増感作用をもたない色
素あるいは可視光を実質的に吸収しない物質であって、
強色増感を示す物質を乳剤中に含んでもよい（例えば米
国特許2,933,390号、同3,635,721号、同3,743,510号、
同3,615,613号、同3,615,641号、同3,617,295号、同3,6
35,721号に記載のもの）。A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be contained in the emulsion (for example, U.S. Pat.Nos. 2,933,390, 3,635,721, 3,743,510,
No. 3,615,613, No. 3,615,641, No. 3,617,295, No. 3,6
No. 35,721).
これらの増感色素を乳剤中に添加する時期は化学熟成時
もしくはその前後でもよいし、米国特許第4,183,756
号、同第4,225,666号に従ってハロゲン化銀粒子の核形
成前後でもよい。These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after chemical ripening, and U.S. Pat. No. 4,183,756.
No. 4,225,666, before or after nucleation of silver halide grains.
添加量は一般にハロゲン化銀１モル当たり10-8ないし10
-2モル程度である。The addition amount is generally 10 -8 to 10 per mol of silver halide.
-It is about 2 mol.
本発明においては、画像形成物質として高温状態下で銀
イオンが銀に還元される際、この反応に対応して、ある
いは逆対応して可動性色素を生成するか、あるいは放出
する化合物、すなわち色素供与物質を使用する。In the present invention, when the silver ion is reduced to silver as an image forming substance under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or in the opposite response, that is, a dye Use donor material.
本発明で使用しうる色素供与性物質の例としてはまず、
酸化カップリング反応によって色素を形成する化合物
（カプラー）を挙げることができる。このカプラーは４
当量カプラーでも、２当量カプラーでもよい。また、耐
拡散基を脱離基に持ち、酸化カップリング反応により拡
散性色素を形成する２当量カプラーも好ましい。現像薬
およびカプラーの具体例はジェームズ著「ザ セオリー
オブザ フォトグラフィック プロセス」第４版（T.
H.James“The Theory of the Photographic Process"）
291〜334頁、および354〜361頁、特開昭58−123533号、
同58−149046号、同58−149047号、同59−111148号、同
59−124399号、同59−174835号、同59−231539号、同59
−231540号、同60−2950号、同60−2951号、同60−1424
2号、同60−23474号、同60−66249号等に詳しく記載さ
れている。Examples of dye-donor substances that can be used in the present invention are as follows.
A compound (coupler) that forms a dye by an oxidative coupling reaction can be mentioned. This coupler is 4
It may be an equivalent coupler or a two equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. Specific examples of developing agents and couplers are described in "The Theory of the Photographic Process", 4th edition by James (T.
H.James “The Theory of the Photographic Process”)
291 to 334 pages, and 354 to 361 pages, JP-A-58-123533,
58-149046, 58-149047, 59-111148, and
59-124399, 59-174835, 59-231539, 59
-231540, 60-2950, 60-2951, 60-1424
2, No. 60-23474, No. 60-66249 and the like.
また、別の色素供与性物質の例として、画像状に拡散性
色素を放出乃至拡散する機能を持つ化合物を挙げること
ができる。この型の化合物は次の一般式〔LI〕で表わす
ことができる。As another example of the dye-donating substance, a compound having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula [LI].
（Dye−Ｘ）ｎ−Ｙ 〔LI〕 Dyeは色素基、一時的に短波化された色素基または色素
前駆体基を表わし、Ｘは単なる結合または連結基を表わ
し、Ｙは画像状に潜像を有する感光性銀塩に対応または
逆対応して（Dye−Ｘ）ｎ−Ｙで表わされる化合物の拡
散性に差を生じさせるか、または、Dyeを放出し、放出
されたDyeと（Dye−Ｘ）ｎ−Ｙとの間に拡散性において
差を生じさせるような性質を有する基を表わし、ｎは１
または２を表わし、ｎが２の時、２つのDye−Ｘは同一
でも異なっていてもよい。(Dye-X) n-Y [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, X represents a simple bond or linking group, and Y represents an image-wise latent image. Corresponding to or opposite to the photosensitive silver salt having (Dye-X) n-Y, or causing a difference in diffusivity of the compound represented by (Dye-X) n-Y. X) n-Y represents a group having a property of causing a difference in diffusibility, and n is 1
Or 2 is represented and when n is 2, two Dye-Xs may be the same or different.
一般式〔LI〕で表わされる色素供与性物質の具体例とし
ては、例えば、ハイドロキノン系現像薬と色素成分を連
結した色素現像薬が、米国特許第3,134,764号、同第3,3
62,819号、同第3,597,200号、同第3,544,545号、同第3,
482,972号等に記載されている。また、分子内求核置換
反応により拡散性色素を放出させる物質が米国特許3,98
0,479号等に、イソオキサゾロン環の分子内巻き換え反
応により拡散性色素を放出させる物質が特開昭49−111,
628号等に記載されている。Specific examples of the dye-donating substance represented by the general formula [LI] include, for example, dye developers in which a hydroquinone-based developer and a dye component are linked to each other are disclosed in U.S. Patent Nos. 3,134,764 and 3,3.
62,819, 3,597,200, 3,544,545, 3,
No. 482,972, etc. Also, a substance that releases a diffusible dye by an intramolecular nucleophilic substitution reaction is disclosed in US Pat.
No. 0,479, a substance which releases a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring is disclosed in JP-A-49-111.
It is described in No. 628, etc.
また、別の例としては、色素放出性化合物を色素放出能
力のない酸化体型にして還元剤もしくはその前駆体と共
存させ、現像後、酸化されずに残った還元剤により還元
して拡散性色素を放出させる方式も考案されており、そ
こに用いられる色素供与性物質の具体例が、特開昭53−
110,827号、同54−130,927号、同56−164,342号、同53
−35,533号に記載されている。特願昭60−244873号に
は、同様の機構で拡散性色素を放出する色素供与性物質
として、残存する還元剤によりＮ−Ｏ結合が開裂して拡
散性色素を放出する化合物が記載されている。As another example, a dye-releasing compound is made into an oxidant type having no dye-releasing ability to coexist with a reducing agent or its precursor, and after development, the diffusible dye is reduced by the reducing agent remaining unoxidized. A method of releasing a dye has also been devised, and specific examples of dye-donor substances used therein are disclosed in JP-A-53-
110,827, 54-130,927, 56-164,342, 53
-35,533. Japanese Patent Application No. 60-244873 describes a compound that releases a diffusible dye by cleaving the N—O bond by the remaining reducing agent as a dye-donor substance that releases the diffusible dye by the same mechanism. There is.
また、特開昭59−185333号に記載の、塩基の存在下でド
ナーアクセプター反応を起こし拡散性色素を放出する
が、還元剤の酸化体と反応すると色素放出を実質的に起
こさなくなるような非拡散性の化合物（LDA化合物）も
使用できる。Further, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base to release a diffusible dye, but when it reacts with an oxidant of a reducing agent, the dye is not substantially released. A non-diffusible compound (LDA compound) can also be used.
これらの方式はいずれも現像の起こらなかった部分で拡
散性色素が放出または拡散する方式であり、現像の起こ
ったところでは色素は放出も拡散もしない。In all of these methods, the diffusible dye is released or diffused in a portion where development has not occurred, and the dye is neither released nor diffused where development has occurred.
一方、現像の起こった部分で拡散性色素を放出させる物
質として、拡散性色素を脱離基に持つカプラーであって
還元剤の酸化体との反応により拡散性色素を放出する物
質（DDRカプラー）が、英国特許第1,330,524号、特公昭
48−39,165号、米国特許第3,443,940号等に記載されて
おり、本発明に好ましく使用される。On the other hand, as a substance that releases the diffusible dye in the developed portion, it is a coupler that has the diffusible dye as a leaving group and that releases the diffusible dye by the reaction with the oxidant of the reducing agent (DDR coupler). However, British Patent No. 1,330,524, Japanese Patent Publication Sho
48-39,165, U.S. Pat. No. 3,443,940, etc. and are preferably used in the present invention.
また、これらの還元剤を用いる方式では還元剤の酸化分
解物による画像の汚染が深刻な問題となるためこの問題
を改良する目的で、還元剤を必須としない、それ自身が
還元性を持つ色素放出性化合物（DRR化合物）も考案さ
れており、本発明に特に有利に用いられる。その代表例
は、米国特許第3,928,312号、同第4,053,312号、同第4,
055,428号、同第4,336,322号、特開昭59−65839号、同5
9−69839号、同53−3819号、同51−104,343号、リサー
チ・ディスクロージャー誌17465号、米国特許第3,725,0
62号、同第3,728,113号、同第3,4443,939号、特開昭58
−116537号、同57−179840号、米国特許第4,500,626号
等に記載されている色素供与性物質である。この種の色
素供与性物質の具体例としては前述の米国特許第4,500,
626号の第22欄〜第44欄に記載の化合物を挙げることが
できるが、なかでも前記米国特許に記載の化合物（１）
〜（３）、（10）〜（13）、（16）〜（19）、（28）〜
（30）、（33）〜（35）、（38）〜（40）、（42）〜
（64）が好ましい。また特願昭59−246468号の80〜87頁
に記載の化合物も有用である。Further, in the method using these reducing agents, the image contamination due to the oxidative decomposition product of the reducing agents becomes a serious problem, and for the purpose of improving this problem, a reducing agent is not essential, and a dye having a reducing property itself. Releasing compounds (DRR compounds) have also been devised and are used particularly advantageously in the present invention. Representative examples thereof are U.S. Pat.Nos. 3,928,312, 4,053,312, and 4,
055,428, 4,336,322, JP-A-59-65839, 5
9-69839, 53-3819, 51-104,343, Research Disclosure 17465, U.S. Pat.
No. 62, No. 3,728,113, No. 3,4443,939, JP-A-58.
-116537, 57-179840, U.S. Pat. No. 4,500,626 and the like. Specific examples of this type of dye-donating substance include the aforementioned U.S. Pat.
The compounds described in Columns 22 to 44 of No. 626 can be mentioned, among which the compound (1) described in the above-mentioned US Patent
~ (3), (10) ~ (13), (16) ~ (19), (28) ~
(30), (33) ~ (35), (38) ~ (40), (42) ~
(64) is preferable. Further, the compounds described on pages 80 to 87 of Japanese Patent Application No. 59-246468 are also useful.
その他、上記に述べた以外の色素供与性物質として、有
機銀塩と色素を結合した色素銀化合物（リサーチ・ディ
スクロージャー誌1978年５月号、54〜58頁等）、熱現像
銀色素漂白法に用いられるアゾ色素（米国特許第4,235,
957号、リサーチ・ディスクロージャー誌、1976年４月
号、30〜32頁等）、ロイコ色素（米国特許第3,985,565
号、同4,022,617号等）なども使用できる。In addition to the above-mentioned dye-donating substances, dye silver compounds in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, p. 54-58, etc.), heat-developable silver dye bleaching method Azo dyes used (U.S. Pat.
957, Research Disclosure, April 1976, pages 30-32, etc.), Leuco dyes (US Pat. No. 3,985,565)
No., No. 4,022,617, etc.) can also be used.
本発明で用いられる色素供与性物質は0.01〜10ミリモル
／m2、好ましくは0.03〜５ミリモル／m2が適当である。The dye-donating substance used in the present invention is suitably 0.01 to 10 mmol / m 2 , preferably 0.03 to 5 mmol / m 2 .
上記の色素供与性化合物および以下に述べる画像形成促
進剤などの疎水性添加剤は米国特許第2,322,027号記載
の方法などの公知の方法により感光要素の層中に導入す
ることができる。この場合には、特開昭59−83154号、
同59−178451号、同59−178452号、同59−178453号、同
59−178454号、同59−178455号、同59−178457号などに
記載のような高沸点有機溶媒を、必要に応じて沸点50℃
〜160℃の低沸点有機溶媒と併用して、用いるとができ
る。The above dye-providing compounds and hydrophobic additives such as the image-forming accelerators described below can be incorporated into the layers of the light-sensitive element by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
59-178451, 59-178452, 59-178453, 59
59-178454, 59-178455, 59-178457, such as a high-boiling organic solvent, as described in the boiling point 50 ℃
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.
高沸点有機溶媒の量は用いられる色素供与性物質1gに対
して10g以下、好ましくは5g以下である。The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, with respect to 1 g of the dye-donor substance used.
また特公昭51−39853号、特開昭51−59943号に記載され
ている重合物による分散法も使用できる。Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.
水に実質的に不溶な化合物の場合には、前記方法以外に
バインダー中に微粒子にして分散含有させることができ
る。In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.
疎水性物質を親水性コロイドに分散する際には、種々の
界面活性剤を用いることができる。例えば特開昭59−15
7636号（37）〜（38）頁に界面活性剤として挙げたもの
を使うことができる。When dispersing the hydrophobic substance in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-15
The surfactants listed on pages 7636 to (38) of No. 7636 can be used.
本発明において感光要素中に還元性物質を含有させるの
が望ましい。還元性物質としては一般に還元剤として公
知なものの他、前記の還元性を有する色素供与性物質も
含まれる。また、それ自身は還元性を持たないが現像過
程で求核試薬や熱の作用により還元性を発現する還元剤
プレカーサーも含まれる。In the present invention, it is desirable to incorporate a reducing substance in the photosensitive element. Examples of the reducing substance include those generally known as a reducing agent, and the dye-donating substance having the above-described reducing property. Further, a reducing agent precursor which does not have reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process is also included.
本発明に用いられる還元剤の例としては、米国特許4,50
0,626号の第49〜50欄、同4,483、914号の第30〜31欄、
特開昭60−140335号の第（17）〜（18）頁、特開昭60−
128438号、同60−128436号、同60−128439号、同60−12
8437号等に記載の還元剤が利用できる。また、特開昭56
−138,736号、同57−40,245号、米国特許第4,330,617号
等に記載されている還元剤プレカーサーも利用できる。Examples of reducing agents used in the present invention include US Pat.
0,626 columns 49-50, 4,483, 914 columns 30-31,
JP-A-60-140335, pages (17) to (18), JP-A-60-
128438, 60-128436, 60-128439, 60-12
The reducing agents described in 8437 and the like can be used. In addition, JP-A-56
The reducing agent precursors described in, for example, -138,736, 57-40,245, and U.S. Pat. No. 4,330,617 can also be used.
米国特許第3,039,869号に開示されているもののような
種々の還元剤の組合せも用いることができる。Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.
本発明に於いては還元剤の添加量は銀１モルに対して0.
01〜20モル、特に好ましくは0.1〜10モルである。In the present invention, the amount of reducing agent added is 0.
The amount is 01 to 20 mol, particularly preferably 0.1 to 10 mol.
本発明においては感光要素に現像の活性化と同時に画像
の安定化を図る化合物を用いることができる。好ましく
は用いられる具体的化合物については米国特許4,500,62
6号の第51〜52欄に記載されている。In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive element. Specific compounds preferably used are described in U.S. Pat.
No. 6 columns 51-52.
本発明においては種々のカブリ防止剤または写真安定剤
を使用することができる。その例としては、リサーチ・
ディスクロージャー誌1978年12月号第24〜25頁に記載の
アゾール類やアザインデン類、特開昭59−168442号記載
の窒素を含むカルボン酸類およびリン酸類、あるいは特
開昭59−111636号記載のメルカプト化合物およびその金
属塩、特願昭60−228267号に記載されているアセチレン
化合物類などが用いられる。Various antifoggants or photographic stabilizers can be used in the present invention. For example, research
Disclosure, December 1978, pages 24 to 25, azoles and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto described in JP-A-59-111636. Compounds and metal salts thereof, and acetylene compounds described in Japanese Patent Application No. 60-228267 are used.
本発明においては、感光要素に必要に応じて画像調色剤
を含有することができる。有効な調色剤の具体例につい
ては特願昭59−268926号92〜93頁に記載の化合物があ
る。In the present invention, the light-sensitive element may contain an image toning agent, if necessary. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92 to 93.
本発明に用いられる感光要素は、必要に応じて熱現像感
光要素用として知られている各種添加剤や、感光層以外
の層、例えば保護層、中間層、帯電防止層、ハレーショ
ン防止層、色素固定要素との剥離を容易にするための剥
離層、マット層などを有することができる。各種添加剤
としては、リサーチ・ディスクロージャー誌1978年６月
号９頁〜15頁、特願昭59−209563号などに記載されてい
る可塑剤、マット剤、鮮鋭度改良用染料、ハレーション
防止染料、界面活性剤、螢光増白剤、スベリ防止剤、酸
化防止剤、退色防止剤などの添加剤がある。The photosensitive element used in the present invention is, if necessary, various additives known for heat-developable photosensitive elements and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer and a dye. It may have a release layer, a matte layer or the like for facilitating release from the fixing element. Examples of various additives include plasticizers, matting agents, sharpness improving dyes and antihalation dyes described in Research Disclosure, June 1978, pages 9 to 15 and Japanese Patent Application No. 59-209563. There are additives such as surfactants, fluorescent brighteners, anti-slip agents, antioxidants, and anti-fading agents.
特に保護層には、接着防止のために有機、無機のマット
剤を含ませるのが通常である。また、この保護層には媒
染剤、紫外線吸収剤を含ませてもよい。保護層、中間層
はそれぞれ２層以上から構成されていてもよい。In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. The protective layer and the intermediate layer may each be composed of two or more layers.
また、中間層には退色防止や混色防止のための還元剤
や、紫外線吸収剤、二酸化チタンなどの白色顔料を含ま
せてもよい。白色顔料は感度を向上させる目的で中間層
のみならず乳剤層に添加してもよい。Further, the intermediate layer may contain a reducing agent for preventing discoloration or color mixture, an ultraviolet absorber, or a white pigment such as titanium dioxide. The white pigment may be added to the emulsion layer as well as the intermediate layer for the purpose of improving the sensitivity.
一方、本発明に用いる色素固定要素は、熱現像により生
成または放出された色素を固定する層を少なくとも１層
有する。この色素固定層は媒染剤を含有する層であって
もよいし、特開昭57−179840号、同57−198458号等に記
載されている色素受容性のポリマーから構成された層で
もよい。On the other hand, the dye fixing element used in the present invention has at least one layer for fixing the dye generated or released by heat development. This dye-fixing layer may be a layer containing a mordant, or may be a layer composed of a dye-accepting polymer described in JP-A Nos. 57-179840 and 57-198458.
本発明に好ましく用いられる色素固定要素は媒染剤とバ
インダーを含む層を少なくとも１層有する。媒染剤は写
真分野で公知のものを用いることができ、その具体例と
しては特願昭59−209563号に記載のものを挙げることが
できる。色素固定要素には必要に応じて画像の保存時の
安定性を増す目的で各種の化合物、例えば酸化防止剤、
退色防止剤、紫外線吸収剤、金属錯体などを単独あるい
は組み合わせて用いてもよい。又、白色度の改良のため
特願昭59−248351号に記載の螢光増白剤を用いたり、酸
化チタンなどの白色顔料を用いその使用量を調節するこ
とも有用である。他の添加剤として、硬膜剤、親水性熱
溶剤、可塑剤、スベリ剤、マット剤、塩基または塩基プ
レカーサーの析出を防止することを目的とした親水性ポ
リマー、高吸水性ポリマー、寸度安定性を増加させるた
めの分散状ビニル化合物、界面活性剤（塗布適性の改
良、帯電防止、接着防止などのため）などを含ませても
よい。これらの添加剤の具体例は特願昭59−209563号の
101頁〜120頁に記載されている。The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include those described in Japanese Patent Application No. 59-209563. The dye-fixing element may optionally contain various compounds for the purpose of increasing the storage stability of the image, for example, an antioxidant,
An anti-fading agent, an ultraviolet absorber, a metal complex and the like may be used alone or in combination. Further, in order to improve the whiteness, it is also useful to use the fluorescent whitening agent described in Japanese Patent Application No. 59-248351 or to adjust the amount of the whitening agent such as titanium oxide used. As other additives, hardening agents, hydrophilic thermal solvents, plasticizers, slip agents, matting agents, hydrophilic polymers for the purpose of preventing the precipitation of bases or base precursors, superabsorbent polymers, dimensional stability A dispersed vinyl compound for increasing the property, a surfactant (for improving coating suitability, preventing static electricity, preventing adhesion, etc.) may be included. Specific examples of these additives are described in Japanese Patent Application No. 59-209563.
It is described on pages 101 to 120.
色素固定要素は１層により構成されていてもよいし、２
層以上から構成されていてもよい。例えば保護層、剥離
層、カール防止層などの補助層を設けることができる。
特に保護層を設けるのは有用である。The dye fixing element may be composed of one layer or 2
It may be composed of more than one layer. For example, auxiliary layers such as a protective layer, a peeling layer, and a curl prevention layer can be provided.
In particular, it is useful to provide a protective layer.
本発明において感光要素及び／又は色素固定要素には画
像形成促進剤を用いることができる。画像形成促進剤に
は銀塩酸化剤と還元剤との酸化還元反応の促進、色素供
与性物質からの色素の生成または色素の分解あるいは拡
散性色素の放出等の反応の促進および、感光材料層から
色素固定層への色素の移動の促進等の機能があり、物理
化学的な機能からは前記の塩基または塩基プレカーサ
ー、求核性化合物、高沸点有機溶媒（オイル）、熱溶
剤、界面活性剤、銀または銀イオンと相互作用を持つ化
合物等に分類される。ただし、これらの物質群は一般に
複合機能を有しており、上記の促進効果のいくつかを合
せ持つのが常である。これらの詳細については特願昭59
−213978号の67〜71頁に記載されている。In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, the above-mentioned base or base precursor, nucleophilic compound, high boiling organic solvent (oil), thermal solvent, surfactant , And compounds that interact with silver or silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. For details of these, Japanese Patent Application No. 59
-213978, pages 67-71.
本発明の感光要素及び／又は色素固定要素には、現像時
の処理温度および処理時間の変動に対し、常に一定の画
像を得る目的で種々の現像停止剤を用いることができ
る。In the light-sensitive element and / or the dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development.
ここでいう現像停止剤とは、適正現像後、速やかに塩基
を中和または塩基と反応して膜中の塩基濃度を下げ現像
を停止する化合物または銀および銀塩と相互作用して現
像を抑制する化合物である。具体的には、加熱により酸
を放出する酸プレカーサー、加熱により共存する塩基と
置換反応を起す親電子化合物、または含窒素ヘテロ環化
合物、メルカプト化合物およびその前駆体等が挙げられ
る（例えば特願昭58−216928号、同59−48305号、同59
−85834号または同59−85836号に記載の化合物など）。The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof (for example, Japanese Patent Application No. 58-216928, 59-48305, 59
-85834 or 59-85836, etc.).
また加熱によりメルカプト化合物を放出する化合物も有
用であり、例えば特願昭59−190173号、同59−268926
号、同59−246468号、同60−26038号、同60−22602号、
同60−26039号、同60−24665号、同60−29892号、同59
−176350号、に記載の化合物がある。Further, a compound which releases a mercapto compound by heating is also useful, for example, Japanese Patent Application Nos. 59-190173 and 59-268926.
No. 59-246468, No. 60-26038, No. 60-22602,
60-26039, 60-24665, 60-29892, 59
-176350, there is a compound described.
本発明の感光要素及び／又は色素固定要素のバインダー
には親水性のものを用いることができる。親水性バイン
ダーとしては、透明か半透明の親水性バインダーが代表
的であり、例えばゼラチン、ゼラチン誘導体等のタンパ
ク質、セルロース誘導体や、デンプン、アラビヤゴム等
の多糖類のような天然物質と、ポリビニルアルコール、
ポリビニルピロリドン、アクリルアミド重合体等の水溶
性のポリビニル化合物のような合成重合物質を含む。ま
た、ラテックスの形で用いられ、写真材料の寸度安定性
を増加させる分散状ビニル化合物も使用できる。これら
のバインダーは単独であるいは組合わせて用いることが
できる。A hydrophilic binder may be used as the binder of the photosensitive element and / or the dye fixing element of the present invention. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and for example, gelatin, proteins such as gelatin derivatives, cellulose derivatives, starch, natural substances such as polysaccharides such as arabic gum, and polyvinyl alcohol,
Includes synthetic polymeric materials such as polyvinylpyrrolidone, water soluble polyvinyl compounds such as acrylamide polymers. It is also possible to use a dispersed vinyl compound which is used in the form of a latex and which increases the dimensional stability of the photographic material. These binders can be used alone or in combination.
本発明においてバインダーは１m2あたり20g以下の塗布
量であり、好ましくは10g以下さらに好ましくは7g以下
が適当である。In the present invention, the binder is applied in an amount of 20 g or less per 1 m 2 , preferably 10 g or less, more preferably 7 g or less.
バインダー中に色素供与性物質などの疎水性化合物と共
に分散される高沸点有機溶媒とバインダーとの比率はバ
インダー1gに対して溶媒1cc以下、好ましくは0.5cc以
下、さらに好ましくは0.3cc以下が適当である。The ratio of the high-boiling organic solvent and the binder dispersed together with the hydrophobic compound such as the dye-providing substance in the binder is 1 cc or less of the solvent per 1 g of the binder, preferably 0.5 cc or less, and more preferably 0.3 cc or less. is there.
本発明の感光要素及び／又は色素固定要素の構成層（写
真乳剤層、色素固定層など）には無機または有機の硬膜
剤を含有してよい。The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and / or dye fixing element of the present invention may contain an inorganic or organic hardener.
硬膜剤の具体例は、特願昭59−268926号明細書94頁ない
し95頁、同60−231093号５頁ないし８頁、特開昭59−15
7639号等（38）頁に記載のものが挙げられ、これらは単
独または組合わせて用いることができる。Specific examples of the hardener are disclosed in Japanese Patent Application No. 59-268926, pages 94 to 95, 60-231093, pages 5 to 8, JP-A-59-15.
No. 7639 and the like, page 38, are mentioned, and these can be used alone or in combination.
また色素移動を促進するために、常温では固体であり高
温では溶解する親水性熱溶剤を感光要素または色素固定
要素に内蔵させてもよい。親水性熱溶剤は感光要素、色
素固定要素のいずれに内蔵させてもよく、両方に内蔵さ
せてもよい。また内蔵させる層も乳剤層、中間層、保護
層、色素固定層いずれでもよいが、色素固定層および／
またはその隣接層に内蔵させるのが好ましい。親水性熱
溶剤の例としては、尿素類、ピリジン類、アミド類、ス
ルホンアミド類、イミド類、アルコール類、オキシム類
その他の複素環類がある。また、色素移動を促進するた
めに、高沸点有機溶剤を感光要素及び／又は色素固定要
素に含有させておいてもよい。In order to promote dye transfer, a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature may be incorporated in the photosensitive element or the dye fixing element. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The built-in layer may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer.
Alternatively, it is preferably incorporated in the adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, a high-boiling point organic solvent may be contained in the light-sensitive element and / or the dye-fixing element in order to promote dye transfer.
本発明の感光要素及び／又は色素固定要素に使用される
支持体は、処理温度に耐えることのできるものである。
一般的な支持体としては、ガラス、紙、重合体フィル
ム、金属およびその類似体が用いられるばかりでなく、
特願昭59−268926号明細書の95頁〜96頁に支持体として
記載されているものが使用できる。The support used in the light-sensitive element and / or the dye-fixing element of the present invention can withstand the processing temperature.
As a general support, not only glass, paper, polymer film, metal and its analogues are used,
The support described on pages 95 to 96 of Japanese Patent Application No. 59-268926 can be used.
感光要素及び／又は色素固定要素は、加熱現像もしくは
色素の拡散転写のための加熱手段としての導電性の発熱
体層を有する形態であってもよい。The light-sensitive element and / or the dye-fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of a dye.
この場合の透明または不透明の発熱要素は、抵抗発熱体
として従来公知の技術を利用して作ることができる。抵
抗発熱体としては、半導性を示す無機材料の薄膜を利用
する方法と導電性微粒子をバインダーに分散した有機物
薄膜を利用する方法とがある。これらの方法に利用でき
る材料は、特願昭59−151815号明細書等に記載のものを
利用できる。In this case, the transparent or opaque heating element can be manufactured by using a conventionally known technique as a resistance heating element. As the resistance heating element, there are a method of using a thin film of a semiconductive inorganic material and a method of using an organic thin film in which conductive fine particles are dispersed in a binder. Materials usable in these methods include those described in Japanese Patent Application No. 59-151815.
本発明の色素固定要素には、媒染層の脆性を改良するた
めに、流動パラフィンのような油滴を含有させてもよ
い。また同様の目的で、ガラス転位点の低い重合体ラテ
ックスを含有させることもできる。The dye-fixing element of the present invention may contain oil droplets such as liquid paraffin in order to improve the brittleness of the mordant layer. Further, for the same purpose, a polymer latex having a low glass transition point may be contained.
本発明において熱現像感光層、保護層、中間層、下塗
層、バック層、色素固定層その他の層の塗布法は米国特
許4,500,626号の第55〜56欄に記載の方法が適用でき
る。In the present invention, as the coating method for the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer and other layers, the methods described in US Pat. No. 4,500,626, columns 55 to 56 can be applied.
感光要素へ画像を記録するための画像露光の光源として
は、可視光をも含む輻射線を用いることができる。一般
には、通常のカラープリントに使われる光源、例えばタ
ングステンランプ、水銀燈、ヨードランプなどのハロゲ
ンランプ、キセノンランプ、レーザー光源、CRT水源、
発光ダイオード（LED）等、特願昭59−268926号の100頁
や米国特許4,500626号の第56欄に記載の光源を用いるこ
とができる。Radiation that also contains visible light can be used as a light source for image exposure for recording an image on the photosensitive element. Generally, light sources used for normal color printing, such as halogen lamps such as tungsten lamps, mercury lamps, iodine lamps, xenon lamps, laser light sources, CRT water sources,
A light source such as a light emitting diode (LED) described on page 100 of Japanese Patent Application No. 59-268926 or column 56 of US Pat. No. 4,500,626 can be used.
（実施例） 以下、本発明の具体的実施例を示し、本発明をさらに詳
細に説明する。(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention.
実施例１ 流動パラフィンのゼラチン分散物の作り方について述べ
る。Example 1 A method for preparing a gelatin dispersion of liquid paraffin will be described.
10％ゼラチン水溶液100gにデデシルベンゼンスルホン酸
ナトリウムの５％水溶液5mlを加え混合した後、流動パ
ラフィンを20g加えてホモブレンダーにて10,000rpmで６
分間乳化分散する。After adding 5 ml of 5% aqueous solution of sodium dedecylbenzene sulfonate to 100 g of 10% gelatin aqueous solution and mixing, 20 g of liquid paraffin was added and the mixture was mixed with a homoblender at 10,000 rpm at 6 rpm.
Emulsify and disperse for a minute.
このようにして調製した流動パラフィンの分散物を用い
て表−１の如き構成の色素固定材料Ｒ−１〜Ｒ−11を作
製した。Using the liquid paraffin dispersion thus prepared, dye fixing materials R-1 to R-11 having the constitutions shown in Table 1 were prepared.
次に感光材料の作り方について述べる。 Next, how to make a photosensitive material will be described.
第１層用のハロゲン化銀乳剤の作り方について述べる。The method for preparing the silver halide emulsion for the first layer will be described.
乳剤（Ｉ） 良く攪拌しているゼラチン水溶液（水1000ml中にゼラチ
ン20gと塩化ナトリウム2gとを溶解させて75℃に保温し
たもの）に臭化カリウム56gと塩化ナトリウム7gとを含
む水溶液600mlと硝酸銀水溶液（水600ml中に硝酸銀0.59
モルを溶解させたもの）を同時に等流量で60分かけて添
加した。水洗、脱塩後ゼラチン40gと水200mlを加えてpH
を6.5、pAgを7.9に調整し、チオ硫酸ナトリウムと４−
ヒドロキシ−６−メチル−1,3,3a,7−テトラザインデン
を用いて最適の化学増感を行ない、平均粒径0.4μの六
面体単分散乳剤（Ｉ）700gを得た。Emulsion (I) 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride in a well stirred gelatin aqueous solution (20 g of gelatin and 2 g of sodium chloride dissolved in 1000 ml of water and kept at 75 ° C.) and silver nitrate Aqueous solution (silver nitrate 0.59 in 600 ml of water
(Mol dissolved) was added simultaneously at a constant flow rate over 60 minutes. After washing with water and desalting, add 40 g of gelatin and 200 ml of water to adjust the pH.
Was adjusted to 6.5 and pAg was adjusted to 7.9, and sodium thiosulfate and 4-
Optimum chemical sensitization was carried out using hydroxy-6-methyl-1,3,3a, 7-tetrazaindene to obtain 700 g of a hexahedral monodisperse emulsion (I) having an average grain size of 0.4 µ.
第３層用のハロゲン化銀乳剤の作り方について述べる。The method for preparing the silver halide emulsion for the third layer will be described.
乳剤（II） 下記処方により乳剤Ａ）、Ｂ）を調製し、半量ずつ混合
し乳剤（II）とした。Emulsion (II) Emulsions A) and B) were prepared according to the following formulation, and half of each was mixed to prepare an emulsion (II).
水600mlを含むビーカー中に、ゼラチン20g、臭化カリウ
ム1.2gおよび25％アンモニア水6ccを入れ攪拌溶解させ
た。この溶液を50℃に保ちながら硝酸銀100gを水600ml
に溶解させた液および臭化カリウム116gと沃化カリウム
4gとを水1000mlに溶解させた液をコントロールドダブル
ジェット法で、液のpAgを8.9に保ちながら50分間で添加
した。その時、ハロゲン溶液と硝酸銀溶液の添加開始と
同時に下記の色素（Ａ）0.15gをメタノール75mlに溶解
させた液の添加をはじめ25分間で全量を添加した。In a beaker containing 600 ml of water, 20 g of gelatin, 1.2 g of potassium bromide and 6 cc of 25% ammonia water were put and dissolved with stirring. While keeping this solution at 50 ° C, add 100 g of silver nitrate to 600 ml of water.
Liquid dissolved in and 116 g of potassium bromide and potassium iodide
A solution prepared by dissolving 4 g and 1000 ml of water was added by the controlled double jet method over 50 minutes while keeping the pAg of the solution at 8.9. At that time, at the same time when the addition of the halogen solution and the silver nitrate solution was started, the total amount was added in 25 minutes including the addition of a solution prepared by dissolving 0.15 g of the following dye (A) in 75 ml of methanol.
水洗、脱塩後ゼラチン20gと水100mlを加えてpHを6.3に
調整し、臭化カリウムを加えてpAgを9.3とした。次にチ
オ硫酸ナトリウムを用いて最適の化学増感を行ない粒子
サイズ0.5μ、ジャガイモ形状のパンクロ増感沃臭化銀
乳剤（Ａ）700gを得た。 After washing with water and desalting, 20 g of gelatin and 100 ml of water were added to adjust the pH to 6.3, and potassium bromide was added to adjust the pAg to 9.3. Next, optimum chemical sensitization was carried out using sodium thiosulfate to obtain 700 g of a potato-shaped panchromatically sensitized silver iodobromide emulsion (A) having a grain size of 0.5 μm.
さらに最初に用いる25％アンモニア水が2.5ccである以
外は同じである乳剤（Ｂ）も得た。この場合、粒子サイ
ズは、0.3μであった。Further, the same emulsion (B) was obtained except that the 25% aqueous ammonia used initially was 2.5 cc. In this case, the particle size was 0.3μ.
第５層用の乳剤の作り方について述べる。The method for preparing the emulsion for the fifth layer will be described.
乳剤（III）は下記処方により乳剤（Ａ）および（Ｂ）
を調製し、半量づつ混合して乳剤（III）とした。Emulsion (III) has the following formulation and is emulsions (A) and (B)
Was prepared and mixed by half to give an emulsion (III).
乳剤（Ａ）の調製法 良く攪拌しているゼラチン水溶液（水1000ml中にゼラチ
ン20gと塩化ナトリウム2gとを溶解させて60℃に保温し
たもの）に臭化カリウムと塩化ナトリウムとを含む（合
わせて0.59モル）水溶液600mlと0.59モルの硝酸銀を含
む水溶液600mlとを同時に等流量で25分かけて添加し、B
r80モル％でサイズが0.25μの立方体単分散塩臭化銀粒
子を作った。その際ハロゲン化銀粒子形成開始と同時に
下記の色素（Ｉ）0.16gをメタノール400ccに溶解した液
を15分かけてゼラチン水溶液中に添加した。Preparation of emulsion (A) A well-stirred aqueous gelatin solution (20 g of gelatin and 2 g of sodium chloride dissolved in 1000 ml of water and kept at 60 ° C.) containing potassium bromide and sodium chloride (combined) 0.59 mol) aqueous solution (600 ml) and an aqueous solution containing 0.59 mol of silver nitrate (600 ml) are simultaneously added at an equal flow rate over 25 minutes.
Cubic monodisperse silver chlorobromide grains having a size of 0.25μ were prepared at r80 mol%. Simultaneously with the start of silver halide grain formation, a solution prepared by dissolving 0.16 g of the following dye (I) in 400 cc of methanol was added to the aqueous gelatin solution over 15 minutes.
水洗、脱塩後ゼラチン40gと水200mlを加えてpHを6.4
に、pAgを7.8に調整し、チオ硫酸ナトリウムと塩化金酸
と４−ヒドロキシ−６−メチル−1,3,3a,7−テトラザイ
ンデンを用いて最適の化学増感を行なった。After washing and desalting, 40 g of gelatin and 200 ml of water were added to adjust the pH to 6.4.
Then, the pAg was adjusted to 7.8, and optimum chemical sensitization was performed using sodium thiosulfate, chloroauric acid and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene.
乳剤の収量は700gである。The yield of emulsion is 700 g.
乳剤（Ｂ）の調製法 良く攪拌しているゼラチン水溶液（水1000ml中にゼラチ
ン20gと塩化ナトリウム2gおよび化合物 を0.015g溶解させて75℃に保温したもの）に臭化カリウ
ムと塩化ナトリウムとを含む（合わせて0.59モル）水溶
液600mlと0.59モルの硝酸銀を含む水溶液600mlとを60分
かけて添加し、Br80モル％でサイズが0.5μの立方体単
分散塩臭化銀粒子を作った。その際ハロゲン化銀粒子形
成開始と同時に乳剤（Ａ）と同じ色素（Ｉ）0.16gをメ
タノール400ccに溶解した液を30分かけてゼラチン水溶
液中に添加した。水洗、脱塩後ゼラチン40gと水200mlを
加えてpHを6.4にpAgを8.0に調整し、トリエチルチオ尿
素と核酸分解物を用いて最適の化学増感を行なった。 Preparation method of emulsion (B) Gelatin aqueous solution (20 g of gelatin and 2 g of sodium chloride and the compound in 1000 ml of water with good stirring) Was dissolved in 0.015 g and kept at 75 ° C.), 600 ml of an aqueous solution containing potassium bromide and sodium chloride (0.59 mol in total) and 600 ml of an aqueous solution containing 0.59 mol of silver nitrate were added over 60 minutes, and Br80 Cubic monodisperse silver chlorobromide grains with a size of 0.5μ in mol% were made. At that time, simultaneously with the start of silver halide grain formation, a solution prepared by dissolving 0.16 g of the same dye (I) as in the emulsion (A) in 400 cc of methanol was added to the aqueous gelatin solution over 30 minutes. After washing with water and desalting, 40 g of gelatin and 200 ml of water were added to adjust pH to 6.4 and pAg to 8.0, and optimal chemical sensitization was performed using triethylthiourea and a nucleic acid decomposition product.
乳剤の収量は700gである。The yield of emulsion is 700 g.
有機銀塩の作り方について述べる。How to make an organic silver salt is described.
有機銀塩（１） ベンゾトリアゾール銀乳剤の作り方について述べる。Organic Silver Salt (1) A method for preparing a benzotriazole silver emulsion will be described.
ゼラチン28gとベンゾトリアゾール13.2gを水300mlに溶
解した。この溶液を40℃に保ち攪拌した。この溶液に硝
酸銀17gを水100mlに溶かした液を２分間で加えた。28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 ml of water. This solution was kept at 40 ° C. and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.
このベンゾトリアゾール銀乳剤のpHを調整し、沈降さ
せ、過剰の塩を除去した。その後、pHを6.30に合わせ、
収量400gのベンゾトリアゾール銀乳剤を得た。The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then adjust the pH to 6.30,
A yield of 400 g of benzotriazole silver emulsion was obtained.
有機銀塩（２） ゼラチン20gと４−アセチルアミノフェニルプロピオー
ル酸5.9gを0.1％水酸化ナトリウム水溶液1000mlとエタ
ノール200mlに溶解した。Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of 0.1% sodium hydroxide aqueous solution and 200 ml of ethanol.
この溶液を40℃に保ち攪拌した。This solution was kept at 40 ° C. and stirred.
この溶液に硝酸銀4.5gを水200mlに溶かした液を５分間
で加えた。A solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added to this solution over 5 minutes.
この分散物のpHを調整し、沈降させ過剰の塩を除去し
た。この後、pHを6.3に合わせ収量300gの有機銀塩
（２）の分散物を得た。The pH of this dispersion was adjusted and allowed to settle to remove excess salt. After that, the pH was adjusted to 6.3 to obtain a 300 g organic silver salt (2) dispersion.
次に、色素供与性物質のゼラチン分散物の作り方につい
て述べる。Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.
イエローの色素供与性物質（Ａ）を5g、界面活性剤とし
て、コハク酸−２−エチル−ヘキシルエステルスルホン
酸ソーダ0.5g、トリイソノニルフォスフェート2.5gを秤
量し、酢酸エチル30mlを加え、約60℃に加熱溶解させ、
均一な溶液とした。この溶液と石灰処理ゼラチンの10％
溶液30gとを攪拌混合した後、ホモジナイザーで10分
間、10000rpmにて分散した。この分散液をイエローの色
素供与性物質の分散物と言う。5 g of the yellow dye-donating substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 2.5 g of triisononyl phosphate were weighed and added with 30 ml of ethyl acetate, Dissolve by heating to 60 ℃,
A homogeneous solution was obtained. 10% of this solution and lime-processed gelatin
After stirring and mixing 30 g of the solution, the mixture was dispersed at 10,000 rpm for 10 minutes with a homogenizer. This dispersion is called a yellow dye-donor substance dispersion.
マゼンタの色素供与性物質（Ｂ）を使う事と高沸点溶媒
としてトリクレジルフォスフェートを2.5g使う以外は、
上記方法により同様にしてマゼンタの色素供与性物質の
分散物を作った。Other than using the magenta dye-donating substance (B) and 2.5 g of tricresyl phosphate as a high boiling solvent,
A magenta dye-donor dispersion was similarly prepared by the above method.
イエローの色素分散物と同様にして、シアンの色素供与
性物質（Ｃ）を使いシアンの分散物を作った。A cyan dispersion was prepared using the cyan dye-donor (C) in the same manner as the yellow dye dispersion.
色素供与性物質 以上に述べた乳剤乳化物を用いて表−２の如き多層構成
のカラー感光材料Ｐ−１〜Ｐ−９を作った。Dye donating substance Using the emulsion emulsions described above, color light-sensitive materials P-1 to P-9 having a multilayer structure as shown in Table 2 were prepared.
（剥離テスト方法） 感光材料の塗布面に水をバーコート法により6g/m2塗布
し、直ちに色素固定材料の膜面と接するように重ね合せ
て100℃のヒートローラーに通し、つづいて95℃のヒー
トブロックにて20秒間加熱後、両材料を剥離した。 (Peeling test method) 6 g / m 2 of water was applied to the coated surface of the light-sensitive material by the bar coating method, immediately superposed so as to be in contact with the film surface of the dye-fixing material, and passed through a heat roller at 100 ° C, followed by 95 ° C After heating for 20 seconds in the heat block of No. 2, both materials were peeled off.
剥離性が悪いと、感光材料と色素固定材料の塗布膜が接
着してしまい剥離できないか、または無理に剥離すると
感光材料または色素固定材料のどちらかの塗布膜が剥れ
てしまう。If the releasability is poor, the coating film of the light-sensitive material and the dye-fixing material adhere to each other and cannot be peeled, or if they are peeled off by force, the coating film of either the light-sensitive material or the dye-fixing material peels.
剥離性の良いものは、容易に剥離され色素固定材料の塗
布膜面の光沢性も良好である。Those having a good peeling property are easily peeled off and the glossiness of the coating film surface of the dye fixing material is also good.
剥離テストの結果を表−４に示す。The results of the peel test are shown in Table-4.
また色素固定材料をトレイ中に多数枚重ねて、上側に位
置するものから順にローラーでトレイから取り出すテス
トをしたところ、Ｒ−１やＲ−９〜11を用いた場合は一
度の操作で２〜５枚が同時に取り出されてしまう支障が
あったが、本発明のＲ−２〜８は一枚づつ正常に取り出
すことができた。 In addition, a large number of dye-fixing materials were piled up in a tray, and a test of taking out from the tray with rollers in order from the one located on the upper side was carried out. When R-1 and R-9 to 11 were used, 2 Although there was a problem that five sheets were taken out at the same time, R-2 to 8 of the present invention could be taken out one by one normally.
更に、該感光材料Ｐ−１〜Ｐ−９にタングステン電球を
用い、連続的に濃度が変化しているＧ、Ｒ、IR三色分解
フィルター（Ｇは500〜600nm、Ｒは600〜700nmのバント
パスフィルター、IRは700nm以上透過のフィルターを用
い構成した）を通して、500ルックスで１秒露光した。
この露光済みの感光材料の乳剤面に12g/m2の水をバーコ
ート法により均一に塗布し、直ちに色素固定材料Ｒ−１
〜Ｒ−11を表−４に示した組み合せで膜面が接するよう
に重ね合せた。両材料を90℃のヒートブロック上で25秒
間加熱した後、色素固定材料を感光材料からひきはがす
とテストNo.2〜6,10〜16,20,21については色素固定材料
上に、Ｇ、Ｒ、IRの３色分解フィルターに対応してそれ
ぞれイエロー、マゼンタ、シアンの鮮明な色像が得られ
た。しかし、テストNo.1では剥離できないため、画像の
観察ができず、またテストNo.7〜９及び17〜19のものは
表面に一部感光材料の塗布膜が付着しており、かつ光沢
性も劣っていた。Further, a tungsten light bulb is used for the photosensitive materials P-1 to P-9, and G, R, and IR three-color separation filters (G is 500 to 600 nm, R is 600 to 700 nm) whose density is continuously changed. It was exposed for 1 second at 500 lux through a pass filter and an IR configured with a filter that transmits 700 nm or more).
12 g / m 2 of water was uniformly applied to the emulsion surface of the exposed light-sensitive material by the bar coating method, and immediately the dye fixing material R-1 was used.
.About.R-11 were superposed by the combinations shown in Table 4 so that the film surfaces were in contact with each other. After heating both materials on a 90 ° C heat block for 25 seconds, the dye fixing material was peeled off from the light-sensitive material. For Test Nos. 2 to 6, 10 to 16, 20, and 21, G, G, Clear color images of yellow, magenta, and cyan were obtained corresponding to the three color separation filters of R and IR, respectively. However, the image cannot be observed in Test No. 1 because it cannot be peeled off, and in Test Nos. 7 to 9 and 17 to 19, the coating film of the photosensitive material is partially adhered to the surface and the gloss is high. Was also inferior.
実施例２ 実施例１と同じ乳剤を用い、表−５の組成をもつ感光材
料２−Ａを作成した。色素供与性物質としては下記のも
のを用いた。分散物の作り方は実施例１と同じである。Example 2 Using the same emulsion as in Example 1, a photosensitive material 2-A having the composition shown in Table-5 was prepared. The following were used as the dye-providing substance. The method of making the dispersion is the same as in Example 1.
感光材料２−Ｂは、保護層の界面活性剤Ａの代りに本発
明の化合物（３）を30mg添加すること以外は感光材料２
−Ａと同様にして作成した。The light-sensitive material 2-B is a light-sensitive material 2 except that 30 mg of the compound (3) of the present invention is added instead of the surfactant A in the protective layer.
Prepared in the same manner as in -A.
次に色素固定材料の作り方について述べる。 Next, how to make the dye fixing material will be described.
実施例１の色素固定材料Ｒ−１において、硬膜剤*1とし
て1,2−ビス（ビニルスルフォニルアセトアミド）エタ
ンを用いる以外は色素固定材料Ｒ−１と同様にして色素
固定材料Ｒ−21を作製した。A dye fixing material R-21 was prepared in the same manner as the dye fixing material R-1 except that 1,2-bis (vinylsulfonylacetamide) ethane was used as the hardener * 1 in the dye fixing material R-1 of Example 1. It was made.
更に、該色素固定材料Ｒ−21において界面活性剤Ａの代
りに本発明の化合物（２）を用いる以外は色素固定材料
Ｒ−21と同様にして色素固定材料Ｒ−22を作製した。Further, a dye fixing material R-22 was prepared in the same manner as the dye fixing material R-21 except that the compound (2) of the present invention was used in place of the surfactant A in the dye fixing material R-21.
実施例１と同様に剥離性テストをおこなった。結果を表
−６に示す。A peelability test was conducted in the same manner as in Example 1. The results are shown in Table-6.
実施例３ ポリエチレンテレフタレートフィルムの支持体上に、次
の第１層（最下層）〜第６層（最上層）を塗布して多層
構成のカラー感光材料3Aを作成した。 Example 3 The following first layer (lowermost layer) to sixth layer (uppermost layer) were coated on a support of a polyethylene terephthalate film to prepare a color photosensitive material 3A having a multilayer structure.
第５層と第１層用のハロゲン化銀乳剤の作り方をのべ
る。 How to make silver halide emulsions for the fifth and first layers is described.
良く攪拌しているゼラチン水溶液（水1000ml中にゼラチ
ン20gと塩化ナトリウム3gを含み75℃に保温したもの）
に塩化ナトリウムと臭化カリウムを含有している水溶液
600mlと硝酸銀水溶液（水600mlに硝酸銀0.59モルを溶解
させたもの）を同時に40分間にわたって等流量で添加し
た。このようにして平均粒子サイズ0.40μの単分散立方
体塩臭化銀乳剤（臭素50モル％）を調製した。Well-stirred gelatin aqueous solution (1,000 ml of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C)
Aqueous solution containing sodium chloride and potassium bromide
600 ml and an aqueous solution of silver nitrate (600 ml of water in which 0.59 mol of silver nitrate were dissolved) were simultaneously added at an equal flow rate for 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol%) having an average grain size of 0.40 μm was prepared.
水洗、脱塩後チオ硫酸ナトリウム5mgと４−ヒドロキシ
−６−メチル−1,3,3a,7−テトラザインデン20mgを添加
して60℃で化学増感を行なった。乳剤の収量は600gであ
った。After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added and chemical sensitization was performed at 60 ° C. The yield of emulsion was 600 g.
第３層用のハロゲン化銀乳剤およびベンゾトリアゾール
銀乳剤の作り方は実施例１の乳剤IIおよび有機銀塩
（１）とそれぞれ同様である。The method for preparing the silver halide emulsion and the benzotriazole silver emulsion for the third layer is the same as that for the emulsion II and the organic silver salt (1) of Example 1, respectively.
次に色素供与性物質のゼラチン分散物の作り方について
述べる。Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.
イエローの色素供与性物質（Ａ）を5g、界面活性剤とし
て、コハク酸−２−エチル−ヘキシルエステルスルホン
酸ソーダ0.5g、トリイソノニルフォスフェート10gを秤
量し、酢酸エチル30mlを加え、約60℃に加熱溶解させ、
均一な溶液とした。この溶液と石灰処理ゼラチンの10％
溶液100gとを攪拌混合した後、ホモジナイザーで10分
間、10,000rpmにて分散した。この分散液をイエローの
色素供与性物質の分散物と言う。5 g of the yellow dye-donor substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 10 g of triisononyl phosphate were weighed, and 30 ml of ethyl acetate was added to the mixture to give about 60 Dissolve by heating to ℃,
A homogeneous solution was obtained. 10% of this solution and lime-processed gelatin
After mixing 100 g of the solution with stirring, the mixture was dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a yellow dye-donor substance dispersion.
下記のマゼンタの色素供与性物質（Ｂ）を使う事と高沸
点溶媒としてトリクレジルフォスフェートを7.5g使う以
外は上記方法により同様にしてマゼンタの色素供与性物
質の分散物を作った。A dispersion of the magenta dye-donor substance was prepared in the same manner as above except that the magenta dye-donor substance (B) described below was used and 7.5 g of tricresyl phosphate was used as the high boiling point solvent.
下記のシアンの色素供与性物質（Ｃ）を使い、イエロー
の色素分散物と同様にシアンの色素供与性物質の分散物
を作った。A cyan dye-donor dispersion was made in the same manner as the yellow dye dispersion using the cyan dye-donor (C) below.
感光材料3Aで用いた第６層の界面活性剤*7の代りに本発
明の化合物（２）を100mgを用いること以外は感光材料3
Aと全く同様にして感光材料3Bを作った。上記多層構成
のカラー感光材料に、タングステン電球を用い、連続的
に濃度が変化しているＧ、Ｒ、IR三色分解フィルター
（Ｇは500〜600nm、Ｒは600〜700nmのバンドパスフィル
ター、IRは700nm以上透過するフィルターを用い構成し
た）を通して500ルックスで１秒露光した。 Light-sensitive material 3 except that 100 mg of compound (2) of the present invention was used instead of the surfactant * 7 in the sixth layer used in light-sensitive material 3A.
A light-sensitive material 3B was prepared in the same manner as A. A tungsten light bulb is used for the above-mentioned multi-layered color light-sensitive material, and G, R, and IR three-color separation filters whose densities are continuously changed (G is 500 to 600 nm, R is 600 to 700 nm bandpass filter, IR Was constructed using a filter transmitting 700 nm or more) and exposed at 500 lux for 1 second.
これらの感光材料3A,3Bを150℃に加熱したヒートブロッ
ク上で20秒間加熱した。These photosensitive materials 3A and 3B were heated on a heat block heated to 150 ° C. for 20 seconds.
次に実施例１の色素固定材料Ｒ−１およびＲ−３でピコ
リン酸グアニジウムを用いない以外はそれぞれ同様にし
て作製した色素固定材料Ｒ−31およびＲ−32を用いて、
色素固定材料の膜面側に１m2当り12mlの水を供給した
後、加熱処理の終った上記感光材料とそれぞれ膜面が接
するように固定材料と重ね合せた。90℃のヒートブロッ
ク上で20秒加熱した後、色素固定材料を感光材料からひ
きはがすと、色素固定材料上にＧ、Ｒ、IRの３色分解フ
ィルターに対応して、それぞれイエロー、マゼンタ、シ
アンの色像が得られた。Next, using the dye fixing materials R-31 and R-32 prepared in the same manner, respectively, except that guanidinium picolinate was not used in the dye fixing materials R-1 and R-3 of Example 1,
After supplying 12 ml of water per 1 m 2 to the film surface side of the dye fixing material, the dye fixing material was superposed with the fixing material so that the film surface was brought into contact with the light-sensitive material which had been subjected to the heat treatment. After heating on a 90 ° C heat block for 20 seconds, the dye fixing material was peeled off from the photosensitive material, and yellow, magenta, and cyan corresponding to the three color separation filters G, R, and IR on the dye fixing material, respectively. A color image of was obtained.
また、本発明の化合物を感光材料または色素固定材料の
少なくとも一方に用いている場合には、両者の剥離は極
めて容易に行えたが、感光材料3Aと色素固定材料Ｒ−31
の組合せでは剥離ができなかった。Further, when the compound of the present invention was used in at least one of the light-sensitive material and the dye-fixing material, the peeling between the two was extremely easy, but the light-sensitive material 3A and the dye-fixing material R-31 were used.
The combination could not be peeled off.
Claims (1)
銀、バインダーおよび熱現像により拡散性の色素を生成
または放出する色素供与性物質を含有する感光要素を像
露光後または像露光と同時に加熱し、生成または放出さ
れた拡散性色素を色素固定要素の色素固定層へ転写し次
いで感光要素と色素固定要素を剥離する画像形成方法に
おいて、前記色素固定要素の少なくとも最上層に下記一
般式（Ｉ）で表される界面活性剤を含有することを特徴
とする画像形成方法。 式中、Rf、Rf′は、炭素数５〜16の、パーフルオロアル
キル基もしくはω位に水素原子１個を有するパーフルオ
ロアルキル基、または炭素数５〜16のパーフルオロアル
ケニル基を表わす。R1，R2は水素原子、アルキル基、ア
ルケニル基、アラルキル基を表わし、R1とR2の炭素数の
総和は５〜22である。 A,A′は −CONHCH2 n，−CO−または を表わす。（ここで、n,n′は１〜５の整数を表わし、
Ｒ′は水素原子または低級アルキル基を表わす。） a,b,c,dは各々０または１を表わすが、ａとｂおよびａ
とｃが同時に０になることはない。Ｚはスルホン酸又は
その塩、カルボン酸又はその塩、リン酸又はその塩、−
OSO3M（ここでＭは水素原子又はアルカリ金属を表わ
す）、CH2CH2OmＨ（ここでｍは１〜10の整数を表わ
す）、オニウム塩またはベタイン基を表わす。1. A photosensitive element containing in the photosensitive layer at least a photosensitive silver halide, a binder and a dye-donor substance which produces or releases a diffusible dye upon thermal development is heated after or at the same time as image exposure. In the image forming method, in which the generated or released diffusible dye is transferred to the dye-fixing layer of the dye-fixing element and then the light-sensitive element and the dye-fixing element are peeled off, at least the uppermost layer of the dye-fixing element is represented by the following general formula (I): An image forming method comprising a surfactant represented by: In the formula, Rf and Rf ′ represent a perfluoroalkyl group having 5 to 16 carbon atoms, a perfluoroalkyl group having one hydrogen atom at the ω position, or a perfluoroalkenyl group having 5 to 16 carbon atoms. R 1 and R 2 represent a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group, and the total number of carbon atoms of R 1 and R 2 is 5 to 22. A, A ′ is −CONHCH 2 n , −CO− or Represents (Here, n and n'represent an integer of 1 to 5,
R'represents a hydrogen atom or a lower alkyl group. ) A, b, c, d each represent 0 or 1, but a, b and a
And c cannot be 0 at the same time. Z is sulfonic acid or its salt, carboxylic acid or its salt, phosphoric acid or its salt,-
OSO 3 M (where M represents a hydrogen atom or an alkali metal), CH 2 CH 2 O m H (where m represents an integer of 1 to 10), an onium salt or a betaine group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089511A JPH07120016B2 (en) | 1986-04-18 | 1986-04-18 | Image forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089511A JPH07120016B2 (en) | 1986-04-18 | 1986-04-18 | Image forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62245259A JPS62245259A (en) | 1987-10-26 |
| JPH07120016B2 true JPH07120016B2 (en) | 1995-12-20 |
Family
ID=13972806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61089511A Expired - Lifetime JPH07120016B2 (en) | 1986-04-18 | 1986-04-18 | Image forming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07120016B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6803180B2 (en) | 1999-12-13 | 2004-10-12 | Fuji Photo Film Co., Ltd. | Information recording material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59206832A (en) * | 1983-05-10 | 1984-11-22 | Konishiroku Photo Ind Co Ltd | Photographic element |
| JP3361534B2 (en) * | 1991-07-26 | 2003-01-07 | 富士通テン株式会社 | Pump motor drive controller |
-
1986
- 1986-04-18 JP JP61089511A patent/JPH07120016B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62245259A (en) | 1987-10-26 |
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