JPH11174619A - Silver halide photosensitive material - Google Patents
Silver halide photosensitive materialInfo
- Publication number
- JPH11174619A JPH11174619A JP35410597A JP35410597A JPH11174619A JP H11174619 A JPH11174619 A JP H11174619A JP 35410597 A JP35410597 A JP 35410597A JP 35410597 A JP35410597 A JP 35410597A JP H11174619 A JPH11174619 A JP H11174619A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- pigment
- dye
- silver
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 178
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 174
- 239000004332 silver Substances 0.000 title claims abstract description 174
- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000000049 pigment Substances 0.000 claims abstract description 118
- 239000000839 emulsion Substances 0.000 claims abstract description 95
- 230000005540 biological transmission Effects 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000011161 development Methods 0.000 claims abstract description 23
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229940065287 selenium compound Drugs 0.000 claims abstract description 8
- 150000003343 selenium compounds Chemical class 0.000 claims abstract description 8
- 150000003498 tellurium compounds Chemical class 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 113
- 238000012545 processing Methods 0.000 claims description 45
- 239000000084 colloidal system Substances 0.000 claims description 33
- 239000011241 protective layer Substances 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 9
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 8
- 229940045105 silver iodide Drugs 0.000 claims description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 6
- 150000004056 anthraquinones Chemical class 0.000 claims description 6
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 claims description 6
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical group [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 60
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 46
- 239000002245 particle Substances 0.000 abstract description 33
- 230000035945 sensitivity Effects 0.000 abstract description 14
- 238000011109 contamination Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- VAYROLOSUUAGTR-UHFFFAOYSA-N [Ag].[I] Chemical compound [Ag].[I] VAYROLOSUUAGTR-UHFFFAOYSA-N 0.000 abstract 1
- XUAJZOHXBBRXOX-UHFFFAOYSA-M [Ag]Br.[I] Chemical compound [Ag]Br.[I] XUAJZOHXBBRXOX-UHFFFAOYSA-M 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 149
- 235000013339 cereals Nutrition 0.000 description 76
- 150000001875 compounds Chemical class 0.000 description 60
- 239000000243 solution Substances 0.000 description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- 206010070834 Sensitisation Diseases 0.000 description 41
- 230000008313 sensitization Effects 0.000 description 41
- 239000000126 substance Substances 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 34
- 238000000576 coating method Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 32
- 239000003795 chemical substances by application Substances 0.000 description 31
- 108010010803 Gelatin Proteins 0.000 description 29
- 229920000159 gelatin Polymers 0.000 description 29
- 239000008273 gelatin Substances 0.000 description 29
- 235000019322 gelatine Nutrition 0.000 description 29
- 235000011852 gelatine desserts Nutrition 0.000 description 29
- 239000006185 dispersion Substances 0.000 description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 28
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- 230000001235 sensitizing effect Effects 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000011230 binding agent Substances 0.000 description 18
- 239000004816 latex Substances 0.000 description 17
- 229920000126 latex Polymers 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- 229910001961 silver nitrate Inorganic materials 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 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 11
- 238000001035 drying Methods 0.000 description 11
- 102000039446 nucleic acids Human genes 0.000 description 11
- 108020004707 nucleic acids Proteins 0.000 description 11
- 150000007523 nucleic acids Chemical class 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 244000172533 Viola sororia Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000005070 ripening Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 235000019646 color tone Nutrition 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 229910052688 Gadolinium Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000006224 matting agent Substances 0.000 description 7
- 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 7
- 229910052711 selenium Inorganic materials 0.000 description 7
- 239000011669 selenium Substances 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 235000010323 ascorbic acid Nutrition 0.000 description 6
- 239000011668 ascorbic acid Substances 0.000 description 6
- 229960005070 ascorbic acid Drugs 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 229910052714 tellurium Inorganic materials 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical compound OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 4
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052775 Thulium Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000843 anti-fungal effect Effects 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 4
- 235000019239 indanthrene blue RS Nutrition 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical class N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical class SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 3
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000001000 anthraquinone dye Substances 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229940097275 indigo Drugs 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 3
- 229940116357 potassium thiocyanate Drugs 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 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 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003567 thiocyanates Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 125000005627 triarylcarbonium group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 2
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical class SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 2
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical compound C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 2
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 2
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 2
- 229930024421 Adenine Natural products 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- FYOWZTWVYZOZSI-UHFFFAOYSA-N thiourea dioxide Chemical compound NC(=N)S(O)=O FYOWZTWVYZOZSI-UHFFFAOYSA-N 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- BVBALDDYDXBEKK-UHFFFAOYSA-N tributoxy(selanylidene)-$l^{5}-phosphane Chemical compound CCCCOP(=[Se])(OCCCC)OCCCC BVBALDDYDXBEKK-UHFFFAOYSA-N 0.000 description 1
- NJPOTNJJCSJJPJ-UHFFFAOYSA-N tributyl benzene-1,3,5-tricarboxylate Chemical compound CCCCOC(=O)C1=CC(C(=O)OCCCC)=CC(C(=O)OCCCC)=C1 NJPOTNJJCSJJPJ-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- KTFAZNVGJUIWJM-UHFFFAOYSA-N trimethyl(sulfanylidene)-$l^{5}-phosphane Chemical compound CP(C)(C)=S KTFAZNVGJUIWJM-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- ZFVJLNKVUKIPPI-UHFFFAOYSA-N triphenyl(selanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=[Se])C1=CC=CC=C1 ZFVJLNKVUKIPPI-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、良好な画像色調を
有し、ケイ光増感紙等に対する汚染性が改善可能である
ハロゲン化銀写真写真材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having a good image tone and capable of improving the stainability on fluorescent intensifying screens and the like.
【0002】[0002]
【従来の技術】ハロゲン化銀乳剤の被覆力は乳剤製造業
者にとって極めて関心の深いものである。その理由は、
高被覆力の乳剤を使用すれば、一定の光学濃度を保つた
めに必要な銀量を節約できるからである。BACKGROUND OF THE INVENTION The covering power of silver halide emulsions is of great interest to emulsion manufacturers. The reason is,
This is because the use of an emulsion having a high covering power can save the amount of silver required to maintain a constant optical density.
【0003】高アスペクト比で粒子厚みの小さい平板粒
子を用いることにより、著しく現像銀被覆力が上がるこ
とが、米国特許4,411,986号、同4,434,226号、同4,413,
053号、同4,414,304号、同4,414,306号、および同4,43
5,501号等に開示されている。The use of tabular grains having a high aspect ratio and a small grain thickness significantly increases the developing silver covering power, as described in US Pat. Nos. 4,411,986, 4,434,226 and 4,413,
Nos. 053, 4,414,304, 4,414,306, and 4,43
No. 5,501 and the like.
【0004】また、厚みが0.07μmをきる極薄平板粒子
に関しては、特開昭62-99751号、特開昭62-115435号、
特開平6-43605号、特開平6-43606号等に開示されてい
る。Further, ultra-thin tabular grains having a thickness of less than 0.07 μm are disclosed in JP-A-62-99751, JP-A-62-115435,
It is disclosed in JP-A-6-43605 and JP-A-6-43606.
【0005】欧州特許(EP)0699944A号、EP0699946A号、
EP0699947A号、特開平8-101476号、特開平8-101475号、
特開平8-101473号、特開平8-101472号、特開平8-69069
号、米国特許5,494,789号には、エピタキシャル部位を
有するアスペクト比の高い平板粒子に関する技術が開示
されている。[0005] European patents (EP) 0699944A, EP0699946A,
EP0699947A, JP-A-8-101476, JP-A-8-101475,
JP-A-8-101473, JP-A-8-101472, JP-A-8-69069
No. 5,494,789 discloses a technique relating to tabular grains having an epitaxial portion and having a high aspect ratio.
【0006】しかしながら、上述の高い銀被覆力を与え
る乳剤粒子の現像銀の色調は、粒子サイズや粒子厚みに
依存するが、ほとんど例外なく黄色味を帯びて画像観察
者に不快な印象を与える。この黄色味を帯びるのは、粒
子サイズや粒子厚みの減少に伴い、現像銀もそのサイズ
と厚みが減少し、青色光成分の散乱が増加し、黄色味の
強い光となるためである。このような現象は、ハロゲン
化銀乳剤として微粒子乳剤(例えば平均粒子サイズ0.
4μm 以下)や粒子厚みの薄い平板状粒子(例えば、粒
子厚み0.4μm以下)を用いたときに特に問題となる。一
般に、現像銀の色調を整えるために色調剤と呼ばれるも
のがよく用いられている。色調剤としては、例えば、あ
る種のメルカプト化合物等が用いられる。しかしなが
ら、このような従来からよく知られている色調剤を高感
度のハロゲン化銀粒子から成る乳剤に適用しても、著し
い減感作用を引き起こし実用化できない。[0006] However, the color tone of the developed silver of the emulsion grains giving the high silver covering power depends on the grain size and grain thickness, but almost always has a yellow tint, giving an unpleasant impression to an image observer. The reason for the yellowish tint is that as the grain size and grain thickness decrease, the size and thickness of the developed silver also decrease, the scattering of blue light components increases, and the yellowish light becomes strong. Such a phenomenon is caused by a fine grain emulsion (for example, having an average grain size of 0.
This is particularly problematic when tabular grains having a small grain thickness (for example, grain thickness of 0.4 μm or less) are used. Generally, in order to adjust the color tone of developed silver, a so-called tone agent is often used. As the color tone agent, for example, a certain kind of mercapto compound is used. However, even if such a conventionally well-known toning agent is applied to an emulsion composed of silver halide grains having high sensitivity, a remarkable desensitizing effect is caused, and it cannot be put to practical use.
【0007】そこで、特開昭60-154251号、特開昭62-27
6539号、特開昭61-285445号、特開平5-204085号に記載
されているように、現像銀色調がニュートラルな黒にな
るように、感材中に実質的に水不溶性の染料を含有させ
て色調を調節することが広く行われている。また、特開
平4-234035号、特開平7-199394号、欧州特許655645A1号
には、感材中に顔料を含有させることにより、現像銀色
調の調節と分光増感色素による処理後の残色の改良とを
行うことが開示されている。Therefore, Japanese Patent Application Laid-Open Nos. 60-154251 and 62-27
No. 6539, JP-A-61-285445, JP-A-5-204085, containing a substantially water-insoluble dye in the light-sensitive material so that the developed silver tone becomes neutral black. It is widely used to adjust the color tone. Also, JP-A-4-234035, JP-A-7-199394, and EP 655645A1, by including a pigment in the photographic material, control of the developed silver tone and residual color after processing with a spectral sensitizing dye. It is disclosed that an improvement of
【0008】ところが、平板粒子のアスペクト比がさら
に高くなると、透過の現像銀色調が黄色味を帯びてくる
のみならず、反射の現像銀色調も赤茶色を帯びてきて非
常に不快な印象を与える。However, when the aspect ratio of the tabular grains is further increased, not only the developed silver tone of transmission becomes yellowish but also the developed silver tone of reflection becomes reddish brown, giving a very unpleasant impression. .
【0009】一般に、透過光観察時においても外部光が
存在する場合には一定の割合で反射光も含まれることが
多く、現像銀の反射色調も黒色であることが望まれる。
しかしながら、この問題に関し、上述の従来技術では充
分とはいえなかった。In general, even when transmitted light is observed, when external light is present, reflected light is often included at a constant rate, and it is desired that the reflected color tone of developed silver be black.
However, with respect to this problem, the above-mentioned prior art was not sufficient.
【0010】[0010]
【発明が解決しようとする課題】本発明の目的は、第一
に、画像銀の透過および反射の黒色度が改良され、かつ
高感度で、高い銀被覆力を有し、残色の少ないハロゲン
化銀写真感光材料を提供することである。第二に、これ
らに加えて、ケイ光増感紙等に対する汚染性の少ないハ
ロゲン化銀写真感光材料を提供することである。第三
に、さらに、これらに加えて、現像処理後の画像の認識
性に優れたハロゲン化銀写真感光材料を提供することで
ある。SUMMARY OF THE INVENTION An object of the present invention is, first, to improve the blackness of transmission and reflection of image silver, and to provide a high sensitivity, high silver coverage, and low residual color. An object of the present invention is to provide a silver halide photographic light-sensitive material. Secondly, in addition to these, it is an object of the present invention to provide a silver halide photographic light-sensitive material having less contamination to fluorescent intensifying screens and the like. Thirdly, it is another object of the present invention to provide a silver halide photographic light-sensitive material having excellent image recognizability after development processing.
【0011】[0011]
【課題を解決するための手段】本発明の目的は以下によ
り達成された。 (1) 支持体上に少なくとも一層のハロゲン化銀乳剤
層を有する青色染色された医療用ハロゲン化銀写真感光
材料であって、前記ハロゲン化銀乳剤層に含有されるハ
ロゲン化銀粒子の全投影面積の50%以上がアスペクト
比が5以上の平板状粒子で占められており、前記平板状
粒子が平均ヨウ化銀含有率1モル%以下のヨウ臭化銀ま
たは臭化銀の組成を有し、かつセレン化合物および/ま
たはテルル化合物により化学増感されており、前記ハロ
ゲン化銀乳剤層および/または前記ハロゲン化銀乳剤層
よりも上層の親水性コロイド層中に、570〜650n
mの間に極大吸収波長を有する顔料および/または染料
が含有されており、かつ前記顔料および/または染料の
含有量が、現像処理後の未露光部白色透過濃度のうち、
前記顔料および/または染料の寄与が50%以上である
量であることを特徴とするハロゲン化銀写真感光材料。 (2) 前記顔料がアントラキノン系顔料を含む上記
(1)のハロゲン化銀写真感光材料。 (3) 前記顔料が金属フタロシアニン系顔料とジオキ
サジン系顔料とを含む上記(1)または(2)のハロゲ
ン化銀写真感光材料。 (4) 前記顔料および/または染料が、前記ハロゲン
化銀乳剤層よりも上層で表面保護層よりも下層にある親
水性コロイド層中に含有される上記(1)〜(3)のい
ずれかのハロゲン化銀写真感光材料。 (5) 現像処理後の未露光部白色光透過濃度のうち、
前記顔料および/または染料の寄与が80%以上である
上記(1)〜(4)のいずれかのハロゲン化銀写真感光
材料。 (6) 前記支持体が染色されておらず、前記支持体に
下塗層が存在するときは、この下塗層も染色されていな
い上記(1)〜(5)のいずれかのハロゲン化銀写真感
光材料。The object of the present invention has been attained by the following. (1) A blue-dyed medical silver halide photographic material having at least one silver halide emulsion layer on a support, wherein all projections of silver halide grains contained in the silver halide emulsion layer are provided. 50% or more of the area is occupied by tabular grains having an aspect ratio of 5 or more, and the tabular grains have a silver iodobromide or silver bromide composition having an average silver iodide content of 1 mol% or less. And sensitized by a selenium compound and / or a tellurium compound, and 570 to 650 n in the silver halide emulsion layer and / or the hydrophilic colloid layer above the silver halide emulsion layer.
m, a pigment and / or a dye having a maximum absorption wavelength is contained, and the content of the pigment and / or the dye is in the unexposed portion white transmission density after the development processing.
A silver halide photographic light-sensitive material, wherein the contribution of the pigment and / or dye is 50% or more. (2) The silver halide photographic light-sensitive material according to the above (1), wherein the pigment contains an anthraquinone pigment. (3) The silver halide photographic material as described in the above item (1) or (2), wherein the pigment contains a metal phthalocyanine pigment and a dioxazine pigment. (4) Any one of the above (1) to (3), wherein the pigment and / or dye is contained in a hydrophilic colloid layer above the silver halide emulsion layer and below the surface protective layer. Silver halide photographic material. (5) Of the unexposed area white light transmission density after the development processing,
The silver halide photographic light-sensitive material according to any one of the above (1) to (4), wherein the contribution of the pigment and / or dye is 80% or more. (6) When the support is not dyed and an undercoat layer is present on the support, the silver halide according to any one of (1) to (5) above, wherein the undercoat layer is not dyed. Photosensitive material.
【0012】[0012]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明のハロゲン化銀写真感光材料は青色染色さ
れた医療用ハロゲン化銀写真感光材料であり、ハロゲン
化銀乳剤層に含まれるハロゲン化銀粒子の全投影面積の
50%以上がアスペクト比5以上の平板状粒子で占めら
れており、平板状粒子の組成は平均ヨウ化銀含有率1モ
ル%以下のヨウ臭化銀または臭化銀であり、かつこれら
の粒子はセレン化合物および/またはテルル化合物によ
り化学増感されたものである。また、ハロゲン化銀乳剤
層やこれより上層の親水性コロイド層には、所定の顔料
および/または染料が含まれており、現像処理後の未露
光部白色光透過濃度のうち、顔料および/または染料の
寄与が50%以上となるような含有量で含まれている。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The silver halide photographic light-sensitive material of the present invention is a medical silver halide photographic light-sensitive material stained with blue, and the aspect ratio is 5 or more of 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion layer. And the composition of the tabular grains is silver iodobromide or silver bromide having an average silver iodide content of 1 mol% or less, and these grains are composed of a selenium compound and / or a tellurium compound. Is chemically sensitized by Further, the silver halide emulsion layer and the hydrophilic colloid layer above the silver halide emulsion layer contain a predetermined pigment and / or dye. The content is such that the contribution of the dye is 50% or more.
【0013】これにより、画像銀の黒色度が改良され、
高感度で残色の少ないハロゲン化銀写真感光材料が得ら
れる。これに対し、上記の高アスペクト比の平板状粒子
のハロゲン化銀粒子の全投影面積に占める割合が50%
未満となると、感度の低下が著しくなり、また平均ヨウ
化銀含有率が1モル%を超えると残色が発生する。一
方、顔料や染料を上記の所定の層中に含有させないもの
としたり、現像処理後の未露光部白色透過濃度に対する
顔料や染料の寄与が50%未満となるような含有量であ
ると銀色調の悪化がみられる。As a result, the blackness of the image silver is improved,
A silver halide photographic light-sensitive material having high sensitivity and little residual color can be obtained. On the other hand, the ratio of the tabular grains having the high aspect ratio to the total projected area of the silver halide grains is 50%.
If it is less than 1, the sensitivity is remarkably reduced, and if the average silver iodide content exceeds 1 mol%, a residual color is generated. On the other hand, if the content of the pigment or the dye is not contained in the above-mentioned predetermined layer, or if the content of the pigment or the dye is less than 50% to the unexposed area white transmission density after the development processing, the silver tone is increased. Is worsened.
【0014】また、銀色調の改良を図る上では、ハロゲ
ン化銀乳剤層より上層に位置する中間層や保護層等に顔
料や染料を含有させることが好ましい。In order to improve the silver tone, it is preferable to include a pigment or a dye in an intermediate layer or a protective layer located above the silver halide emulsion layer.
【0015】なお、ケイ光増感紙等に対する汚染をなく
すという観点からは、顔料や染料を表面保護層より下層
となる中間層やハロゲン化銀乳剤層等に含有させること
が好ましい。From the viewpoint of eliminating contamination on the fluorescent intensifying screen and the like, it is preferable to include a pigment or a dye in the intermediate layer or the silver halide emulsion layer below the surface protective layer.
【0016】こうしたことから、顔料や染料は表面保護
層とハロゲン化銀乳剤層との間にある中間層等に含有さ
せることが最も好ましい。For these reasons, it is most preferable that the pigment or dye is contained in an intermediate layer between the surface protective layer and the silver halide emulsion layer.
【0017】また、現像処理後の画像の認識性を良化す
る上では、未露光部白色透過濃度に対する顔料や染料の
80%以上であることが好ましく、支持体(下塗層が存
在するときは下塗層を含む)は染色ないし着色されてい
ないことが好ましい。In order to improve the recognizability of the image after the development processing, it is preferable that the content of the pigment or dye is at least 80% of the unexposed portion white transmission density. Is preferably not dyed or colored.
【0018】さらに詳細に本発明を説明する。本発明の
ハロゲン化銀写真感光材料は、支持体上に少なくとも1
層のハロゲン化銀乳剤層を有している。ハロゲン化銀乳
剤層は1層でもよいし、2層以上(好ましくは4層以
下)でもよい。The present invention will be described in further detail. The silver halide photographic light-sensitive material of the present invention comprises at least one photographic material on a support.
A silver halide emulsion layer. The number of silver halide emulsion layers may be one, or two or more (preferably four or less).
【0019】本発明のハロゲン化銀写真感光材料は、ハ
ロゲン化銀乳剤層および/またはハロゲン化銀乳剤層よ
りも上層の親水性コロイド層中に、570〜650nm、より好
ましくは580〜640nmの間に極大吸収波長を有する顔料お
よび/または染料が含まれている。本発明の顔料および
/または染料は単独で用いられても、組み合わされて用
いられてもよい。どちらの場合でも、その最大吸収波長
が570nm〜650nmであることが好ましく、580〜640nmであ
ることがより好ましい。The silver halide photographic light-sensitive material of the present invention may be incorporated in a silver halide emulsion layer and / or a hydrophilic colloid layer above the silver halide emulsion layer in a range of 570 to 650 nm, more preferably 580 to 640 nm. Contains a pigment and / or dye having a maximum absorption wavelength. The pigment and / or dye of the present invention may be used alone or in combination. In either case, the maximum absorption wavelength is preferably from 570 to 650 nm, more preferably from 580 to 640 nm.
【0020】本発明に用いられる顔料としては、市販の
ものの他、各種文献に記載されている公知のものが利用
できる。文献に関してはカラーインデックス(The Soci
etyof Dyers and Colourists編)、「改訂新版顔料便
覧」日本顔料技術協会編(1989年刊)、「最新顔料
応用技術」CMC出版(1986年刊)、「印刷インキ
技術」CMC出版(1984年刊)、W.Herbst,K.Hunge
r共著によるIndustrial Organic Pigments(VCH Verlags
gesellshaft、1993年刊)等がある。具体的には、
有機顔料ではアゾ顔料(アゾレーキ顔料、不溶性アゾ顔
料、縮合アゾ顔料、キレートアゾ顔料)、多環式顔料
(フタロシアニン系顔料、アントラキノン系原料、ペリ
レンおよびペリノン系顔料、インジゴ系顔料、キナクリ
ドン系顔料、ジオキサジン系顔料、イソインドリノン系
顔料、キノフタロン系顔料、ジケトピロロピロール系顔
料等)、染付けレーキ顔料(酸性または塩基性染料のレ
ーキ顔料)、アジン顔料等、および無機顔料を用いるこ
とができる。中でも好ましい青味の色調を得るために
は、フタロシアニン顔料、アントラキノン系のインダン
トロン顔料、染め付けレーキ顔料系のトリアリールカル
ボニウム顔料、インジゴ、無機顔料の群青、コバルトブ
ルーが好ましい。さらに色調を調整するために、赤ない
し紫色の顔料、例えばジオキサジン系顔料、キナクリド
ン系顔料、ジケトピロロピロール系顔料などが上記青色
顔料と併用されていてもよい。特に、アントラキノン系
顔料、あるいは、金属フタロシアニン系顔料とジオキサ
ジン系顔料との併用が好ましい。As the pigment used in the present invention, commercially available pigments and known pigments described in various documents can be used. For literature, see Color Index (The Soci
etyof Dyers and Colorists), “Revised New Edition Pigment Handbook”, edited by the Japan Pigment Technology Association (1989), “Latest Pigment Application Technology”, CMC Publishing (1986), “Printing Ink Technology”, CMC Publishing (1984), W. Herbst, K. Hunge
r Co-authored Industrial Organic Pigments (VCH Verlags
gesellshaft, 1993). In particular,
Organic pigments include azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone-based raw materials, perylene and perinone pigments, indigo-based pigments, quinacridone-based pigments, and dioxazine-based pigments. Pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, etc., dyeing lake pigments (lake pigments of acidic or basic dyes), azine pigments, and inorganic pigments can be used. Among them, phthalocyanine pigments, anthraquinone-based indanthrone pigments, dyed lake pigment-based triarylcarbonium pigments, indigo, and ultramarine blue of inorganic pigments and cobalt blue are preferable for obtaining a preferable bluish color tone. In order to further adjust the color tone, a red or purple pigment such as a dioxazine pigment, a quinacridone pigment, a diketopyrrolopyrrole pigment, or the like may be used in combination with the blue pigment. In particular, it is preferable to use an anthraquinone pigment or a combination of a metal phthalocyanine pigment and a dioxazine pigment.
【0021】以下に好ましい顔料の具体例を列挙する。
青色顔料の例としては、フタロシアニン系のC.I.Pigmen
t Blue 15、同15:1、同15:2、同15:3、同15:4、同15:6
(銅フタロシアニン)、モノクロロないし低塩素化銅フ
タロシアニン、C.I.Pigment Blue 16(無金属フタロシ
アニン)、中心金属がZn、Al、Tiであるフタロシアニ
ン、バット染料としても知られるインダントロン系のC.
I.Pigment Blue 60やそれらのハロゲン置換体、例えば
C.I.PigmentBlue 64、同21、アゾ系のC.I.Pigment Blue
25、 インジゴ系のC.I.Pigment Blue 66およびレーキ
顔料であるC.I.Pigment Blue 63、トリアリールカルボ
ニウム型酸性染料あるいは塩基性染料のレーキ顔料であ
るC.I.Pigment Blue 1、同2、同3、同9、同10、同14、
同18、同19、同24:1、同24:x、同56、同61、同62が挙げ
られる。赤ないし紫顔料としては、ジオキサジン系のC.
I.Pigment Violet 23、同37、アゾ系のC.I.Pigment Vio
let 同13、同25、同32、同44、同50、C.I.Pigment Red
23、同52:1、同57:1、同63:2、同146、同150、同151、
同175、同176、同185、同187、同245、キナクリドン系
のC.I.Pigment Violet 19、同42、C.I.Pigment Red 12
2、同192、同202、同207、同209、トリアリールカルボ
ニウム系のレーキ顔料であるC.I.Pigment Violet 1、同
2、同3、同27、同39、C.I.Pigment Red 81:1、ペリレン
系のC.I.Pigment Violet 29、アントラキノン系のC.I.P
igmentViolet 5:1、同31、同33、チオインジゴ系のC.I.
Pigment Red 38、同88が挙げられる。Specific examples of preferred pigments will be listed below.
Examples of blue pigments include phthalocyanine-based CI Pigmen
t Blue 15, 15:15, 15: 2, 15: 3, 15: 4, 15: 6
(Copper phthalocyanine), monochloro or low chlorinated copper phthalocyanine, CI Pigment Blue 16 (metal-free phthalocyanine), phthalocyanine whose central metal is Zn, Al, Ti, indanthrone-based C.
I. Pigment Blue 60 and their halogen-substituted products, such as
CIPigmentBlue 64, 21; azo-based CIPigment Blue
25, Indigo-based CI Pigment Blue 66 and lake pigment CI Pigment Blue 63, triarylcarbonium type acidic dye or basic dye lake pigment CI Pigment Blue 1, 2, 3, 9, 9, 10 14,
18, 18, 19:24, 24: x, 56, 61, and 62. As red to purple pigments, dioxazine-based C.
I. Pigment Violet 23, 37, Azo-based CI Pigment Vio
let 13, 25, 32, 44, 50, CI Pigment Red
23, 52: 1, 57: 1, 63: 2, 146, 150, 151,
175, 176, 185, 187, 245, quinacridone-based CI Pigment Violet 19, 42, and CI Pigment Red 12
2, 192, 202, 207, 209, CIigment Violet 1, a triarylcarbonium-based lake pigment,
2, 3, 27, 39, CI Pigment Red 81: 1, Perylene-based CI Pigment Violet 29, Anthraquinone-based CIP
igmentViolet 5: 1, 31 and 33, thioindigo CI
Pigment Red 38 and 88.
【0022】特に本発明に好ましく用いられる顔料の具
体例としては、C.I.Pigment Blue 60[化合物(1)]
が好ましく、C.I.Pigment Blue 15等の銅フタロシアニ
ン[化合物(2)]、および、それと併用してC.I.Pigm
ent Violet 23[化合物(3)]もしくはC.I.Pigment V
iolet 37[化合物(4)]が好ましく用いられる。銅フ
タロシアニンとC.I.Pigment Violet 23もしくはC.I.Pig
ment Violet 37とを併用する場合の使用比率(重量)は
50:1〜1:1、より好ましくは40:1〜3:1である。A specific example of a pigment preferably used in the present invention is CI Pigment Blue 60 [compound (1)].
And copper phthalocyanine [compound (2)] such as CI Pigment Blue 15;
ent Violet 23 [Compound (3)] or CI Pigment V
iolet 37 [compound (4)] is preferably used. Copper phthalocyanine and CIPigment Violet 23 or CIPig
When used together with ment Violet 37, the usage ratio (weight)
It is 50: 1 to 1: 1, more preferably 40: 1 to 3: 1.
【0023】[0023]
【化1】 Embedded image
【0024】[0024]
【化2】 Embedded image
【0025】[0025]
【化3】 Embedded image
【0026】[0026]
【化4】 Embedded image
【0027】本発明に使用できる顔料は、上述の裸の顔
料であっても良いし、表面処理を施された顔料でも良
い。表面処理の方法には、樹脂やワックスを表面コート
する方法、界面活性剤を付着させる方法、反応性物質
(例えば、シランカップリング剤やエポキシ化合物、ポ
リイソシアネートなど)を顔料表面に結合させる方法な
どが考えられ、次の文献等に記載されている。 金属石鹸の性質と応用(幸書房) 印刷インキ技術(CMC出版、1984) 最新顔料応用技術(CMC出版、1986)The pigment which can be used in the present invention may be the above-mentioned naked pigment or a pigment which has been subjected to a surface treatment. Examples of the surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. And are described in the following documents. Properties and application of metal soap (Koshobo) Printing ink technology (CMC Publishing, 1984) Latest pigment application technology (CMC Publishing, 1986)
【0028】本発明において顔料は、バインダー中に分
散されて用いられる。分散剤は、用いるバインダーと顔
料とに合わせて種々のもの、例えば界面活性剤型の低分
子分散剤や高分子型分散剤を用いることができる。分散
剤の例としては、特開平3-69949号、欧州特許第549,486
号等に記載のものを挙げることができる。In the present invention, the pigment is used by being dispersed in a binder. As the dispersant, various ones according to the binder and the pigment to be used, for example, a surfactant type low molecular dispersant or a high molecular dispersant can be used. Examples of dispersants include JP-A-3-69949, EP 549,486.
And the like.
【0029】本発明において顔料は、前記表面処理によ
り有機溶媒中に容易に分散することができるように処理
した顔料を、高沸点溶媒に分散し、親水性コロイド溶液
に加えて乳化分散した状態で用いることもできる。In the present invention, the pigment is prepared by dispersing a pigment, which has been treated so as to be easily dispersible in an organic solvent by the above-mentioned surface treatment, in a high-boiling-point solvent, adding the resultant to a hydrophilic colloid solution, and emulsifying the pigment. It can also be used.
【0030】本発明に使用できる顔料の平均粒径は、分
散後で0.01〜10μmの範囲であることが好ましく、0.05
〜1μmであることがさらに好ましい。The average particle size of the pigment that can be used in the present invention is preferably in the range of 0.01 to 10 μm after dispersion,
More preferably, it is 1 μm.
【0031】顔料をバインダー中へ分散する方法として
は、インク製造やトナー製造時に用いられる公知の分散
技術が使用できる。分散機としては、サンドミル、アト
ライター、パールミル、スーパーミル、ボールミル、イ
ンペラー、デスパーサー、KDミル、コロイドミル、ダ
イナトロン、3本ロールミル、加圧ニーダー等が挙げら
れる。詳細は「最新顔料応用技術」(CMC出版、19
86)に記載がある。As a method for dispersing the pigment in the binder, known dispersion techniques used in the production of inks and toners can be used. Examples of the dispersing machine include a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 19
86).
【0032】本発明に用いる染料としては、水不溶性で
現像処理後も感材中に染料として存在しうるものであ
り、ピラゾロール染料、アントラキノン染料、アゾ染
料、アゾメチン染料、インドアニリン染料、オキソノー
ル染料、カルボシアニン染料、スチリル染料、トリフェ
ニルメタン染料等の中から、極大吸収波長が570nm〜650
nm、より好ましくは580〜640nmであるものが用いられ
る。この明細書では、染料が示す極大吸収波長とは、染
料を感材中に存在させた状態における極大吸収波長を意
味する。上記染料の内で、現像処理に対する安全性や、
光堅牢性や減感、カブリ、ステイン等写真性に対する影
響を考慮すると、ピラゾロール染料、アントラキノン染
料、アゾ染料、アゾメチン染料、インドアニリン染料の
うちから好ましいものが用いられる。さらに好ましく
は、ピラゾロール染料およびアントラキノン染料であ
る。本発明に用いられる染料の具体的な例を以下に示
す。The dyes used in the present invention are water-insoluble and can be present as dyes in the photographic material even after development processing, and include pyrazolol dyes, anthraquinone dyes, azo dyes, azomethine dyes, indoaniline dyes, oxonol dyes, Among carbocyanine dyes, styryl dyes, triphenylmethane dyes, etc., the maximum absorption wavelength is 570 nm to 650
nm, more preferably 580 to 640 nm. In this specification, the maximum absorption wavelength of a dye means the maximum absorption wavelength in a state where the dye is present in a light-sensitive material. Among the above dyes, safety for development processing,
Considering the effects on photographic properties such as light fastness, desensitization, fog, and stain, preferred ones are used among pyrazolol dyes, anthraquinone dyes, azo dyes, azomethine dyes, and indoaniline dyes. More preferred are a pyrazolol dye and an anthraquinone dye. Specific examples of the dye used in the present invention are shown below.
【0033】[0033]
【化5】 Embedded image
【0034】[0034]
【化6】 Embedded image
【0035】[0035]
【化7】 Embedded image
【0036】[0036]
【化8】 Embedded image
【0037】本発明に用いる染料は種々の公知の方法で
分散することができる。 本発明の染料を直接、乳剤層や親水性コロイド層に
溶解もしくは分散させる方法、あるいは、水性溶液また
は溶媒に溶解もしくは分散させた後、乳剤層や親水性コ
ロイド層に用いる方法。適当な溶媒、例えば、メチルア
ルコール、エチルアルコール、プロピルアルコール、メ
チルセロソルブ、特開昭48-9715号、米国特許3,756,830
号に記載のハロゲン化アルコール、アセトン、水、ピリ
ジン等、または、これらの混合溶媒などの中に溶解さ
れ、溶液の形で添加することもできる。The dye used in the present invention can be dispersed by various known methods. A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye is dissolved or dispersed in an aqueous solution or a solvent and then used in the emulsion layer or the hydrophilic colloid layer. Suitable solvents, for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, U.S. Pat.
The compound may be dissolved in a halogenated alcohol, acetone, water, pyridine, or the like described in the above item, or a mixed solvent thereof, and added in the form of a solution.
【0038】 化合物をオイル、すなわち実質的に水
不溶で沸点が約160℃以上の高沸点溶媒に溶解した液を
親水性コロイド溶液に加えて分散する方法。この高沸点
溶媒としては、米国特許2,322,027号に記載されている
ような、例えば、フタール酸アルキルエステル(ジブチ
ルフタレート、ジオクチルフタレート等)、リン酸エス
テル(ジフェニルフォスフェート、トリフェニルフォス
フェート、トリクレジルフォスフェート、ジオクチルブ
チルフォスフェート)、クエン酸エステル(例えばアセチ
ルクエン酸トリブチル)、安息香酸エステル(例えば安息
香酸オクチル)、アルキルアミド(例えばジエチルラウリ
ルアミド)、脂肪酸エステル類(例えばジブトキシエチル
サクシネート、ジエチルアゼレート)、トリメシン酸エ
ステル類(例えばトリメシン酸トリブチル)などが使用で
きる。また、沸点約30℃ないし約150℃の有機溶媒、例
えば酢酸エチル、酢酸ブチル等の低級アルキルアセレー
ト、プロピオン酸エチル、二級ブチルアルコール、メチ
ルイソブチルケトン、β-エトキシエチルアセテート、
メチルセロソルブアセテートや水に溶解しやすい溶媒、
例えばメタノールやエタノール等のアルコールを用いる
こともできる。ここで、染料と高沸点溶媒との使用比率
としては10〜1/10(重量比)が好ましい。A method of dispersing the compound by dissolving the compound in an oil, that is, a solvent substantially insoluble in water and having a boiling point of about 160 ° C. or higher, in a hydrophilic colloid solution. Examples of the high boiling point solvent include, as described in U.S. Pat.No.2,322,027, for example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphate ester (diphenyl phosphate, triphenyl phosphate, tricresyl) Phosphate, dioctyl butyl phosphate), citrate (e.g., tributyl acetyl citrate), benzoate (e.g., octyl benzoate), alkylamide (e.g., diethyl laurylamide), fatty acid esters (e.g., dibutoxyethyl succinate, Diethyl azelate), trimesic esters (eg, tributyl trimesate) and the like can be used. Organic solvents having a boiling point of about 30 ° C. to about 150 ° C., for example, ethyl acetate, lower alkyl acetates such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
Methyl cellosolve acetate and water-soluble solvents,
For example, alcohols such as methanol and ethanol can be used. Here, the use ratio of the dye to the high boiling point solvent is preferably 10 to 1/10 (weight ratio).
【0039】 本発明の染料およびその他の添加物
を、写真乳剤層やその他の親水性コロイド層に充填ポリ
マーラテックス組成物として含有させる方法。前記ポリ
マーラテックスとしては、例えば、ポリウレタンポリマ
ー、ビニルモノマーから重合されるポリマー等を用いる
ことができる。適当なビニルモノマーとしては、アクリ
ル酸エステル(メチルアクリレート、エチルアクリレー
ト、ブチルアクリレート、ヘキシルアクリレート、オク
チルアクリレート、ドデシルアクリレート、グリシジル
アクリレート等)、α-置換アクリル酸エステル(メチル
メタクリレート、ブチルメタクリレート、オクチルメタ
クリレート、グリシジルメタクリレート等)、アクリル
アミド(ブチルアクリルアミド、ヘキシルアクリルアミ
ド等)、α-置換アクリルアミド(ブチルメタクリルアミ
ド、ジブチルメタクリルアミド等)、ビニルエステル(酢
酸ビニル、酪酸ビニル等)、ハロゲン化ビニル(塩化ビニ
ル等)、ハロゲン化ビニリデン(塩化ビニリデン等)、ビ
ニルエーテル(ビニルメチルエーテル、ビニルオクチル
エーテル等)、スチレン、側鎖置換スチレン(α-メチル
スチレン等)、核置換スチレン(ヒドロキシスチレン、ク
ロロスチレン、メチルスチレン等)、エチレン、プロピ
レン、ブチレン、ブタジエン、アクリロニトリル等を挙
げることができる。これらは単独でも2種以上を組み合
わせてもよいし、他のビニルモノマーをマイナー成分と
して混合してもよい。他のビニルモノマーとしては、イ
タコン酸、アクリル酸、メタアクリル酸、ヒドロキシア
ルキルアクリレート、ヒドロキシアルキルメタクリレー
ト、スルホアルキルアクリレート、スルホアルキルメタ
クリレート、スチレンスルホン酸等が挙げられる。これ
ら充填ポリマーラテックスは、特公昭51-39853号、特開
昭51-59943号、特開昭53-137131号、特開昭54-32552
号、特開昭54-107941号、特開昭55-133465号、特開昭56
-19043号、特開昭56-19047号、特開昭56-126830号、特
開昭58-149038号に記載の方法に準じて製造できる。こ
こで、染料とポリマーラテックスとの使用比率としては
10〜1/10(重量比)が好ましい。なお、ラテックスは、
通常、高分子(ポリマー)が乳化剤の作用によってコロ
イド状に水中に分散した乳濁液をさすが、ここでのポリ
マーラテックスはラテックス中のポリマーをいう。A method of incorporating the dye and other additives of the present invention into a photographic emulsion layer or other hydrophilic colloid layer as a filled polymer latex composition. As the polymer latex, for example, a polyurethane polymer, a polymer polymerized from a vinyl monomer, or the like can be used. Suitable vinyl monomers include acrylates (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, glycidyl acrylate, etc.), α-substituted acrylates (methyl methacrylate, butyl methacrylate, octyl methacrylate, Glycidyl methacrylate), acrylamide (butyl acrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinyl acetate, vinyl butyrate, etc.), vinyl halide (vinyl chloride, etc.), Vinylidene halides (vinylidene chloride, etc.), vinyl ethers (vinyl methyl ether, vinyl octyl ether, etc.), styrene, side-chain substituted styrene (α- Rusuchiren etc.), nucleus-substituted styrene (hydroxystyrene, chlorostyrene, methyl styrene, etc.), ethylene, propylene, butylene, butadiene, and acrylonitrile can. These may be used alone or in combination of two or more kinds, or other vinyl monomers may be mixed as a minor component. Examples of other vinyl monomers include itaconic acid, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, and styrene sulfonic acid. These filled polymer latex, JP-B-51-39853, JP-A-51-59943, JP-A-53-137131, JP-A-54-32552
No., JP-A-54-107941, JP-A-55-133465, JP-A-56
-19043, JP-A-56-19047, JP-A-56-126830, and JP-A-58-149038. Here, as the usage ratio of the dye and the polymer latex,
10 to 1/10 (weight ratio) is preferred. In addition, latex is
Usually, an emulsion in which a macromolecule (polymer) is colloidally dispersed in water by the action of an emulsifier is used. Here, the polymer latex refers to a polymer in the latex.
【0040】 染料イオンと反対の荷電をもつ親水性
ポリマーを媒染剤として層に共存させ、これと染料分子
との相互作用によって、染料を特定層中に局在化させる
方法。ポリマー媒染剤とは、二級および三級アミノ基を
含むポリマー、含窒素複素環部分をもつポリマー、これ
らの四級カチオン基を含むポリマーなどで、分子量が50
00以上のもの、特に好ましくは10000以上のものであ
る。例えば、米国特許2,548,564号明細書等に記載され
ているビニルピリジンポリマーおよびビニルピリジニウ
ムカチオンポリマー;米国特許4,124,386号明細書等に開
示されているビニルイミダゾリウムカチオンポリマー;
米国特許3,625,694号明細書等に開示されているゼラチ
ン等と架橋可能なポリマー媒染剤;米国特許3,958,995号
明細書、特開昭54-115228号公報等に開示されている水
性ゾル型媒染剤;米国特許3,898,088号明細書等に開示さ
れている水不溶性媒染剤;米国特許4,168,976号明細書等
に開示されている染料と共有結合することのできる反応
性媒染剤;英国特許685,475号等に記載されているジアル
キルアミノアルキルエステル残基を有するエチレン不飽
和化合物から導かれたポリマー;英国特許850,281号に記
載されているようなポリビニルアルキルケトンとアミノ
グアニジンとの反応によって得られる生成物;米国特許
3,445,231号に記載されているような2-メチル-1-ビニル
イミダゾールから導かれたポリマーなどを挙げることが
できる。A method in which a hydrophilic polymer having a charge opposite to that of a dye ion coexists in a layer as a mordant, and the dye is localized in a specific layer by an interaction between the dye and a dye molecule. Polymer mordants include polymers containing secondary and tertiary amino groups, polymers having a nitrogen-containing heterocyclic moiety, and polymers containing these quaternary cationic groups, and having a molecular weight of 50.
It is preferably at least 00, particularly preferably at least 10,000. For example, vinylpyridine polymers and vinylpyridinium cationic polymers described in U.S. Pat.No. 2,548,564 and the like; vinylimidazolium cationic polymers disclosed in U.S. Pat.No.4,124,386 and the like;
U.S. Pat.No. 3,898,088; U.S. Pat.No. 3,898,088; U.S. Pat.No.3,988,088; U.S. Pat. Water-insoluble mordant disclosed in U.S. Pat. No. 4,168,976; a reactive mordant capable of covalently bonding to a dye disclosed in U.S. Pat.No. 4,168,976; dialkylaminoalkyl described in British Patent No. 685,475, etc. Polymers derived from ethylenically unsaturated compounds with ester residues; products obtained by the reaction of a polyvinyl alkyl ketone with aminoguanidine as described in GB 850,281; US Patent
Polymers derived from 2-methyl-1-vinylimidazole as described in 3,445,231 can be mentioned.
【0041】 化合物を界面活性剤を用いて溶解する
方法。有用な界面活性剤としては、オリゴマーまたはポ
リマーであってもよく、この重合体の詳細については、
特開昭53-138726号、特開昭60-200251号、特開昭60-203
935号、特願昭59-12766号に記載されている。A method in which a compound is dissolved using a surfactant. Useful surfactants may be oligomers or polymers; for details of the polymers, see
JP-A-53-138726, JP-A-60-200251, JP-A-60-203
935 and Japanese Patent Application No. 59-12766.
【0042】 上記で、高沸点溶媒に代えて、また
は高沸点溶媒と併用して、親水性ポリマーを用いる方
法。この方法に関しては、例えば西独特許1,957,467号
に記載されている。In the above method, a hydrophilic polymer is used in place of the high boiling point solvent or in combination with the high boiling point solvent. This method is described, for example, in West German Patent 1,957,467.
【0043】 特開昭59-113434号に記載されている
ような末端にカルボキシル基、スルホン酸基などを有す
るポリマーによるマイクロカプセル法。また、上記で得
た親水性コロイド分散媒中に、例えば特公昭51-39835号
記載の親油性ポリマーのヒドロゾルを添加してもよい。
親水性コロイドとしては、ゼラチンが代表的なものであ
るが、その他写真用に使用しうるものとして従来知られ
ているものはいずれも使用できる。A microcapsule method using a polymer having a carboxyl group, a sulfonic acid group or the like at a terminal as described in JP-A-59-113434. Further, for example, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion medium obtained above.
As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids usable for photography can be used.
【0044】本発明において、ハロゲン化銀乳剤層およ
び/またはハロゲン化銀乳剤層よりも上層の親水性コロ
イド層中の顔料および/または染料の含有量は、現像処
理後の未露光部白色光透過濃度のうち、顔料および/ま
たは染料の寄与が50%以上、好ましくは80%以上となる量
が好ましい。濃度寄与の評価法としては、具体的には、
未露光の試料を定着、水洗のみ行うか、あるいは、現像
工程で脱色するような染料が入っている場合にはさらに
現像、定着、水洗を行う。いずれの場合でも分光増感色
素の残色を取り除くために充分な水洗を行い、乾燥させ
る。この試料の白色光透過濃度と用いた支持体の白色光
透過濃度との差が顔料および/または染料の白色光透過
濃度であり、この濃度が現像処理後の未露光部白色光透
過濃度のうちに占める割合を顔料および/または染料の
濃度寄与とする。また、白色光透過濃度とは、視感度補
正フィルターを用いて測定するのであれば特に規定はな
いが、例えば、コーニングフィルター4-76を用いたり、
マクベス濃度計のビジュアルフィルターを用いることが
好ましい。In the present invention, the content of the pigment and / or dye in the silver halide emulsion layer and / or the hydrophilic colloid layer above the silver halide emulsion layer is determined by determining the unexposed white light transmission after the development processing. The concentration is preferably such that the contribution of the pigment and / or dye is at least 50%, preferably at least 80%. As a method of evaluating the concentration contribution, specifically,
The unexposed sample is only fixed and washed, or, if a dye which decolorizes in the developing step is contained, further developed, fixed and washed. In any case, washing is carried out sufficiently to remove the residual color of the spectral sensitizing dye, followed by drying. The difference between the white light transmission density of this sample and the white light transmission density of the support used is the white light transmission density of the pigment and / or dye. Is the concentration contribution of the pigment and / or dye. The white light transmission density is not particularly limited as long as it is measured using a visibility correction filter, for example, using a Corning filter 4-76,
It is preferable to use a visual filter of a Macbeth densitometer.
【0045】顔料および/または染料の添加量として
は、感材片面当たり1mg/m2〜100mg/m2が好ましく、20mg
/m2〜70mg/m2がより好ましい。添加する位置としては、
ハロゲン化銀乳剤層および/またはハロゲン化銀乳剤層
よりも上層の親水性コロイド層が好ましい。本発明の目
的の1つは、現像銀の好ましくない反射光成分を現像銀
よりも上の位置で吸収することである。従って、本発明
の顔料および/または染料は、ハロゲン化銀乳剤層に添
加することだけでは不充分な場合があり、ハロゲン化銀
乳剤層よりも支持体から遠い位置にある親水性コロイド
層に添加することがより好ましい。添加される親水性コ
ロイド層は、最も上層に設けられた保護層であってもよ
く、保護層と乳剤層との間に設けられた中間層であって
もよい。[0045] The addition amount of the pigment and / or dye, is preferably sensitive material per surface 1mg / m 2 ~100mg / m 2 , 20mg
/ m 2 to 70 mg / m 2 is more preferred. As a position to add,
A silver halide emulsion layer and / or a hydrophilic colloid layer above the silver halide emulsion layer are preferred. One of the objects of the present invention is to absorb the undesired reflected light component of the developed silver at a position above the developed silver. Therefore, the pigments and / or dyes of the present invention may not be sufficiently added to the silver halide emulsion layer alone, and may be added to the hydrophilic colloid layer located farther from the support than the silver halide emulsion layer. Is more preferable. The hydrophilic colloid layer to be added may be a protective layer provided on the uppermost layer, or may be an intermediate layer provided between the protective layer and the emulsion layer.
【0046】ハロゲン化銀感光材料中での顔料および/
または染料の固定性が低い場合には、ケイ光増感紙や自
動現像機への汚染が生じる場合があるので、顔料および
/または染料は中間層に添加されることが最も好まし
い。Pigment in silver halide light-sensitive material and / or
Alternatively, when the fixing property of the dye is low, contamination of the fluorescent intensifying screen and the automatic developing machine may occur. Therefore, the pigment and / or the dye are most preferably added to the intermediate layer.
【0047】また、本発明に用いられる支持体として
は、硝酸セルロース、酢酸セルロース、酢酸酪酸セルロ
ース、ポリスチレン、ポリ塩化ビニル、ポリエチレンテ
レフタレート、ポリカーボネート等の半合成または合成
高分子から成るフィルム、バライタ層およびα-オレフ
ィンポリマー(例えばポリエチレン、ポリプロピレン、
エチレン/ブテン共重合体)等を塗布、または、ラミネ
ートした紙等である。Examples of the support used in the present invention include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc .; α-olefin polymer (for example, polyethylene, polypropylene,
Paper or the like on which an ethylene / butene copolymer) or the like is applied or laminated.
【0048】本発明の支持体は染料や顔料を用いて着色
(染色)されていてもよく、また写真乳剤層等との接着
をよくするための下塗層も染料や顔料を用いて着色され
ていてもよい。本発明においては、前述のように、ハロ
ゲン化銀乳剤層および/またはハロゲン化銀乳剤層より
も上層の親水性コロイド層が顔料および/または染料で
着色されているので、支持体の着色は未露光部の濃度が
高くなりすぎない程度であることが好ましく、現像処理
後の未露光部白色光透過濃度のうち、支持体の着色の寄
与(下塗層が存在するときは下塗層による寄与も含む)
が50%未満、好ましくは48%以下、より好ましくは20%未
満、よりさらに好ましくは18%以下、特に好ましくは10%
未満、より特に好ましくは8%以下であり、支持体(下
塗層が存在するときは下塗層も含む)はまったく着色さ
れていないことが最も好ましい。このとき、本発明の感
光材料の現像処理後の未露光部白色光透過濃度として
は、0.15〜0.35であり、0.15〜0.25が好ましい。なお、
ここでの現像処理は、いわゆる現像のみならず、定着、
水洗等を含む一連の処理をいうものとする。The support of the present invention may be colored (dyed) using a dye or a pigment, and the undercoat layer for improving the adhesion to a photographic emulsion layer or the like may also be colored using a dye or a pigment. May be. In the present invention, as described above, since the silver halide emulsion layer and / or the hydrophilic colloid layer above the silver halide emulsion layer is colored with a pigment and / or a dye, the support is not colored. It is preferable that the density of the exposed portion is not excessively high, and among the unexposed portion white light transmission density after the development processing, the contribution of the coloring of the support (contribution by the undercoat layer when the undercoat layer is present) Also included)
Is less than 50%, preferably 48% or less, more preferably less than 20%, even more preferably 18% or less, particularly preferably 10%
It is most preferred that the support (including the undercoat layer, if present) is not colored at all. At this time, the white light transmission density of the unexposed area after the development processing of the photosensitive material of the present invention is 0.15 to 0.35, and preferably 0.15 to 0.25. In addition,
The development processing here is not only so-called development, but also fixing,
It refers to a series of processing including washing with water.
【0049】次に本発明に用いられる平板状ハロゲン化
銀乳剤について説明する。本発明のハロゲン化銀写真感
光材料に用いられるハロゲン化銀乳剤は、臭化銀、沃臭
化銀等のいずれのハロゲン化銀組成を有するものであっ
てもよい。Next, the tabular silver halide emulsion used in the present invention will be described. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention may have any silver halide composition such as silver bromide and silver iodobromide.
【0050】ただし、沃化銀含有量については1モル%
以下、好ましくは0モル%以上0.45モル%以下であ
る。The silver iodide content was 1 mol%.
Or less, preferably 0 to 0.45 mol%.
【0051】本発明に好ましく用いられるハロゲン化銀
乳剤について、ハロゲン化銀粒子の投影面積の円相当径
の平均は、すべてのハロゲン化銀粒子の平均値として計
算される。円相当径の平均は好ましくは0.1μm 以上
2.0μm 以下であるが、特に0.1μm 以上1.8μ
m 以下がより好ましく、さらに0.3μm 以上1.8μ
m 以下が最も好ましい。For the silver halide emulsion preferably used in the present invention, the average of the equivalent circle diameters of the projected areas of the silver halide grains is calculated as the average value of all silver halide grains. The average of the equivalent circle diameters is preferably 0.1 μm or more and 2.0 μm or less, and particularly 0.1 μm or more and 1.8 μm or less.
m or less, more preferably 0.3 μm or more and 1.8 μm or less.
m or less is most preferred.
【0052】ハロゲン化銀乳剤中のハロゲン化銀粒子
は、立方体、八面体、十四面体のような等方的に成長し
たもの、あるいは球形のような多面的結晶型のものを併
用してもよい。The silver halide grains in the silver halide emulsion may be used in combination with isotropically grown ones such as cubes, octahedrons and tetradecahedrons, or polyhedral crystals such as spheres. Is also good.
【0053】平行な双晶面を有し{111}面を主平面
とする平板状粒子のもの、{100}面を主平面とする
平板状粒子であってもよい。Tabular grains having parallel twin planes and having {111} planes as main planes, and tabular grains having {100} planes as main planes may be used.
【0054】本発明に用いられる平板状ハロゲン化銀粒
子の厚みとしては0.05μm 以上0.25μm 以下が
好ましく、0.05μm 以上0.2μm 以下がより好ま
しい。The thickness of the tabular silver halide grains used in the present invention is preferably from 0.05 μm to 0.25 μm, more preferably from 0.05 μm to 0.2 μm.
【0055】平板状ハロゲン化銀粒子のアスペクト比に
関しては1粒子の投影面積の円相当径をその粒子の厚み
で割った値として定義され、本発明では乳剤中のハロゲ
ン化銀粒子の全投影面積の50%以上が、アスペクト比
が5以上であり、5以上30未満であることが好まし
く、さらには5以上25以下であることが好ましい。平
均アスペクト比は5以上、特に5〜20であることが好
ましい。The aspect ratio of tabular silver halide grains is defined as the value obtained by dividing the equivalent circle diameter of the projected area of one grain by the thickness of the grain, and in the present invention, the total projected area of the silver halide grains in the emulsion is determined in the present invention. 50% or more has an aspect ratio of 5 or more, preferably 5 or more and less than 30, and more preferably 5 or more and 25 or less. The average aspect ratio is preferably 5 or more, particularly preferably 5 to 20.
【0056】アスペクト比5以上の平板状ハロゲン化銀
粒子の割合は、好ましくはその投影面積の和が全粒子の
投影面積の和に対して50%以上100%以下であり、
さらに好ましくは70%以上100%以下、最も好まし
いのは90%以上100%以下である。The proportion of tabular silver halide grains having an aspect ratio of 5 or more is preferably such that the sum of the projected areas is 50% or more and 100% or less with respect to the sum of the projected areas of all grains.
It is more preferably 70% or more and 100% or less, and most preferably 90% or more and 100% or less.
【0057】平板状ハロゲン化銀粒子の製法としては、
当業界で知られた方法を適宜、組合せることにより成し
得る。The production method of tabular silver halide grains is as follows.
This can be achieved by appropriately combining methods known in the art.
【0058】本発明の平行な双晶面を有し{111}面
を主平面とする平板状粒子は、特開昭58−12792
7号、特開昭58−113927号、特開昭58−11
3928号に記載された方法等を参照すれば容易に調製
できる。The tabular grains of the present invention having parallel twin planes and having {111} planes as main planes are disclosed in JP-A-58-12792.
7, JP-A-58-113927, JP-A-58-11
It can be easily prepared by referring to the method described in No. 3928 and the like.
【0059】また、pBr1.3以下の比較的低pBr
値の雰囲気中で平板状粒子が重量で40%以上存在する
種晶を形成し、同程度のpBr値に保ちつつ銀およびハ
ロゲン溶液を同時に添加しつつ種晶を成長させることに
より得られる。Also, a relatively low pBr of pBr 1.3 or less
The seed crystal is formed by forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere having the same value, and growing the seed crystal while simultaneously adding silver and a halogen solution while maintaining the same pBr value.
【0060】この粒子成長過程において、新たな結晶核
が発生しないように銀およびハロゲン溶液を添加するこ
とが望ましい。During the grain growth process, it is desirable to add a silver and halogen solution so that no new crystal nuclei are generated.
【0061】平板状ハロゲン化銀粒子の大きさは、温度
調節、溶剤の種類や量の選択、粒子成長時に用いる銀
塩、およびハロゲン化物の添加速度等をコントロールす
ることにより調整できる。The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.
【0062】さらに本発明において、平板状ハロゲン化
銀粒子の中でも単分散六角平板粒子はとりわけ有用な粒
子である。In the present invention, among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains.
【0063】単分散六角平板粒子の構造および製造方法
の詳細は特開昭63−151618号に記載されている
とおりである。The structure of the monodisperse hexagonal tabular grains and the details of the production method are as described in JP-A-63-151618.
【0064】本発明において好ましいハロゲン化銀乳剤
について、結晶構造は一様なものでもよいが、内部と外
部が異質なハロゲン組成からなるものでもよく、層状構
造をなしていてもよい。また、粒子形成中に還元増感銀
核を含んでいることが好ましい。The silver halide emulsion preferred in the present invention may have a uniform crystal structure, or may have a different halogen composition between the inside and the outside, or may have a layered structure. Further, it is preferable that a reduction sensitized silver nucleus is included during grain formation.
【0065】本発明において、英国特許第635841
号、米国特許第3622318号に記載されているよう
な、いわゆるハロゲン変換型(コンバージョン型)の粒
子は特に有効に利用しうるものである。ハロゲン変換量
は銀量に対し0.05モル%〜0.45モル%が好まし
く、特に0.1モル%〜0.3モル%がより好ましい。In the present invention, British Patent No. 635841
No. 3,622,318, so-called halogen conversion type (conversion type) particles can be used particularly effectively. The halogen conversion amount is preferably 0.05 mol% to 0.45 mol%, more preferably 0.1 mol% to 0.3 mol%, based on the silver amount.
【0066】沃臭化銀乳剤においては、内部および/ま
たは表面に高ヨード層を有する構造の粒子が特に好まし
い。In the silver iodobromide emulsion, grains having a structure having a high iodine layer inside and / or on the surface are particularly preferable.
【0067】また本発明において好ましい平板状ハロゲ
ン化銀粒子の表面を高ヨード型にコンバージョンするこ
とにより、より高感度なハロゲン化銀乳剤を得ることが
できる。Further, by converting the surface of tabular silver halide grains preferred in the present invention to a high iodine type, a silver halide emulsion with higher sensitivity can be obtained.
【0068】上記方法でハロゲン変換を行う際に、ハロ
ゲン化銀溶剤を存在させる方法は特に有効である。好ま
しい溶剤としては、チオエーテル化合物、チオシアン酸
塩、4置換チオ尿素が挙げれられる。中でもチオエーテ
ル化合物とチオシアン酸塩は特に有効であり、チオシア
ン酸塩はハロゲン化銀1モル当たり0.5g〜5g、チ
オエーテルは0.2g〜3gの使用が好ましい。In carrying out the halogen conversion by the above method, a method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and 4-substituted thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and it is preferable to use 0.5 g to 5 g of thiocyanate and 0.2 g to 3 g of thioether per 1 mol of silver halide.
【0069】本発明の平板状粒子は、転位線を有するハ
ロゲン化銀粒子を用いることが好ましい。The tabular grains of the present invention are preferably silver halide grains having dislocation lines.
【0070】平板粒子の転位線は、例えば J. F. Hamil
ton, Phot. Sci. Eng., 11、57、(1967)や
T. Shiozawa, J. Soc. Phot. Sci. Japan, 35、21
3、(1972)に記載されている、低温での透過型電
子顕微鏡を用いた直接的な方法により観察することがで
きる。すなわち、乳剤から粒子に転位が発生するほどの
圧力をかけないように注意して取り出したハロゲン化銀
粒子を電子顕微鏡観察用のメッシュにのせ、電子線によ
る損傷(プリントアウト等)を防ぐように試料を冷却し
た状態で透過法により観察を行う。この時粒子の厚みが
厚いほど電子線が透過しにくくなるので、高圧型(厚さ
0.25μmの粒子に対して200kV以上)の電子顕微
鏡を用いた方がより鮮明に観察することができる。この
ような方法により得られた粒子の写真から、主平面に対
して垂直方向から見た場合の各粒子についての転位の位
置および数を求めることができる。The dislocation lines of tabular grains are described, for example, in JF Hamil
ton, Phot. Sci. Eng., 11, 57, (1967)
T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 21
3, (1972), can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for an electron beam to pass through. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). From the photograph of the particles obtained by such a method, the position and the number of dislocations for each particle when viewed from the direction perpendicular to the main plane can be obtained.
【0071】また、ハロゲン化銀粒子形成または物理熟
成の過程において、カドミウム塩、亜鉛塩、鉛塩、タリ
ウム塩、イリジウム塩またはその錯塩、ロジウム塩また
はその錯塩、鉄塩またはその錯塩などを共存させてもよ
い。In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, etc. are allowed to coexist. You may.
【0072】本発明における化学増感としては、セレン
化合物および/またはテルル化合物による化学増感、す
なわちセレン増感および/またはテルル増感が用いられ
る。これと併用して本発明ではセレン増感、テルル増感
以外のカルコゲン増感である硫黄増感や金増感を行って
もよく、特に金増感を組み合わせることが好ましい。As the chemical sensitization in the present invention, chemical sensitization with a selenium compound and / or tellurium compound, that is, selenium sensitization and / or tellurium sensitization is used. In combination with this, in the present invention, sulfur sensitization or gold sensitization, which is a chalcogen sensitization other than selenium sensitization and tellurium sensitization, may be performed, and it is particularly preferable to combine gold sensitization.
【0073】セレン増感においては、不安定セレン化合
物を用い、特公昭43−13489号、同44−157
48号、特開平4−25832号、同4−109240
号、同4−271341号、同5−40324号各公報
に記載されている不安定セレン化合物を用いることがで
きる。具体的には、コロイド状金属セレン、セレノ尿素
類(例えば、N,N−ジメチルセレノ尿素、トリフルオ
ルメチルカルボニル−トリメチルセレノ尿素、アセチル
−トリメチルセレノ尿素)、セレノアミド類(例えば、
セレノアセトアミド、N,N−ジエチルフェニルセレノ
アミド)、フォスフィンセレニド類(例えば、トリフェ
ニルフォスフィンセレニド、ペンタフルオロフェニルト
リフェニルフォスフィンセレニド)、セレノフォスフェ
ート類(例えば、トリ−p−トリルセレノフォスフェー
ト、トリ−n−ブチルセレノフォスフェート)、セレノ
ケトン類(例えば、セレノベンゾフェノン)、イソセレ
ノシアネート類、セレノカルボン酸類、セレノエステル
類、ジアシルセレニド類などを用いればよい。またさら
に、特公昭46−4553号、同52−34492号各
公報に記載の非不安定セレン化合物、例えば亜セレン
酸、セレノシアン化カリウム、セレナゾール類、セレニ
ド類なども用いることもできる。In selenium sensitization, an unstable selenium compound is used, and JP-B-43-13489 and JP-B-44-157.
No. 48, JP-A-4-25832, JP-A-4-109240
Unstable selenium compounds described in JP-A Nos. 4-271341 and 5-40324 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg,
Selenoacetamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (eg, tri-p-) Tolyl selenophosphate, tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters, diacyl selenides, and the like may be used. Further, non-labile selenium compounds described in JP-B-46-4553 and JP-B-52-34492, for example, selenous acid, potassium selenocyanide, selenazoles, selenides and the like can also be used.
【0074】テルル増感においては、不安定テルル化合
物を用い、カナダ特許800958号、英国特許第1,
295,462号、同1,396,696号各明細書、
特開平4−204640号、同4−271341号、同
4−333043号、同5−303157号各公報に記
載されている不安定テルル化合物を用いることができ
る。具体的には、テルロ尿素類(例えば、テトラメチル
テルロ尿素、N,N’−ジメチルエチレンテルロ尿素、
N,N’−ジフェニルエチレンテルロ尿素)、フォスフ
ィンテルリド類(例えば、ブチル−ジイソプロピルフォ
スフィンテルリド、トリブチルフォスフィンテルリド、
トリブトキシフォスフィンテルリド、エトキシ−ジフェ
ニルフォスフィンテルリド)、ジアシル(ジ)テルリド
類(例えば、ビス(ジフェニルカルバモイル)ジテルリ
ド、ビス(N−フェニル−N−メチルカルバモイル)ジ
テルリド、ビス(N−フェニル−N−メチルカルバモイ
ル)テルリド、ビス(N−フェニル−N−ベンジルカル
バモイル)テルリド、ビス(エトキシカルボニル)テル
リド)、イソテルロシアナート類、テルロアミド類、テ
ルロヒドラジド類、テルロエステル類(例えば、ブチル
ヘキシルテルロエステル)、テルロケトン類(例えば、
テルロアセトフェノン)、コロイド状テルル、(ジ)テ
ルリド類、その他のテルル化合物(ポタシウムテルリ
ド、テルロペンタチオネートナトリウム塩)などを用い
ればよい。In tellurium sensitization, an unstable tellurium compound is used, and Canadian Patent No. 800958, British Patent No. 1,
295,462, 1,396,696 each specification,
Unstable tellurium compounds described in JP-A-4-204640, JP-A-4-271341, JP-A-4-330343, and JP-A-5-303157 can be used. Specifically, telluroureas (e.g., tetramethyltellurourea, N, N'-dimethylethylenetellurourea,
N, N′-diphenylethylene tellurourea), phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride,
Tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride, diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl) -N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isosterocyanates, telluramides, tellurohydrazides, telluroesters (for example, butylhexyltelluro) Esters), telluroketones (for example,
Telluroacetophenone), colloidal tellurium, (di) tellurides, other tellurium compounds (potassium telluride, telluropentathionate sodium salt) and the like may be used.
【0075】硫黄増感においては、不安定硫黄化合物を
用い、P. Grafkides著、Chimie etPhysique Photograph
ique (Paul Momtel社刊、1987年、第5版)、Research
Disclosure 誌307巻307105号などに記載され
ている不安定硫黄化合物を用いることができる。具体的
には、チオ硫酸塩(例えば、ハイポ)、チオ尿素類(例
えば、ジフェニルチオ尿素、トリエチルチオ尿素、N−
エチル−N’−(4−メチル−2−チアゾリル)チオ尿
素、カルボキシメチルトリメチルチオ尿素)、チオアミ
ド類(例えば、チオアセトアミド)、ローダニン類(例
えば、ジエチルローダニン、5−ベンジリデン−N−エ
チル−ローダニン)、フォスフィンスルフィド類(例え
ば、トリメチルフォスフィンスルフィド)、チオヒダン
トイン類、4−オキソ−オキサゾリジン−2−チオン
類、ジスルフィド類またはポリスルフィド類(例えば、
ジモルフォリンジスルフィド、シスチン、レンチオニ
ン)、メルカプト化合物(例えば、システィン)、ポリ
チオン酸塩、元素状硫黄などの公知の硫黄化合物および
活性ゼラチンなども用いることができる。In the sulfur sensitization, an unstable sulfur compound is used, and P. Grafkides, Chimie et Physique Photograph
ique (Paul Momtel, 1987, 5th edition), Research
Unstable sulfur compounds described in Disclosure 307, 307105 and the like can be used. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, N-
Ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethyl rhodanine, 5-benzylidene-N-ethyl-) Rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg,
Known sulfur compounds such as dimorpholine disulfide, cystine, lenthionine), mercapto compounds (for example, cysteine), polythionates, elemental sulfur, and active gelatin can also be used.
【0076】金増感については、前述のP. Grafkides
著、Chimie et Physique Photographique (Paul Momtel
社刊、1987年、第5版)、Research Disclosure 誌30
7巻307105号などに記載されている金塩を用いる
ことができる。具体的には、塩化金酸、カリウムクロロ
オーレート、カリウムオーリチオシアネート、硫化金、
金セレナイドにくわえて米国特許第2,642,361
号、同5,049,484号、同5,049,485号
各明細書などに記載の金化合物も用いることができる。
また、白金、パラジウム、イリジウムなどの貴金属塩を
加えてもよい。Regarding gold sensitization, see the aforementioned P. Grafkides.
Written by Chimie et Physique Photographique (Paul Momtel
Publishing Company, 1987, 5th edition), Research Disclosure Magazine 30
Gold salts described in Vol. 7, No. 307105, etc. can be used. Specifically, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
US Patent No. 2,642,361 in addition to gold selenide
And gold compounds described in JP-A-5,049,484 and JP-A-5,049,485 can also be used.
Further, a noble metal salt such as platinum, palladium, and iridium may be added.
【0077】本発明で用いられるカルコゲン増感剤の使
用量は、使用するハロゲン化銀粒子、化学増感条件など
により変わるが、ハロゲン化銀1モル当り10-8〜10
-2モル、好ましくは、10-7〜5×10-3モル程度を用
いる。The amount of the chalcogen sensitizer used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical sensitization, etc., but is preferably 10 -8 to 10 per mol of silver halide.
-2 mol, preferably about 10 -7 to 5 × 10 -3 mol is used.
【0078】本発明で用いられる金増感剤および貴金属
増感剤の使用量は、ハロゲン化銀1モル当り10-7〜1
0-2モル程度を用いる。本発明における化学増感の条件
に特に制限はないが、pAgとしては6〜11が好まし
く、より好ましくは7〜10であり、pHとしては4〜
10が好ましく、温度としては40〜95℃が、さらに
は45〜85℃が好ましい。The amount of the gold sensitizer and the noble metal sensitizer used in the present invention is from 10 -7 to 1 per mol of silver halide.
About 0 -2 mol is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pAg is preferably from 6 to 11, more preferably from 7 to 10, and the pH is from 4 to
10 is preferable, and the temperature is preferably 40 to 95C, more preferably 45 to 85C.
【0079】還元増感については、前述のP. Grafkides
著、Chimie et Physique Photographique (Paul Momtel
社刊、1987年、第5版)、Research Disclosure 誌30
7巻307105号などに記載されている公知の還元性
化合物を用いることができる。具体的には、アミノイミ
ノメタンスルフィン酸(別名、二酸化チオ尿素)、ボラ
ン化合物(例えば、ジメチルアミンボラン)、ヒドラジ
ン化合物(例えば、ヒドラジン、p−トリルヒドラジ
ン)、ポリアミン化合物(例えば、ジエチレントリアミ
ン、トリエチレンテトラミン)、塩化第1スズ、シラン
化合物、レダクトン類(例えば、アスコルビン酸)、亜
硫酸塩、アルデヒド化合物、水素ガスなどを用いればよ
い。また高pHや銀イオン過剰(いわゆる銀熟成)の雰
囲気で還元増感を施してもよい。Regarding reduction sensitization, see the aforementioned P. Grafkides
Written by Chimie et Physique Photographique (Paul Momtel
Publishing Company, 1987, 5th edition), Research Disclosure Magazine 30
Known reducing compounds described in Vol. 7, No. 307105, etc. can be used. Specifically, aminoiminomethanesulfinic acid (also called thiourea dioxide), borane compound (for example, dimethylamine borane), hydrazine compound (for example, hydrazine, p-tolylhydrazine), polyamine compound (for example, diethylenetriamine, triethylene Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like may be used. The reduction sensitization may be performed in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening).
【0080】本発明のハロゲン化銀乳剤は、化学増感工
程において粒子の表面もしくはその一部がハロゲン変換
されていてもよい。ハロゲン変換を施す方法としては、
臭化カリウム、臭化ナトリウム等の水溶性臭化物塩、沃
化カリウム等の水溶性沃化物塩等を単独もしくは組み合
わせて用いることができ、それらを固体のまま、または
水溶液、またはゼラチン分散物として添加することがで
きる。また、臭化銀、沃臭化銀、沃化銀のハロゲン化銀
微粒子を添加することも好ましく用いられ、それらは単
独もしくは組み合わせて用いることもできる。微粒子で
添加する場合、微粒子の平均球相当径は0.1μm 以下
のものが好ましく、0.05μm 以下のものがより好ま
しい。また微粒子は、反応容器の近傍に設けた混合機に
硝酸銀水溶液と任意の組成のハロゲン化アルカリ水溶液
とを供給して連続的に調製し、ただちに反応容器に添加
することもできるし、予め別の容器でバッチ式に調製し
た後に添加することもできる。また、必要により、ハロ
ゲン化銀微粒子にはイリジウム、ロジウム、白金等の重
金属のイオンまたは化合物を含ませることも可能であ
る。In the silver halide emulsion of the present invention, the surface of the grains or a part thereof may be halogen-converted in the chemical sensitization step. As a method of performing halogen conversion,
Water-soluble bromide salts such as potassium bromide and sodium bromide, and water-soluble iodide salts such as potassium iodide can be used alone or in combination, and they are added as a solid or as an aqueous solution or a gelatin dispersion. can do. It is also preferable to add silver halide fine grains of silver bromide, silver iodobromide, and silver iodide, and these can be used alone or in combination. When added as fine particles, the fine particles preferably have an average equivalent sphere diameter of 0.1 μm or less, more preferably 0.05 μm or less. The fine particles can be prepared continuously by supplying an aqueous solution of silver nitrate and an aqueous solution of an alkali halide having an arbitrary composition to a mixer provided near the reaction vessel, and can be immediately added to the reaction vessel, or can be added to the reaction vessel in advance. It can also be added after being prepared in a batch manner in a container. If necessary, silver halide fine particles may contain ions or compounds of heavy metals such as iridium, rhodium, and platinum.
【0081】本発明の乳剤調製時、例えば粒子形成時、
脱塩工程、化学増感時、塗布前に金属イオンの塩を存在
させることは、目的に応じて好ましい。粒子にドープす
る場合には粒子形成時に、粒子表面の修飾あるいは化学
増感剤として用いる時は粒子形成後、化学増感終了前に
添加することが好ましい。粒子全体にドープする場合と
粒子のコア部のみ、あるいはシェル部のみ、あるいはエ
ピタキシャル部分にのみ、あるいは平板粒子にのみドー
プする方法も選べる。Mg、Ca、Sr、Ba、Al、
Sc、Y、LaCr、Mn、Fe、Co、Ni、Cu、
Zn、Ga、Ru、Rh、Pd、Re、Os、Ir、P
t、Au、Cd、Hg、Tl、In、Sn、Pb、Bi
などを用いることができる。これらの金属は、アンモニ
ウム塩、酢酸塩、硝酸塩、硫酸塩、燐酸塩、水酸塩ある
いは6配位錯塩、4配位錯塩など粒子形成時に溶解させ
ることができる塩の形であれば添加できる。例えばCd
Br2 、CdCl2 、Cd(NO3)2 、Pb(NO3)
2 、Pb(CH3 COO)2、K3 〔Fe(CN)6〕、
(NH4)4 〔Fe(CN)6〕、K3 IrCl6 、(NH
4)3 RhCl6 、K4 Ru(CN)6などが挙げられる。
配位化合物のリガンドは、ハロ、アコ、シアノ、シアネ
ート、チオシアネート、ニトロシル、チオニトロシル、
オキソ、カルボニルの中から選ぶことができる。これら
は金属化合物を1種類のみ用いてもよいが、2種あるい
は3種以上を組み合せて用いてよい。When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, during the chemical sensitization, and before coating, the presence of a metal ion salt is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them after the grains are formed and before the completion of the chemical sensitization, when modifying the grain surface or when using as a chemical sensitizer. The case of doping the whole grain and the method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the tabular grain of the grain can be selected. Mg, Ca, Sr, Ba, Al,
Sc, Y, LaCr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts which can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, and six-coordinate and four-coordinate complexes. For example, Cd
Br 2 , CdCl 2 , Cd (NO 3 ) 2 , Pb (NO 3 )
2 , Pb (CH 3 COO) 2 , K 3 [Fe (CN) 6 ],
(NH 4 ) 4 [Fe (CN) 6 ], K 3 IrCl 6 , (NH
4 ) 3 RhCl 6 , K 4 Ru (CN) 6 and the like.
The ligand of the coordination compound is halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl,
You can choose from oxo and carbonyl. These may use only one kind of metal compound, or may use two or more kinds in combination.
【0082】米国特許第3,772,031 号に記載されている
ようなカルコゲン化合物を乳剤調製中に添加する方法も
有用な場合がある。S、Se、Te以外にもシアン塩、
チオシアン塩、セレノシアン酸、炭酸塩、リン酸塩、酢
酸塩を存在させてもよい。In some cases, a method of adding a chalcogen compound during emulsion preparation as described in US Pat. No. 3,772,031 is useful. In addition to S, Se, Te, cyanide salt,
Thiocyanates, selenocyanates, carbonates, phosphates, acetates may be present.
【0083】いわゆる化学増感助剤の存在下に化学増感
することもできる。有用な化学増感助剤には、アザイン
デン、アザピリダジン、アザピリミジンのような、化学
増感の過程でカブリを抑制し、かつ感度を増大するもの
として知られた化合物が用いられる。化学増感助剤改質
剤の例は、米国特許第2,131,038 号、同3,411,914 号、
同3,554,757 号、特開昭58-126526 号および前述ダフィ
ン著「写真乳剤化学」、138 〜143 頁に記載されてい
る。Chemical sensitization can be carried out in the presence of a so-called chemical sensitization auxiliary. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity in the course of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.Nos. 2,131,038 and 3,411,914.
No. 3,554,757, JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143.
【0084】本発明の乳剤の製造工程中に銀に対する酸
化剤を用いることが好ましい。銀に対する酸化剤とは、
金属銀に作用して銀イオンに変換させる作用を有する化
合物をいう。特に、ハロゲン化銀粒子の形成過程および
化学増感過程において副生するきわめて微小な銀粒子
を、銀イオンに変換させる化合物が有効である。ここで
生成する銀イオンは、ハロゲン化銀、硫化銀、セレン化
銀等の水に難溶の銀塩を形成してもよく、また、硝酸銀
等の水に易溶の銀塩を形成してもよい。銀に対する酸化
剤は、無機物であっても、有機物であってもよい。無機
の酸化剤としては、オゾン、過酸化水素およびその付加
物(例えば、NaBO2 ・H2 O2 ・3H2 O、2Na
CO3 ・3H2 O2 、Na4 P2 O7 ・2H2 O2 、2
Na2 SO4 ・H2 O2 ・2H2 O)、ペルオキシ酸塩
(例えばK2 S2 O8 、K2 C2 O6 、K2 P2 O8)、
ペルオキシ錯体化合物(例えば、K2 〔Ti(O2 )C
2 O4 〕・3H2 O、4K2 SO4 ・Ti(O2 )OH
・SO4 ・2H2 O、Na3〔VO(O2 )(C2 H4)2
・6H2 O)、過マンガン酸塩(例えば、KMnO
4 )、クロム酸塩(例えば、K2 Cr2 O7)などの酸素
酸塩、沃素や臭素などのハロゲン元素、過ハロゲン酸塩
(例えば過沃素酸カリウム)、高原子価の金属の塩(例
えば、ヘキサシアノ第二鉄酸カリウム)およびチオスル
フォン酸塩などがある。It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts very fine silver particles by-produced in the process of forming silver halide grains and in the step of chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO 2 .H 2 O 2 .3H 2 O, 2Na
CO 3 · 3H 2 O 2, Na 4 P 2 O 7 · 2H 2 O 2, 2
Na 2 SO 4 .H 2 O 2 .2H 2 O), peroxyacid salts (eg, K 2 S 2 O 8 , K 2 C 2 O 6 , K 2 P 2 O 8 ),
Peroxy complex compounds (for example, K 2 [Ti (O 2 ) C
2 O 4 ] .3H 2 O, 4K 2 SO 4 .Ti (O 2 ) OH
· SO 4 · 2H 2 O, Na 3 [VO (O 2) (C 2 H 4) 2
6H 2 O), permanganate (eg, KMnO)
4 ), oxyacid salts such as chromate (eg, K 2 Cr 2 O 7 ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high-valent metals (eg, For example, potassium hexacyanoferrate) and thiosulfonate.
【0085】また、有機の酸化剤としては、p−キノン
などのキノン類、過酢酸や過安息香酸などの有機過酸化
物、活性ハロゲンを放出する化合物(例えば、N−ブロ
ムサクシイミド、クロラミンT、クロラミンB)が例と
して挙げられる。Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B).
【0086】前述の還元増感と銀に対する酸化剤を併用
するのは好ましい態様である。It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination.
【0087】本発明の乳剤は通常、分光増感される。こ
れらに用いられる色素としては、例えばシアニン色素、
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等が挙げ
られる。特に有用な色素は、シアニン色素、メロシアニ
ン色素および複合メロシアニン色素に属する色素であ
る。これらの色素類には、塩基性複素環核として、シア
ニン色素類に通常利用される核のいずれをも適用でき
る。すなわち、ピロリン核、オキサゾリン核、チアゾリ
ン核、セレナゾリン核、ピロール核、オキサゾール核、
チアゾール核、セレナゾール核、イミダゾール核、テト
ラゾール核、ピリジン核、テルラゾール核等;これらの
核に脂環式炭化水素環が縮合した核;および、これらの
核に芳香族炭化水素環が縮合した核、すなわち、インド
レニン核、ベンズインドレニン核、インドール核、ベン
ズオキサゾール核、ナフトオキサゾール核、ベンズイミ
ダゾール核、ナフトイミダゾール核、ベンゾチアゾール
核、ナフトチアゾール核、ベンゾセレナゾール核、ナフ
トセレナゾール核、キノリン核、ベンゾテルラゾール核
等が適用できる。これらの複素環核は炭素原子上に置換
されていてもよい。The emulsion of the present invention is usually subjected to spectral sensitization. Examples of the dye used for these include a cyanine dye,
Examples include merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. As these dyes, any of nuclei usually used for cyanine dyes can be applied as basic heterocyclic nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a selenazoline nucleus, a pyrrole nucleus, an oxazole nucleus,
A thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, a tellurazole nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, That is, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, quinoline nucleus And a benzotellurazole nucleus. These heterocyclic nuclei may be substituted on carbon atoms.
【0088】メロシアニン色素または複合メロシアニン
色素には、ケトメチレン構造を有する核として、通常メ
ロシアニン色素に利用される核のいずれをも適用でき
る。特に有用な核として、ピラゾリン−5−オン核、チ
オヒダントイン核、2- チオオキサゾリジン-2,4-ジ
オン核、チアゾリジン-2,4-ジオン核、ローダニン
核、チオバルビツール酸核、2−チオセレナゾリジン-
2,4−ジオン核等の5員、6員の複素環核等を適用す
ることができる。As the merocyanine dye or composite merocyanine dye, any nucleus generally used for merocyanine dyes can be applied as the nucleus having a ketomethylene structure. Particularly useful nuclei include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, and 2-thio Selenazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-dione nucleus can be applied.
【0089】これらの増感色素は単独に用いても良い
が、組み合わせて用いても良い。増感色素の組み合わせ
は、特に強色増感の目的でしばしば用いられる。その代
表例は、米国特許第2,688,545 号、同第2,977,229 号、
同第3,397,060 号、同第3,522,052 号、同第3,527,641
号、同第3,617,293 号、同第3,628,964 号、同第3,666,
480 号、同第3,672,898 号、同第3,679,428 号、同第3,
703,377 号、同第3,769,301 号、同第3,614,609 号、同
第3,837,862 号、同第4,026,707 号、英国特許第1,344,
281 号、同第1,507,803 号各明細書、特公昭43-4936
号、同第53-12375号、特開昭52-110618 号、同52-10992
5 号各公報等に記載されている。These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Representative examples are U.S. Patent Nos. 2,688,545 and 2,977,229,
No. 3,397,060, No. 3,522,052, No. 3,527,641
No. 3,617,293, No. 3,628,964, No. 3,666,
No. 480, No. 3,672,898, No. 3,679,428, No. 3,
Nos. 703,377, 3,769,301, 3,614,609, 3,837,862, 4,026,707, and British Patent 1,344,
Nos. 281 and 1,507,803, Japanese Patent Publication No. 43-4936
No. 53-12375, JP-A-52-110618, JP-A-52-10992
It is described in each gazette of No. 5.
【0090】さらにまた、これらの増感色素は、それ自
身分光増感作用を示さない色素、あるいは可視光を実質
的に吸収しない物質であって増感色素と組み合わせるこ
とによって分光増感の著しい増加を示す、いわゆる強色
増感剤と称せられて知られているいかなる化合物と組み
合わせて用いてもよい。強色増感剤の代表例としては、
特開昭59-142541 号公報等に記載のビスピリジニウム塩
化合物、特公昭59-18691号公報等に記載のスチルベン誘
導体、特公昭49-46932号公報等に教示されている臭化カ
リウム、ヨウ化カリウム等の水溶性臭化物、水溶性ヨウ
化物、米国特許第3,743,510 号明細書等に記載の芳香族
化合物とホルムアルデヒドとの縮合物、カドミウム塩
類、アザインデン化合物等が挙げられる。Further, these sensitizing dyes are dyes which do not themselves exhibit spectral sensitization, or which are substances which do not substantially absorb visible light and which are combined with sensitizing dyes to significantly increase spectral sensitization. May be used in combination with any compound known as a so-called supersensitizer. Representative examples of supersensitizers include:
Bispyridinium salt compounds described in JP-A-59-142541, stilbene derivatives described in JP-B-59-18691, potassium bromide and iodide taught in JP-B-49-46932, etc. Water-soluble bromides such as potassium, water-soluble iodides, condensates of aromatic compounds with formaldehyde described in US Pat. No. 3,743,510, etc., cadmium salts, azaindene compounds and the like.
【0091】増感色素は化学熟成後、または化学熟成前
に添加される。本発明のハロゲン化銀粒子に対しては、
増感色素は化学熟成中または化学熟成以前(例えば、粒
子形成時、物理熟成時)に添加されることが、最も好ま
しい。The sensitizing dye is added after chemical ripening or before chemical ripening. For the silver halide grains of the present invention,
It is most preferable that the sensitizing dye is added during or before chemical ripening (for example, during grain formation or physical ripening).
【0092】分光増感色素をハロゲン化銀乳剤中に含有
させるには、それらを直接乳剤中に分散してもよいし、
あるいは水、メタノール、エタノール、プロパノール、
アセトン、メチルセロソルブ、2,2,3,3−テトラフルオ
ロプロパノール、2,2,2−トリフルオロエタノール、3
−メトキシ−1−プロパノール、3−メトキシ−1−ブ
タノール、1−メトキシ−2−プロパノール、N,N−
ジメチルホルムアミド等の溶媒単独もしくは混合溶媒に
溶解して乳剤に添加してもよい。また、米国特許第3,46
9,987号明細書等に記載のように、色素を揮発性の有機
溶剤に溶解し、この溶液を水または親水性コロイド中に
分散し、この分散物を乳剤中へ添加する方法、特公昭46
-24185号等に記載のように、水不溶性色素を溶解するこ
となしに水溶性溶剤中に分散させ、この分散物を乳剤中
へ添加する方法、特公昭44-23389号、特公昭44-27555
号、特公昭57-22091号等に記載されているように、色素
を酸に溶解し、この溶液を乳剤中へ添加したり、酸また
は塩基を共存させて水溶液とし、乳剤中へ添加する方
法、米国特許第3,822,135号、米国特許第4,006,025号明
細書等に記載のように、界面活性剤を共存させて水溶液
あるいはコロイド分散物としたものを乳剤中へ添加する
方法、特開昭53-102733号、特開昭58-105141号に記載の
ように、親水性コロイド中に色素を直接分散させ、その
分散物を乳剤中へ添加する方法、特開昭51-74624号に記
載のように、レッドシフトさせる化合物を用いて色素を
溶解し、この溶液を乳剤中へ添加する方法等を用いるこ
ともできる。また、溶解に超音波を使用することもでき
る。In order to incorporate spectral sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion,
Or water, methanol, ethanol, propanol,
Acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3
-Methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-
It may be added to an emulsion by dissolving it in a solvent such as dimethylformamide alone or in a mixed solvent. Also, U.S. Pat.
No. 9,987, a method of dissolving a dye in a volatile organic solvent, dispersing this solution in water or a hydrophilic colloid, and adding this dispersion to an emulsion,
As described in -24185, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving and adding this dispersion to an emulsion, JP-B-44-23389, JP-B-44-27555
As described in JP-B-57-22091, a method of dissolving a dye in an acid and adding this solution to an emulsion or adding an acid or a base to form an aqueous solution and adding it to an emulsion As described in U.S. Pat.No. 3,822,135 and U.S. Pat.No.4,006,025, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion is disclosed in JP-A-53-102733. As described in JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, as described in JP-A-51-74624, It is also possible to use a method in which a dye is dissolved using a compound that causes a red shift, and this solution is added to the emulsion. Also, ultrasonic waves can be used for dissolution.
【0093】本発明に用いられる写真乳剤には、感光材
料の製造工程、保存中あるいは写真処理中のカブリを防
止し、あるいは写真性能を安定化させる目的で、種々の
化合物を含有させることができる。すなわチアゾール
類、例えばベンゾチアゾリウム塩、ニトロイミダゾール
類、ニトロベンズイミダゾール類、クロロベンズイミダ
ゾール類、ブロモベンズイミダゾール類、メルカプトチ
アゾール類、メルカプトベンゾチアゾール類、メルカプ
トベンズイミダゾール類、メルカプトチアジアゾール
類、アミノトリアゾール類、ベンゾトリアゾール類、ニ
トロベンゾトリアゾール類、メルカプトテトラゾール類
(特に、1−フェニル−5−メルカプトテトラゾール)
など;メルカプトピリミジン類;メルカプトトリアジン
類;例えばオキサドリンチオンのようなチオケト化合
物;アザインデン類、例えばトリアザインデン類、テト
ラアザインデン類(特に、4−ヒドロキシ−6−メチル
(1, 3, 3a, 7)テトラアザインデン)、ペンタア
ザインデン類などのようなカブリ防止剤または安定剤と
して知られた、多くの化合物を加えることができる。例
えば米国特許第3,954,474 号、同3,982,947 号、特公昭
52-28660号に記載されたものを用いることができる。好
ましい化合物の一つに特願昭62-47225号に記載された化
合物がある。カブリ防止剤および安定剤は粒子形成前、
粒子形成中、粒子形成後、水洗工程、水洗後の分散時、
化学増感前、化学増感中、化学増感後、塗布前のいろい
ろな時期に目的に応じて添加することができる。The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Many compounds known as antifoggants or stabilizers, such as tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947,
Those described in JP-A-52-28660 can be used. One of the preferred compounds is a compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers before particle formation,
During particle formation, after particle formation, water washing step, at the time of dispersion after water washing,
It can be added according to the purpose at various times before, during, after chemical sensitization and before coating.
【0094】本発明において、化学増感終了前に核酸ま
たはその分解生成物を共存させて化学増感することも好
ましい。核酸またはその分解生成物については、特開昭
62−67541号記載のものを用いることができる。
本発明に用いられる核酸としては、デオキシリボ核酸
(DNA)およびリボ核酸(RNA)を包含し、また、
核酸分解物としては、分解途中のものやアデニン、グア
ニン、ウラシル、シトシンおよびチミン等の単体が挙げ
られる。特に好ましい核酸分解生成物としては、アデニ
ンが挙げられる。これらは単独で、あるいは組み合わせ
て用いることができる。この場合、核酸と核酸分解生成
物とを組み合わせて用いても良いことはもちろんであ
る。この核酸またはその分解生成物の添加量は、核酸分
解生成物の種類により異なるが、ハロゲン化銀1モル当
たり20mg以上、好ましくは100mg〜1g の範囲であ
る。これらの核酸あるいは核酸分解生成物は、単独で
も、あるいは2種類以上組み合わせて用いる場合でも、
添加量の合計は前述の量で充分である。In the present invention, it is also preferable to carry out chemical sensitization in the presence of a nucleic acid or a decomposition product thereof before the completion of chemical sensitization. As the nucleic acid or a decomposition product thereof, those described in JP-A-62-67541 can be used.
The nucleic acid used in the present invention includes deoxyribonucleic acid (DNA) and ribonucleic acid (RNA).
Examples of the nucleic acid degradation products include those in the course of degradation and simple substances such as adenine, guanine, uracil, cytosine, and thymine. Particularly preferred nucleolytic products include adenine. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid decomposition product may be used in combination. The amount of the nucleic acid or the decomposition product thereof varies depending on the type of the nucleic acid decomposition product, but is in the range of 20 mg or more, preferably 100 mg to 1 g per mol of silver halide. These nucleic acids or nucleic acid degradation products may be used alone or in combination of two or more.
The above-mentioned amount is sufficient for the total amount of addition.
【0095】本発明の感光材料には、画像を鮮明にする
目的で、必要に応じてクロスオーバー光カット層を感光
性乳剤層と支持体の間に設けることができる。クロスオ
ーバー光カット層には、感光波長域に応じた染料を添加
する。染料は、現像処理後に有害な吸収を残さないもの
であればどのようなものでも使用できる。染料を固体微
粒子分散状態で添加する方法は、特開平2−26493
6号、特開平3−210553号、特開平3−2105
54号、特開平3−238447号、特開平4−140
38号、特開平4−14039号、特開平4−1256
35号、特開平4−338747号、特開平6−275
89号等に記載されている。使用できる染料は、例え
ば、特開平4−211542号記載の一般式(I)〜(V
II)の染料、化合物例I−1〜I−37、II−1〜II−
6、III−1〜III−36、IV−1〜IV−16、V−1〜V
−6、VI−1〜VI−13、VII−1〜VII−5。特開平8
−73767号記載の一般式(1)の染料、化合物例1
〜6。特開平8−87091号記載の一般式(VIII)〜
(XII)の染料、化合物例VIII−1〜VIII−5、IX−1
〜IX−10、X−1〜X−21、XI−1〜XI−6、XII−
1〜XII−7。In the light-sensitive material of the present invention, a crossover light cut layer may be provided between the light-sensitive emulsion layer and the support, if necessary, for the purpose of sharpening an image. A dye corresponding to the photosensitive wavelength region is added to the crossover light cut layer. Any dye can be used as long as it does not leave harmful absorption after the development processing. A method of adding a dye in a solid fine particle dispersion state is disclosed in JP-A-2-26493.
6, JP-A-3-210553, JP-A-3-2105
No. 54, JP-A-3-23847, JP-A-4-140
No. 38, JP-A-4-14039, JP-A-4-1256
No. 35, JP-A-4-338747, JP-A-6-275
No. 89, etc. Dyes that can be used include, for example, those represented by general formulas (I) to (V)
II) Dyes, Compound Examples I-1 to I-37, II-1 to II-
6, III-1 to III-36, IV-1 to IV-16, V-1 to V
-6, VI-1 to VI-13, VII-1 to VII-5. JP 8
Dyes of the general formula (1) described in -73767, Compound Example 1
~ 6. General formulas (VIII) to-described in JP-A-8-87091
Dyes of (XII), Compound Examples VIII-1 to VIII-5, IX-1
To IX-10, X-1 to X-21, XI-1 to XI-6, XII-
1 to XII-7.
【0096】これらの他に、公知の染料を媒染剤に吸着
させる方法、公知の染料をオイルに溶解し油滴状に乳化
分散する方法、特開平3−5748号記載の染料を無機
物表面に吸着させる方法、特開平2−298939号記
載の染料をポリマーに吸着させる方法等も利用すること
ができる。クロスオーバー光カット層の感光材料への添
加方法は、各明細書に記載されているものが利用でき
る。In addition to these, a method of adsorbing a known dye to a mordant, a method of dissolving a known dye in oil and emulsifying and dispersing it in oil droplets, and a method of adsorbing a dye described in JP-A-3-5748 on an inorganic material surface For example, a method described in JP-A-2-298939, in which a dye is adsorbed on a polymer, can be used. As a method for adding the crossover light-cutting layer to the photosensitive material, those described in each specification can be used.
【0097】本発明の感光材料には、感光材料の位置検
出の目的で、染料を添加してもよい。染料は、検出用セ
ンサーの感度極大波長に応じた吸収スペクトルを有する
ことが好ましく、現像処理後に有害な吸収を残さないも
のであればどのようなものでも使用できる。好ましく
は、700nm〜1400nmに吸収極大を有する染料また
はその微粒子分散物が使用される。例えば、以下のもの
である。The light-sensitive material of the present invention may contain a dye for the purpose of detecting the position of the light-sensitive material. The dye preferably has an absorption spectrum corresponding to the maximum sensitivity wavelength of the detection sensor, and any dye can be used as long as it does not leave harmful absorption after development processing. Preferably, a dye having a maximum absorption at 700 nm to 1400 nm or a fine particle dispersion thereof is used. For example:
【0098】(1)処理時に脱色させる水溶性染料とし
ては、特開平3−211542号記載の一般式(I)〜
(IV)のシアニン染料、ピリリウム染料およびアミニウ
ム染料、化合物例I−1〜I〜6、II−1〜II−4、II
I−1〜III−4、IV−1〜IV−5。(1) Examples of the water-soluble dye to be decolorized at the time of treatment include compounds represented by general formulas (I) to
(IV) cyanine dyes, pyrylium dyes and aminium dyes, examples of compounds I-1 to I-6, II-1 to II-4, II
I-1 to III-4, IV-1 to IV-5.
【0099】(2)処理時に脱色させる固体微粒子分散
状染料としては、特開平3−138640号記載の一般
式(I)〜(IV)のシアニン染料、ピリリウム染料およ
びアミニウム染料、化合物例I−1〜I〜28、II−1
〜II−10、III−1〜III−6、IV−1〜IV−7。(2) As solid fine particle-dispersed dyes to be decolorized at the time of treatment, cyanine dyes, pyrylium dyes and aminium dyes of the general formulas (I) to (IV) described in JP-A-3-138640, Compound Example I-1 ~ I ~ 28, II-1
To II-10, III-1 to III-6, IV-1 to IV-7.
【0100】(3)処理時に脱色させない染料として
は、特願平6−227983号記載の一般式(I)ない
し一般式(II)のカルボキシル基を有するトリカルボシ
アニン染料、化合物例1〜33。特願平6−27929
7号記載の一般式(I)ないし一般式(II)のカルボキ
シル基を有するテトラカルボシアン染料、化合物例1〜
19。特願平7−208569号記載の一般式(1)〜
一般式(3)の酸基を有しないシアニン染料、化合物例
1〜63。特願平7−135118号記載の一般式
[1]のレーキ型シアニン染料、化合物例No.1〜No.3
7。(3) Dyes which are not decolorized during the treatment include tricarbocyanine dyes having a carboxyl group of the general formulas (I) to (II) described in Japanese Patent Application No. 6-227983, and compound examples 1 to 33. Japanese Patent Application No. 6-27929
7, a carboxyl group-containing tetracarbocyan dye represented by formulas (I) to (II);
19. General formulas (1) to 7 described in Japanese Patent Application No. 7-208569.
Cyanine dyes having no acid group of the general formula (3), Compound Examples 1 to 63. Lake-type cyanine dyes of the general formula [1] described in Japanese Patent Application No. 7-135118, Compound Examples No. 1 to No. 3
7.
【0101】これらの他に、特開昭62−299959
号記載のピリリウム染料、特開昭63−131135号
記載の光散乱粒子、特開平1−266536号記載のシ
アニン染料、特開平2−282244号記載のオキソノ
ール染料の固体微粒子分散物、特開平3−136038
号記載のホロポーラ型シアニン染料、特開平7−253
639号記載のポリマー型シアニン染料、特開平7−1
13072号記載のスズドープ酸化インジウム(IT
O)粉末、特願平7−151380号記載のYb3+化合
物も利用することができる。In addition to these, JP-A-62-299959
JP-A-63-135135, light scattering particles described in JP-A-63-131135, cyanine dye described in JP-A-1-266536, solid fine particle dispersion of oxonol dye described in JP-A-2-282244, 136038
JP-A-7-253
No. 639, a polymer type cyanine dye,
No. 13072, tin-doped indium oxide (IT
O) Powders and Yb 3+ compounds described in Japanese Patent Application No. 7-151380 can also be used.
【0102】感光材料の位置検出を目的とする染料の感
光材料への添加方法は、各明細書に記載されているもの
が利用できる。As a method for adding a dye to the light-sensitive material for the purpose of detecting the position of the light-sensitive material, those described in each specification can be used.
【0103】本発明の感材においては、コロイド状シリ
カを含有することができる。コロイド状シリカとは、平
均粒径が1〜1000nm、好ましくは5〜500nm、さ
らに好ましくは5〜100nmであり、その主成分は二酸
化珪素で、少量成分としてアルミナ、あるいはアルギン
酸ナトリウムなどを含んでいてもよい。The light-sensitive material of the present invention may contain colloidal silica. The colloidal silica has an average particle diameter of 1 to 1000 nm, preferably 5 to 500 nm, more preferably 5 to 100 nm, and its main component is silicon dioxide, which contains alumina or sodium alginate as a minor component. Is also good.
【0104】コロイド状シリカの具体例としては、日産
化学(株)(日本、東京)の商品名でスノーテックス2
0、スノーテックス30、スノーテックスC、スノーテ
ックスO等が挙げられる。As a specific example of the colloidal silica, Snowtex 2 is a trade name of Nissan Chemical Co., Ltd. (Tokyo, Japan).
0, Snowtex 30, Snowtex C, Snowtex O and the like.
【0105】本発明の感材においてコロイド状シリカを
含有する層は、表面保護層、中間層、ハロゲン化銀乳剤
層、アンチハレーション層、下塗り層、フィルター層、
バッキング層など任意の親水性コロイド層でもよいが、
特に耐圧力性を目的とする場合においては、表面保護
層、またはハロゲン化銀乳剤層に含有することが好まし
い。In the light-sensitive material of the present invention, the layer containing colloidal silica includes a surface protective layer, an intermediate layer, a silver halide emulsion layer, an antihalation layer, an undercoat layer, a filter layer,
Although any hydrophilic colloid layer such as a backing layer may be used,
In particular, when pressure resistance is intended, it is preferably contained in a surface protective layer or a silver halide emulsion layer.
【0106】コロイド状シリカの含有量としては、含有
される親水性コロイド層の親水性コロイド重量に対して
1〜200wt%が好ましく、特に10〜100wt%
が好ましい。The content of the colloidal silica is preferably from 1 to 200 wt%, more preferably from 10 to 100 wt%, based on the weight of the hydrophilic colloid in the hydrophilic colloid layer contained.
Is preferred.
【0107】また、コロイド状シリカを含有する層にお
いて、必要に応じて可塑性のポリマーラテックスを併用
して含有することが好ましい。The layer containing colloidal silica preferably contains a plastic polymer latex, if necessary.
【0108】本発明の写真感光材料のいずれの層も、水
に対して難溶性のモノマーを重合してなるポリマーラテ
ックスを含有してもよい。Any of the layers of the photographic light-sensitive material of the present invention may contain a polymer latex obtained by polymerizing a water-insoluble monomer.
【0109】こうしたモノマーとしては、例えば特開平
7−230135号の2頁2段目5行目〜17行目記載
のアクリル酸エステル類、メタクリル酸エステル類、ジ
ビニルベンゼン等を用いることができる。As such a monomer, for example, acrylates, methacrylates, divinylbenzene, etc. described on page 2, line 2, lines 5 to 17 of JP-A-7-230135 can be used.
【0110】このようなポリマーラテックスは上記モノ
マーを他のモノマーと共重合してもよく、このときのモ
ノマーとしては、例えば特開平7−230135号の2
頁2段目32行目〜4頁1段目35行目記載のモノマー
を用いることができ、それらのうち、アクリル酸エステ
ル類、メタクリル酸エステル類、ビニルエステル類、ス
チレン類、オレフィン類が好ましく用いられる。In such a polymer latex, the above-mentioned monomer may be copolymerized with another monomer. Examples of the monomer at this time include those described in JP-A-7-230135.
The monomers described on page 2, line 32 to page 4, line 1, line 35 can be used, and among them, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferable. Used.
【0111】前記ポリマーラテックスの例としては、例
えば特開平7−230135号のLx−1〜Lx−21
が挙げられる。なお、ここでのポリマーラテックスも、
前述のように、ラテックス中のポリマーを意味する。Examples of the polymer latex include, for example, Lx-1 to Lx-21 disclosed in JP-A-7-230135.
Is mentioned. The polymer latex here is also
As mentioned above, means the polymer in the latex.
【0112】本発明には、特開平6−194779号の
実施例1に記載のNo.1〜No.8のマット剤を好ましく用
いることができる。また、特開平6−138572号の
[0023]段落に記載の好ましい化合物例1〜9を好
ましく用いることができる。In the present invention, No. 1 to No. 8 matting agents described in Example 1 of JP-A-6-194779 can be preferably used. Further, preferred compound examples 1 to 9 described in paragraph [0023] of JP-A-6-138572 can be preferably used.
【0113】これらのマット剤のサイズなどに関して
は、特開平6−194779号の[0049]段落に記
載のサイズや使用量で好ましく用いることができる。ま
た、2種類以上の粒子サイズのマット剤を混ぜて使うこ
とができる。マット剤の粒子サイズ分布については、目
的に応じてその変動係数が3〜30%の単分散粒子を用
いたり、30%以上の多分散粒子を用いたりできる。With respect to the size and the like of these matting agents, those having the sizes and amounts described in paragraph [0049] of JP-A-6-194779 can be preferably used. In addition, two or more types of matting agents having a particle size can be mixed and used. Regarding the particle size distribution of the matting agent, monodisperse particles having a variation coefficient of 3 to 30% or polydisperse particles of 30% or more can be used according to the purpose.
【0114】本発明のハロゲン化銀写真感光材料の好ま
しい乳剤の塗布量は、銀換算で、片面1m2当たり2.0
g 以下である。好ましくは0.5g 以上1.7g 以下で
ある。さらに好ましくは0.8g 以上1.5g 以下であ
る。[0114] The coating amount of the preferred emulsions of the silver halide photographic light-sensitive material of the present invention, in terms of silver, one side 1 m 2 per 2.0
g or less. Preferably, it is 0.5 g or more and 1.7 g or less. More preferably, it is 0.8 g or more and 1.5 g or less.
【0115】本発明の感材の親水性コロイド層の全ゼラ
チンの塗布量は2.5g以下(片面当たりの総塗布量)
であり、0.5g/m2 以上2.5g/m2 以下が好ま
しい。特に好ましくは1.0g/m2 以上2.1g/m
2 以下である。この場合、保護層のゼラチン塗布量は、
0.2g/m2 以上1.0g/m2 以下が好ましい。The coated amount of all gelatin in the hydrophilic colloid layer of the light-sensitive material of the present invention is 2.5 g or less (total coated amount per one side).
And preferably 0.5 g / m 2 or more and 2.5 g / m 2 or less. Particularly preferably, 1.0 g / m 2 or more and 2.1 g / m 2 or more.
2 or less. In this case, the gelatin coating amount of the protective layer is
It is preferably from 0.2 g / m 2 to 1.0 g / m 2 .
【0116】本発明において、感材の膨潤率は、感材を
21℃の蒸留水に3分間浸漬した後の膜厚値から乾燥状
態の膜厚値を引いた値を膨潤値とし、その値を乾燥状態
の膜厚値で割った値に100を掛けた値で(%)で定義
され、求めることができる。好ましい膨潤率の範囲は2
0%以上220%以下であり、より好ましくは40%以
上150%以下である。In the present invention, the swelling ratio of the light-sensitive material is defined as a value obtained by subtracting the dry film thickness from the film thickness after immersing the light-sensitive material in distilled water at 21 ° C. for 3 minutes. Divided by the dry film thickness value and multiplied by 100, defined as (%) and can be determined. The preferred range of the swelling ratio is 2
It is 0% or more and 220% or less, and more preferably 40% or more and 150% or less.
【0117】一般にハロゲン化銀写真感光材料は、ゼラ
チンのような親水性コロイドをバインダーとする水溶性
塗布液を支持体上に塗布した後、−10〜20℃の乾球
温度の低温空気中で冷却凝固させて、次いで、温度を高
めて乾燥される。通常、塗布直後のゼラチンと水分の重
量比は3000%前後である。In general, a silver halide photographic light-sensitive material is coated on a support with a water-soluble coating solution containing a hydrophilic colloid such as gelatin as a binder and then dried in a low-temperature air at a dry-bulb temperature of -10 to 20 ° C. It is cooled and solidified, and then dried at an elevated temperature. Usually, the weight ratio between gelatin and water immediately after coating is about 3000%.
【0118】この塗布液には、通常、親水性コロイドバ
インダー、ハロゲン化銀粒子、界面活性剤、ポリマーラ
テックスのような可塑剤、ゼラチン硬化剤、染料、増感
色素、マット剤等種々の添加剤が含まれている。The coating solution is usually mixed with various additives such as a hydrophilic colloid binder, silver halide particles, a surfactant, a plasticizer such as a polymer latex, a gelatin hardener, a dye, a sensitizing dye and a matting agent. It is included.
【0119】本発明においては、親水性コロイド層塗布
液を塗布後乾燥する際、ハロゲン化銀乳剤層を有する側
の塗布層全層のバインダー乾量に対して100%以下の
水分量になるまで、湿球温度が20℃以下、好ましくは
19℃〜10℃で乾燥することが好ましい。In the present invention, when the coating solution of the hydrophilic colloid layer is applied and dried, the water content of the coating layer on the side having the silver halide emulsion layer is 100% or less with respect to the dry weight of the binder. It is preferable to dry at a wet bulb temperature of 20 ° C. or lower, preferably 19 ° C. to 10 ° C.
【0120】親水性コロイド層が2層以上同時に塗布
し、乾燥される場合には(すなわち乾燥対象となる塗布
層が2層以上の場合には)、水分量は全層の水分の和
を、バインダー乾量は全層のバインダー乾量(乾燥重
量)の和を表わす。When two or more hydrophilic colloid layers are simultaneously coated and dried (ie, when two or more coating layers are to be dried), the water content is the sum of the water content of all the layers. The binder dry weight represents the sum of the binder dry weight (dry weight) of all layers.
【0121】湿球温度とは、湿り空気の平衡状態での水
滴の温度で、空気の湿度が小さいほど低い。乾燥工程の
恒率乾燥期間においては、乾燥風の湿球温度が塗布試料
の表面温度にほぼ等しい。The wet-bulb temperature is the temperature of a water drop in a humid air equilibrium state, and is lower as the humidity of the air is smaller. During the constant-rate drying period of the drying step, the wet-bulb temperature of the drying air is substantially equal to the surface temperature of the applied sample.
【0122】また、塗布、乾燥後ロール状に巻き取る時
の環境条件は、絶対湿度が1.4wt%以下、好ましく
は1.3〜0.6wt%で巻き取られることが好まし
い。[0122] Further, as for the environmental conditions when winding in a roll after coating and drying, it is preferable that the film is wound at an absolute humidity of 1.4 wt% or less, preferably 1.3 to 0.6 wt%.
【0123】本発明において、塗布、乾燥後ロール状に
巻き取ったハロゲン化銀写真感光材料の製品加工は、絶
対湿度が1.4wt%以下、好ましくは1.3〜0.6
wt%の環境下で加工されるのが好ましい。In the present invention, the product processing of the silver halide photographic light-sensitive material wound up in a roll after coating and drying is performed at an absolute humidity of 1.4% by weight or less, preferably 1.3 to 0.6%.
Processing is preferably performed in an environment of wt%.
【0124】絶対湿度(wt%)とは、湿り空気の状態
を表わし、湿り空気中の水蒸気量(kg)と湿り空気中の
乾き空気の重量(kg)の比を百分率で表わしたものであ
る。The absolute humidity (wt%) represents the state of the humid air, and represents the ratio of the amount of water vapor (kg) in the humid air to the weight (kg) of the dry air in the humid air in percentage. .
【0125】ハロゲン化銀写真感光材料を防湿性のある
包装体内に入れ、包装体内の絶対湿度が1.4wt%以
下、好ましくは1.1〜0.6wt%になるように、そ
の口をヒートシール等で密封し、感光材料が上記絶対湿
度で平衡になっていることをいう。The silver halide photographic light-sensitive material is placed in a moisture-proof package, and its opening is heated so that the absolute humidity in the package is 1.4 wt% or less, preferably 1.1 to 0.6 wt%. Sealing with a seal or the like means that the photosensitive material is in equilibrium with the above absolute humidity.
【0126】さらに、加工終了後、絶対湿度1.4wt
%以下の環境下でシーズニングしてから、同一環境下で
包装体内にヒートシール密封するのは特に好ましい。Further, after the processing is completed, the absolute humidity is 1.4 wt.
%, It is particularly preferable that the package is heat-sealed and sealed in the package under the same environment after seasoning in an environment of not more than%.
【0127】本発明の感光材料に用いられる各種添加剤
に関しては特に制限はなく、例えば特開平2−6853
9号公報の以下の該当箇所に記載のものを用いることが
できる。There are no particular restrictions on the various additives used in the light-sensitive material of the present invention.
No. 9 can be used as described in the following sections.
【0128】 項目該当箇所 1.ハロゲン化銀乳剤と 特開平2−68539号公報第8頁右下欄下から6 その製法 行目から同第10頁右上欄12行目。 2.化学増感方法 同第10頁右上欄13号目から同左下欄16行目。 3.カブリ防止剤・安定 同第10頁左下欄17行目から同第11頁左上欄7 剤 行目および同第3頁左下欄2行目から同第4頁左下 欄。 4.分光増感色素 同第4頁右下欄4行目から同第8頁右下欄。 5.界面活性剤・帯電防 同第11頁左上欄14行目から同第12頁左上欄9 止剤 行目。 6.マット剤・滑り剤・ 同第12頁左上欄10行目から同右上欄10行目。 可塑剤 同第14頁左下欄10行目から同右下欄1行目。 7.親水性コロイド 同第12頁右上欄11行目から同左下欄16行目。 8.硬膜剤 同第12頁左下欄17行目から同第13頁右上欄6 行目。 9.支持体 同第13頁右上欄7行目から20行目。 10.染料・媒染剤 同第13頁右下欄1行目から同第14頁左下欄9行 目。Items Applicable Locations From the lower right column on page 8, lower right column, page 6 of JP-A-2-68539, from the line of production thereof to the upper right column, page 10, line 12 of JP-A-2-68539. 2. Chemical sensitization method: From page 13, upper right column, item 13 to lower left column, line 16 of the same. 3. Antifoggant / Stable page 10, lower left column, line 17 to page 11, upper left column 7 agent line and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactant / Electrostatic Protection Line 11 on page 11, upper left column to line 9, Stopper on page 12, upper left column. 6. Matting agent, slip agent, page 12, top left column, line 10 to top right column, line 10. Plasticizer Same as page 14, lower left column, line 10 to lower right column, line 1. 7. Hydrophilic colloid, page 12, line 11, upper right column to line 16, lower left column. 8. Hardener From page 12, lower left column, line 17 to page 13, upper right column, line 6; 9. Supporting substance: From page 7, line 7 to line 20 in the upper right column. Ten. Dyes and mordants, page 13, lower right column, line 1 to page 14, lower left column, line 9.
【0129】本発明の写真感光材料は、例えば下記の蛍
光体を蛍光増感紙として用い、X線撮影を好ましく行う
ことができる。 ブルー発光蛍光体 Y2 O2 S:Tb、LaOBr:Tb、BaFCl:E
u グリーン発光蛍光体 Gd2 O2 S:Tb、LaO2 S:TbIn the photographic light-sensitive material of the present invention, for example, X-ray photography can be preferably performed using the following phosphors as fluorescent intensifying screens. Blue light-emitting phosphor Y 2 O 2 S: Tb, LaOBr: Tb, BaFCl: E
u Green emitting phosphor Gd 2 O 2 S: Tb, LaO 2 S: Tb
【0130】UV発光蛍光体としては、M’相YTaO
4 単独あるいはGd,Bi,Pb,Ce,Se,Al,
Rb,Ca,Cr,Cd,Nbなどを添加した化合物、
LaOBrにGd,Tm,GdおよびTm,Gdおよび
Ce,Tbを添加した化合物、HfZrの酸化物単独あ
るいはGe,Ti,アルカリ金属などを添加した化合
物、Y2 O3 単独あるいはGd,Euを添加した化合
物、Y2 O2 SにGdを添加した化合物、各種蛍光体の
母体にGd,Tl,Ceを付活剤として用いた化合物な
どがある。特に好ましい化合物としては、M’相YTa
O4 単独あるいはGd,Srを添加した化合物、LaO
BrにGd,Tm,GdおよびTmを添加した化合物、
HfZrの酸化物あるいはGe,Ti,アルカリ金属な
どを添加した化合物である。As the UV-emitting phosphor, M′-phase YTaO
4 alone or Gd, Bi, Pb, Ce, Se, Al,
Compounds to which Rb, Ca, Cr, Cd, Nb, etc. are added,
LaOBr to Gd, Tm, Gd and Tm, Gd and Ce, compounds obtained by adding Tb, oxide alone or Ge, Ti, compounds obtained by adding an alkali metal HfZr, Y 2 O 3 alone or Gd, was added Eu There are compounds, compounds in which Gd is added to Y 2 O 2 S, and compounds in which Gd, Tl, and Ce are used as activators for the base of various phosphors. Particularly preferred compounds include M ′ phase YTa
O 4 alone or Gd, compounds obtained by adding Sr, LaO
A compound obtained by adding Gd, Tm, Gd and Tm to Br,
It is a compound to which an oxide of HfZr or Ge, Ti, alkali metal or the like is added.
【0131】蛍光体の平均粒径は1μm以上20μm以
下がよいが、求められる感度や製造上の問題から変更で
きる。塗布量は400g/mm2 以上2000g/mm2 以
下が好ましいが、求められる感度や画質に応じて一概に
はいえない。また、一枚の増感紙で支持体の近傍から表
面に向かって粒子サイズ分布をつけてもかまわない。こ
の場合一般的には、表面の粒子を大きくすることが知ら
れている。蛍光体の空間充填率は40%以上、好ましく
は60%以上である。The average particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed in accordance with the required sensitivity and manufacturing problems. The coating amount is preferably 400 g / mm 2 or more and 2000 g / mm 2 or less, but cannot be said unconditionally depending on the required sensitivity and image quality. Further, a single intensifying screen may give a particle size distribution from the vicinity of the support to the surface. In this case, it is generally known that particles on the surface are enlarged. The space filling ratio of the phosphor is 40% or more, preferably 60% or more.
【0132】感光材料の両面に蛍光体層を配して撮影す
る場合、X線入射側とその反対側の蛍光体塗布量は変え
ることができる。一般にX線入射側の増感紙による遮蔽
のため、特に高感度システムを必要とする場合、X線入
射側の増感紙の塗布量を小さくすることが知られてい
る。In the case of arranging a phosphor layer on both surfaces of a photosensitive material for photographing, the amount of the phosphor applied on the X-ray incident side and the opposite side can be changed. In general, it is known to reduce the coating amount of the intensifying screen on the X-ray incident side, especially when a high-sensitivity system is required for shielding by the intensifying screen on the X-ray incident side.
【0133】本発明に用いられるスクリーンに使用する
支持体は、紙、金属板、ポリマーシートなどが挙げられ
るが、一般的にはポリエチレンテレフタレートなどのフ
レキシブルなシートが用いられる。支持体には、必要に
応じて、反射剤や光吸収剤が添加されていても表面に別
の層として設けられていてもよい。As the support used for the screen used in the present invention, paper, metal plate, polymer sheet and the like can be mentioned, but a flexible sheet such as polyethylene terephthalate is generally used. The support may be added with a reflecting agent or a light absorbing agent, if necessary, or may be provided as a separate layer on the surface.
【0134】また、必要に応じて、支持体表面に微少に
凹凸を付けたり、蛍光体層との密着力増加のための粘着
層や、導電層を下塗りとして設けることができる。反射
剤としては、酸化亜鉛、酸化チタン、硫酸バリウムなど
が挙げられるが、蛍光体の発光波長が短いことから、酸
化チタン、硫酸バリウムが好ましい。反射剤は、支持体
中あるいは支持体と蛍光体層の間だけでなく、蛍光体層
中に存在せしめても良い。蛍光体層中に存在させる場
合、支持体近傍に偏在させることが好ましい。Further, if necessary, the surface of the support may be provided with minute irregularities, an adhesive layer for increasing the adhesion to the phosphor layer, or a conductive layer may be provided as an undercoat. Examples of the reflecting agent include zinc oxide, titanium oxide, and barium sulfate. Titanium oxide and barium sulfate are preferable because the emission wavelength of the phosphor is short. The reflecting agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it is present in the phosphor layer, it is preferable to be unevenly distributed near the support.
【0135】本発明のスクリーンで用いられる結合剤と
しては、ゼラチンなどの蛋白質、デキストラン、コーン
スターチなどのポリサッカライド、アラビアゴムなど天
然高分子物質;ポリビニルブチラール、ポリ酢酸ビニ
ル、ポリウレタン、ポリアルキルアクリレート、塩化ビ
ニリデン、ニトロセルロース、フッ素含有ポリマー、ポ
リエステルなどの合成高分子物質、またこれらの混合物
やコポリマーが挙げられる。好ましい結合剤としては、
基本的な性能としては、蛍光体からの発光に対して透過
率が高いことが挙げられる。この点において、ゼラチ
ン、コーンスターチ、アクリル系ポリマー、フッ素を含
むオレフィンポリマーやフッ素を含むオレフィンをコポ
リマー成分として含有するポリマー、スチレン/アクリ
ルニトリルコポリマーなどが挙げられる。これらの結合
剤は、架橋剤によって架橋されるような官能器を有して
いてもよい。また、求められる画質性能によって、結合
剤中に蛍光体からの発光に対する吸収剤を添加させた
り、透過率の低い結合剤を用いてもよい。吸収剤として
は、顔料や染料、紫外線吸収化合物があげられる。蛍光
体と結合剤の比率は、一般的に体積比において1:5な
いし50:1、好ましくは1:1ないし15:1であ
る。蛍光体と結合剤の比率は、均一であっても厚さ方向
に不均一であってもよい。The binder used in the screen of the present invention includes proteins such as gelatin, polysaccharides such as dextran and corn starch, and natural high molecular substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, chloride Synthetic high-molecular substances such as vinylidene, nitrocellulose, fluorine-containing polymers and polyesters, and mixtures and copolymers thereof are also included. Preferred binders include:
As a basic performance, a high transmittance with respect to light emission from the phosphor is cited. In this regard, gelatin, corn starch, acrylic polymers, olefin polymers containing fluorine, polymers containing fluorine-containing olefins as copolymer components, styrene / acrylonitrile copolymers and the like can be mentioned. These binders may have functional groups that are crosslinked by the crosslinking agent. Depending on the required image quality performance, an absorber for the emission from the phosphor may be added to the binder, or a binder having a low transmittance may be used. Examples of the absorbent include a pigment, a dye, and an ultraviolet absorbing compound. The ratio of phosphor to binder is generally from 1: 5 to 50: 1, preferably from 1: 1 to 15: 1 by volume. The ratio between the phosphor and the binder may be uniform or non-uniform in the thickness direction.
【0136】蛍光体層は、通常、蛍光体を結合剤溶液中
に分散させた塗布液を用い、塗布法により形成される。
塗布液の溶剤としては、水あるいはアルコール、塩素含
有炭化水素、ケトン、エステル、エーテル芳香族化合物
などの有機溶剤、およびこれらの混合物が挙げられる。The phosphor layer is usually formed by a coating method using a coating solution in which the phosphor is dispersed in a binder solution.
Examples of the solvent for the coating liquid include water or organic solvents such as alcohols, chlorine-containing hydrocarbons, ketones, esters, and ether aromatic compounds, and mixtures thereof.
【0137】塗布液中には、蛍光体粒子のフタル酸、ス
テアリン酸、カプロン酸、界面活性剤などの分散安定剤
や、燐酸エステル、フタル酸エステル、グリコール酸エ
ステル、ポリエステル、ポリエチレングリコールなどの
可塑剤を添加してもよい。In the coating solution, a dispersion stabilizer such as phthalic acid, stearic acid, caproic acid and a surfactant of the phosphor particles, and a plasticizer such as a phosphoric acid ester, a phthalic acid ester, a glycolic acid ester, a polyester and a polyethylene glycol are used. An agent may be added.
【0138】本発明に用いられるスクリーンには、蛍光
体層上に保護層を設けることができる。保護層は、蛍光
体層上に塗布する方法、別途保護層膜を作製しラミネー
トする方法が一般的に用いられる。塗布法においては、
蛍光体層と同時に塗布してもよいし、蛍光体層を塗布乾
燥させた後塗設してもよい。保護層は、蛍光体層の結合
剤と同じ物質でもよいし、異種の物質でもよい。保護層
に用いられる物質としては、蛍光体層の結合剤に挙げた
物質のほか、セルロース誘導体、ポリ塩化ビニル、メラ
ミン、フェノール樹脂、エポキシ樹脂などが挙げられ
る。好ましい物質としては、ゼラチン、コーンスター
チ、アクリル系ポリマー、フッ素を含むオレフィンポリ
マーやフッ素を含むオレフィンをコポリマー成分として
含有するポリマー、スチレン/アクリルニトリルコポリ
マーなどが挙げられる。保護層の厚みは、一般に1μm
以上20μm以下で、2μm以上10μm以下が好まし
く、2μm以上6μm以下がさらに好ましい。本発明の
保護層の表面にエンボス加工を施すことは好ましい。ま
た、保護層中にマット剤を存在させてもよいし、求める
画像によっては発光に対し光散乱性を有している物質、
例えば酸化チタンなどを存在させてもよい。In the screen used in the present invention, a protective layer can be provided on the phosphor layer. As the protective layer, a method of coating on the phosphor layer or a method of separately forming a protective layer film and laminating is used. In the application method,
It may be applied simultaneously with the phosphor layer, or may be applied after the phosphor layer is applied and dried. The protective layer may be the same substance as the binder of the phosphor layer or a different substance. Examples of the substance used for the protective layer include cellulose derivatives, polyvinyl chloride, melamine, phenol resins, epoxy resins, and the like, in addition to the substances listed for the binder of the phosphor layer. Preferred substances include gelatin, corn starch, acrylic polymers, olefin polymers containing fluorine, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. The thickness of the protective layer is generally 1 μm
It is preferably at least 20 μm and at most 2 μm and at most 10 μm, more preferably at least 2 μm and at most 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. Further, a matting agent may be present in the protective layer, or a substance having a light scattering property with respect to light emission depending on a desired image,
For example, titanium oxide or the like may be present.
【0139】本発明に用いられるスクリーンの保護層中
には、表面の滑り性を付与してもよい。好ましい滑り剤
としては、ポリシロキサン骨格含有オリゴマー、パーフ
ルオロアルキル基含有オリゴマーが挙げられる。In the protective layer of the screen used in the present invention, a surface slip property may be imparted. Preferred sliding agents include oligomers containing a polysiloxane skeleton and oligomers containing a perfluoroalkyl group.
【0140】本発明の保護層に導電性を付与してもよ
い。導電性付与剤としては、白色および透明な無機導電
性物質や有機帯電防止剤が挙げられる。好ましい無機導
電性物質としては、ZnO粉末や、ウィスカ、SnO
2 、ITOなどが挙げられる。The protective layer of the present invention may be provided with conductivity. Examples of the conductivity-imparting agent include white and transparent inorganic conductive substances and organic antistatic agents. Preferred inorganic conductive materials include ZnO powder, whiskers, and SnO.
2 , ITO and the like.
【0141】本発明の現像処理の方法としては、米国特
許第5498511号、特開平7−16832号、特開
平8−54712号、特願平8−168670号、特願
平8−198401号に記載の方法を参考にすることが
できる。The developing method of the present invention is described in US Pat. No. 5,498,511, JP-A-7-16832, JP-A-8-54712, Japanese Patent Application No. 8-168670, and Japanese Patent Application No. 8-198401. Method can be referred to.
【0142】本発明の感材を処理する現像液には、現像
主薬としてハイドロキノンやアスコルビン酸あるいはエ
リソルビン酸(アスコルビン酸のジアステレオマー)お
よび/またはそれらの誘導体を用いることが好ましい。
本発明に用いるアスコルビン酸および/またはそれらの
誘導体としては、米国特許第2688549号、特公昭
36−17599号、特開平3−249756号、特開
平4−270343号等に記載されている。具体的に
は、米国特許第2688549号の第1ページ第1カラ
ムの22行目から第1ページ第2カラムの33行目まで
に記載の化合物、特公昭36−17599号の第1ペー
ジ左カラム21行目から26行目に記載の化合物、特開
平3−249756号第4ページに記載の化合物I-1か
らI-8およびII-1からII-4、特開平4−270343号
第4ページ第5カラム40行目から50行目に記載され
ている化合物を用いることができる。これらのうち、ア
スコルビン酸あるいはエリスルビン酸(アスコルビン酸
のジアステレオマー)およびこれらのリチウム塩、ナト
リウム塩、カリウム塩などのアルカリ金属塩が好まし
い。現像主薬は通常0.01モル/リットル〜0.8モ
ル/リットルの量で用いられるのが好ましく、0.1モ
ル/リットル〜0.4モル/リットルの量で用いるのが
特に好ましい。In the developing solution for processing the light-sensitive material of the present invention, it is preferable to use hydroquinone, ascorbic acid, erythorbic acid (a diastereomer of ascorbic acid) and / or a derivative thereof as a developing agent.
Ascorbic acid and / or derivatives thereof used in the present invention are described in U.S. Pat. No. 2,688,549, JP-B-36-17599, JP-A-3-249756, JP-A-4-270343, and the like. Specifically, the compounds described in U.S. Pat. No. 2,688,549 from the first column, first column, line 22 to the first page, second column, line 33, the first page left column of JP-B-36-17599. Compounds described in lines 21 to 26, compounds I-1 to I-8 and II-1 to II-4 described in JP-A-3-249756, page 4, JP-A-4-270343, page 4 The compounds described in the fifth column, lines 40 to 50, can be used. Among these, ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid) and alkali metal salts thereof such as lithium salt, sodium salt and potassium salt are preferable. The developing agent is usually preferably used in an amount of 0.01 mol / l to 0.8 mol / l, and particularly preferably in an amount of 0.1 mol / l to 0.4 mol / l.
【0143】本発明において、現像主薬とともに超加成
性を示す補助現像主薬を併用することが望ましい。超加
成性を示す補助現像主薬としては1−フェニル−3−ピ
ラゾリドン類補助現像主薬がある。1−フェニル−3−
ピラゾリドン類補助現像主薬としては、1−フェニル−
3−ピラゾリドン、1−フェニル−4,4−ジメチル−
3−ピラゾリドン、1−フェニル−4−メチル−4−ヒ
ドロキシメチル−3−ピラゾリドン、1−フェニル−
4,4−ジヒドロキシメチル−3−ピラゾリドン、1−
フェニル−5−メチル−3−ピラゾリドン、1−p−ア
ミノフェニル−4,4−ジメチル−3−ピラゾリドン、
1−p−トリル−4,4−ジメチル−3−ピラゾリド
ン、1−p−トリル−4−メチル−4−ヒドロキシメチ
ル−3−ピラゾリドンなどがある。これらのうち1−フ
ェニル−4−メチル−4−ヒドロキシメチル−3−ピラ
ゾリドンが好ましい。本発明において、現像主薬ととも
に1−フェニル−3−ピラゾリドン類補助現像主薬を組
み合わせて使用する場合には0.001モル/リットル
〜0.1モル/リットルの量で用いられるのが好まし
く、特に後者を0.005モル/リットル〜0.05モ
ル/リットルの量で用いるのが好ましい。In the present invention, it is desirable to use an auxiliary developing agent having superadditivity together with the developing agent. Auxiliary developing agents exhibiting superadditivity include 1-phenyl-3-pyrazolidones auxiliary developing agents. 1-phenyl-3-
As the pyrazolidone auxiliary developing agent, 1-phenyl-
3-pyrazolidone, 1-phenyl-4,4-dimethyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone,
There are 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone is preferred. In the present invention, when a 1-phenyl-3-pyrazolidone auxiliary developing agent is used in combination with the developing agent, it is preferably used in an amount of 0.001 mol / l to 0.1 mol / l, and especially the latter. Is preferably used in an amount of 0.005 mol / liter to 0.05 mol / liter.
【0144】また、超加成性を示す補助現像主薬として
はp−アミノフェノール類補助現像主薬がある。p−ア
ミノフェノール類補助現像主薬としては、N−メチル−
p−アミノフェノール、N−(β−ヒドロキシエチル)
−p−アミノフェノール、N−(4−ヒドロキシフェニ
ル)−グリシン、2−メチル−p−アミノフェノール、
p−ベンジルアミノフェノール等があるが、なかでもN
−メチル−p−アミノフェノールが好ましい。本発明に
おいて、現像主薬とともにp−アミノフェノール類補助
現像主薬を組み合わせて使用する場合には0.001モ
ル/リットル〜0.1モル/リットルの量で用いられる
のが好ましく、特に後者を0.005モル/リットル〜
0.05モル/リットルの量で用いるのが好ましい。The auxiliary developing agents exhibiting superadditivity include p-aminophenol auxiliary developing agents. As p-aminophenols auxiliary developing agents, N-methyl-
p-aminophenol, N- (β-hydroxyethyl)
-P-aminophenol, N- (4-hydroxyphenyl) -glycine, 2-methyl-p-aminophenol,
There are p-benzylaminophenol and the like.
-Methyl-p-aminophenol is preferred. In the present invention, when a p-aminophenol auxiliary developing agent is used in combination with the developing agent, it is preferably used in an amount of 0.001 mol / l to 0.1 mol / l, and in particular, the latter is used in an amount of 0.1 mol / l. 005 mol / l ~
It is preferably used in an amount of 0.05 mol / l.
【0145】現像液に添加するカブリ防止剤としては、
アゾール化合物(例えばベンゾチアゾリウム類、ベンゾ
イミダゾリウム類、イミダゾール類、ベンゾイミダゾー
ル類、ニトロインダゾール類、トリアゾール類、ベンゾ
トリアゾール類、テトラゾール類、トリアジン類等)、
メルカプト化合物(例えばメルカプトチアゾール類、メ
ルカプトベンゾチアゾール類、メルカプトイミダゾール
類、メルカプトベンゾイミダゾール類、メルカプトベン
ゾオキサゾール類、メルカプトチアゾール類、メルカプ
トオキサジアゾール類、メルカプトテトラゾール類、メ
ルカプトピリミジン類、メルカプトトリアジン類等)。
特にベンゾトリアゾール類としては、5−メチルベンゾ
トリアゾール、5−ブロムベンゾトリアゾール、5−ク
ロルベンゾトリアゾール、5−ブチルベンゾトリアゾー
ル、ベンゾトリアゾール等がある。ニトロインダゾール
類としては、5−ニトロインダゾール、6−ニトロイン
ダゾール、4−ニトロインダゾール、7−ニトロインダ
ゾール、3−シアノ−5−ニトロインダゾール等を用い
ることができる。The antifoggant added to the developer includes
Azole compounds (for example, benzothiazolium, benzimidazolium, imidazole, benzimidazole, nitroindazole, triazole, benzotriazole, tetrazole, triazine, etc.),
Mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiazoles, mercaptooxadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, etc.) .
Particularly, benzotriazoles include 5-methylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzotriazole, 5-butylbenzotriazole, benzotriazole and the like. As nitroindazoles, 5-nitroindazole, 6-nitroindazole, 4-nitroindazole, 7-nitroindazole, 3-cyano-5-nitroindazole and the like can be used.
【0146】本発明において、現像液に銀汚れ防止剤と
して特公昭56−46585号、特公昭62−4702
号、特公昭62−4703号、米国特許第425221
5号、米国特許第3318701号、特開昭58−20
3439号、特開昭62−56959号、特開昭62−
178247号、特開平1−200249号、特開平5
−503179号、特開平5−53257号に記載の化
合物を用いることができる。In the present invention, JP-B-56-46585 and JP-B-62-4702 are used as silver stain inhibitors in a developer.
No., JP-B-62-4703, U.S. Pat.
No. 5, U.S. Pat. No. 3,318,701, JP-A-58-20
No. 3439, JP-A-62-56959, JP-A-62-25959.
No. 178247, Japanese Unexamined Patent Application Publication No. 1-2209, Japanese Unexamined Patent Application Publication No.
Compounds described in JP-A-503179 and JP-A-5-53257 can be used.
【0147】定着促進剤としては、特公昭45−357
54号、特開昭58−122535号、同58−122
536号記載のチオ尿素誘導体、分子内に三重結合を有
したアルコール、米国特許第4126459号記載のチ
オエーテル、またはアニオンをフリー化するシクロデキ
ストランエーテル体、クラウンエーテル類、ジアザシク
ロウンデセンやジ(ヒドロキシエチル)ブタミン等が挙
げられる。特開平7−5654号、同6−273898
号に記載のメソイオン系化合物を含むことができる。Examples of the fixing accelerator include JP-B-45-357.
No. 54, JP-A-58-122535 and JP-A-58-122.
No. 536, an alcohol having a triple bond in the molecule, a thioether described in U.S. Pat. No. 4,126,459, or a cyclodextran ether derivative which frees an anion, crown ethers, diazacycloundecene or di ( (Hydroxyethyl) butamine and the like. JP-A-7-5654, 6-273898
And the mesoionic compounds described in (1).
【0148】防黴手段としては、特開昭60−2639
39号に記された紫外線照射法、同60−263940
号に記された磁場を用いる方法、同61−131632
号に記されたイオン交換樹脂を用いて純粋にする方法、
同61−115154号、同62−153952号、特
願昭61−63030号、同61−51396号に記載
の防菌剤を用いる方法を併用することができる。As the antifungal means, Japanese Patent Application Laid-Open No. Sho 60-2639
Ultraviolet irradiation method described in No. 39, No. 60-263940
No. 61-131632 using a magnetic field described in
Purification method using the ion-exchange resin described in No.,
Nos. 61-115154, 62-153952, and Japanese Patent Application Nos. 61-63030 and 61-51396 can be used in combination.
【0149】さらにはL.F.West "Water Quality Criter
ia" Photo.Sci.& Eng.,Vol.9,(1965)、M.W.Beach "Micr
obiological Growth in Motion-picture Processing" S
MTPEJournal Vol. 85(1976)、R.D.Deegan "Photo Proce
ssing Wash Water Biocides" J.Imaging Tech., Vol.1
0,No.6(1984)および特開昭57−8542号、同57−
58143号、同58−105145号、同57−13
2146号、同58−18631号、同57−9753
0号、同57−157244号、特開平6−11858
3号、同8−248589号等に記載されている防菌
剤、防黴剤、界面活性剤等を併用することができる。Further, LFWest "Water Quality Criter"
ia "Photo.Sci. & Eng., Vol. 9, (1965), MWBeach" Micr
obiological Growth in Motion-picture Processing "S
MTPEJournal Vol. 85 (1976), RDDeegan "Photo Proce
ssing Wash Water Biocides "J.Imaging Tech., Vol.1
0, No. 6 (1984) and JP-A-57-8542,
No. 58143, No. 58-105145, No. 57-13
No. 2146, No. 58-18631, No. 57-9753
No. 0, No. 57-157244, JP-A-6-11858
No. 3, No. 8-248589 and the like can be used in combination.
【0150】さらに、水洗浴または安定化浴には、R.T.
Kreinman著、J.Image.Tech.,10(6)242頁(1984)に記載さ
れたイソチアゾリン系化合物、Research Disclosure第
205巻、No.20526(1981年5月号)に掲載された
イソチアゾリン系化合物、同第228巻、No.22845(1
983年4月号)に記載されたイソチアゾリン系化合
物、特願昭61−51396号に記載された化合物等を
防菌剤(Microbiocide)として併用することもできる。そ
の他、「防菌防黴の化学」堀口博著、三井出版(昭和5
7)、「防菌防黴技術ハンドブック」日本防菌防黴学
会、博報堂(昭和61)に記載されているような化合物
を含んでもよい。Further, a washing bath or a stabilizing bath may include RT.
An isothiazoline-based compound described in Kreinman, J. Image.Tech., 10 (6), p. 242 (1984), and an isothiazoline-based compound described in Research Disclosure Vol. 205, No. 20526 (May, 1981). , Vol. 228, No. 22845 (1
The isothiazoline compounds described in Japanese Patent Application No. 61-51396 (April 983, April 1983) and the like can be used in combination as a microbiocide. In addition, "The Chemistry of Bactericidal and Fungicide Protection" by Hiroshi Horiguchi, Mitsui Publishing (Showa 5)
7), "Handbook of antibacterial and antifungal technology" may contain compounds described in Hakuhodo (Showa 61), Japan Society of Antifungal and Antifungal Activities.
【0151】さらに、水洗または安定化浴に防黴手段を
施した水を処理に応じて補充することによって生じる、
水洗または安定化浴からのオーバーフローの一部または
全部は、特開昭60−235133号に記載されている
ように、その前処理工程である定着能を有する処理液の
希釈に利用することもできる。Further, it is produced by replenishing the washing or stabilizing bath with water provided with a fungicide according to the treatment.
Part or all of the overflow from the washing or stabilizing bath can be used for diluting a processing solution having a fixing ability, which is a preprocessing step, as described in JP-A-60-235133. .
【0152】本発明の処理システムにおいては、現像槽
から定着槽、定着槽から水洗槽への感材により持ち出さ
れる液の持ち出し量は、4切り1枚当たり0.01cc以
上2cc以下が好ましく、0.1cc以上1.2cc以下がさ
らに好ましく、特に好ましくは0.1cc以上0.8cc以
下が好ましい。In the processing system of the present invention, the amount of liquid taken out by the photosensitive material from the developing tank to the fixing tank and from the fixing tank to the washing tank is preferably 0.01 cc to 2 cc per 4 pieces. It is more preferably from 0.1 cc to 1.2 cc, particularly preferably from 0.1 cc to 0.8 cc.
【0153】水洗槽が多段である場合は、水洗槽から水
洗槽への持ち出し量は、4切り1枚当たり0.1cc以上
2cc以下が好ましく、0.1cc以上1.2cc以下がより
好ましい。特に好ましくは0.1cc以上0.8cc以下が
好ましい。When the washing tank has multiple stages, the carry-out amount from the washing tank to the washing tank is preferably 0.1 cc or more and 2 cc or less, and more preferably 0.1 cc or more and 1.2 cc or less per 4 pieces. Particularly preferably, it is 0.1 cc or more and 0.8 cc or less.
【0154】水洗槽から乾燥ゾーンに入る際の水洗水の
持ち出し量は、感材4切り1枚当たり0.1cc以上2cc
以下が好ましく、より好ましくは1cc以下であり、さら
に好ましくは0.5cc以下である。The amount of washing water taken out of the washing tank when entering the drying zone should be 0.1 cc or more and 2 cc per 4 pieces of photosensitive material.
Is preferably 1 cc or less, more preferably 0.5 cc or less.
【0155】本発明の感材は迅速処理に適するものであ
り、現像槽に搬入されて乾燥工程を終了するまでの全処
理時間(Dry to Dry)は90秒以下、さらに好ましくは5
〜60秒であることが好ましい。The light-sensitive material of the present invention is suitable for rapid processing, and the total processing time (Dry to Dry) until it is carried into a developing tank and the drying step is completed is 90 seconds or less, and more preferably 5 seconds or less.
It is preferably from 60 seconds to 60 seconds.
【0156】この場合の現像は25〜40℃で5〜30
秒、定着は25〜40℃で5〜40秒、水洗は0〜40
℃で5〜30秒、乾燥は40〜120℃で1〜30秒行
うことが好ましい。また補充量は、各々感材1m2当たり
現像液は30〜650ml、定着液は30〜650ml、水
洗水は30〜50,000mlであることが好ましい。In this case, the development is carried out at 25 to 40 ° C. for 5 to 30 minutes.
Seconds, fixation at 25-40 ° C for 5-40 seconds, washing with water 0-40
Preferably, the drying is performed at a temperature of 40 to 120C for 1 to 30 seconds. The replenishing amounts are preferably 30 to 650 ml for the developing solution, 30 to 650 ml for the fixing solution, and 30 to 50,000 ml for the washing water per 1 m 2 of the light-sensitive material.
【0157】このような処理の詳細については、前出の
特願平8−168670号等の記載を参照することがで
きる。For details of such processing, reference can be made to the description of the above-mentioned Japanese Patent Application No. 8-168670.
【0158】[0158]
【実施例】以下に実施例を示し、本発明を説明する。 実施例1 乳剤A:高アスペクト比(111)AgBr平板状粒子
の調製 水1リットル中に臭化カリウム6.0g、平均粒子量1
万5千の低分子量ゼラチン7.0gを添加し55℃に保
った容器中へ攪拌しながら硝酸銀水溶液37ml(硝酸銀
4.00g)と臭化カリウム5.9gを含む水溶液38
mlをダブルジェット法により37秒間で添加した。次に
ゼラチン18.6gを添加した後70℃に昇温して硝酸
銀水溶液89ml(硝酸銀9.80g)を22分間かけて
添加した。ここで25%のアンモニア水溶液7mlを添加
し、そのままの温度で10分間物理熟成した後100%
酢酸溶液を6.5ml添加した。引き続いて硝酸銀153
gの水溶液と臭化カリウムの水溶液をpAg8.5に保
ちながらコントロールダブルジェット法で35分かけて
添加した。次に2Nのチオシアン酸カリウム溶液15ml
を添加した。5分間そのままの温度で物理熟成したのち
35℃に温度を下げた。The present invention will be described below with reference to examples. Example 1 Emulsion A: Preparation of high aspect ratio (111) AgBr tabular grains 6.0 g of potassium bromide in 1 liter of water, average grain size 1
An aqueous solution containing 37 ml of an aqueous silver nitrate solution (4.00 g of silver nitrate) and 5.9 g of potassium bromide while stirring into a vessel kept at 55 ° C., adding 7.0 g of 15,000 low molecular weight gelatin.
ml was added by the double jet method in 37 seconds. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C., and 89 ml of an aqueous silver nitrate solution (9.80 g of silver nitrate) was added over 22 minutes. Here, 7 ml of 25% ammonia aqueous solution was added, and the mixture was physically aged at the same temperature for 10 minutes, and then 100%
6.5 ml of acetic acid solution was added. Followed by silver nitrate 153
g and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 15 ml of 2N potassium thiocyanate solution
Was added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C.
【0159】この粒子のレプリカの透過型電子顕微鏡写
真像(以下TEMと記す)を観察した。この粒子の形状
特性値は下記のようであった。 (アスペクト比5以上の平板状粒子の全投影面積/全A
gX粒子の投影面積和)×100=a1 =95% (平板状粒子の平均アスペクト比(平均直径/平均厚
さ))=a2 =10.0 (平板状粒子の平均直径)=a3 =1.50μm (平均厚さ)=a4 =0.15μm 直径変動係数18.5%の単分散純臭化銀平板状粒子を
得た。A transmission electron micrograph (hereinafter referred to as TEM) of a replica of the particles was observed. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio of 5 or more / total A)
gX grain projected area sum) × 100 = a 1 = 95% (average aspect ratio of tabular grains (average diameter / average thickness)) = a 2 = 10.0 (average diameter of tabular grains) = a 3 = 1.50 μm (average thickness) = a 4 = 0.15 μm Monodispersed pure silver bromide tabular grains having a diameter variation coefficient of 18.5% were obtained.
【0160】この後、沈降法により可溶性塩類を除去し
た。再び40℃に昇温してゼラチン30gとフェノキシ
エタノール2.35gおよび増粘剤としてポリスチレン
スルホン酸ナトリウム0.8gを添加し、苛性ソーダと
硝酸銀溶液でpH5.90、pAg8.00に調整し
た。Thereafter, the soluble salts were removed by the sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrenesulfonate as a thickener were added, and the mixture was adjusted to pH 5.90 and pAg 8.00 with sodium hydroxide and silver nitrate solution.
【0161】乳剤B:沃化銀含有率の高い高アスペクト
比(111)平板状粒子の調製 乳剤Aの調製時において、アンモニアを用いた物理熟成
後の成長の過程において、臭化カリウム水溶液中に沃化
カリウムを全銀量の1.5%相当添加することで、沃化
銀含有率1.5モル%で、ほぼ乳剤Aと同じ形状特性値
を有する乳剤Bを調製した。Emulsion B: Preparation of High Aspect Ratio (111) Tabular Grains with High Silver Iodide Content During the preparation of Emulsion A, during the growth process after physical ripening using ammonia, the emulsion was placed in an aqueous potassium bromide solution. Emulsion B having a silver iodide content of 1.5 mol% and substantially the same shape characteristic values as Emulsion A was prepared by adding potassium iodide equivalent to 1.5% of the total silver amount.
【0162】乳剤C:低アスペクト比(111)AgB
r平板状粒子の調製 水1リットル中に臭化カリウム6.0g、平均分子量1
万5千の低分子量ゼラチン7.0gを添加し55℃に保
った容器中へ攪拌しながら硝酸銀水溶液37ml(硝酸銀
4.00g)と臭化カリウム5.9gを含む水溶液38
mlをダブルジェット法により37秒間で添加した。次に
ゼラチン18.6gを添加した後70℃に昇温して硝酸
銀水溶液89ml(硝酸銀9.80g)を22分間かけて
添加した。ここで25%のアンモニア水溶液15mlを添
加し、そのままの温度で15分間物理熟成した後100
%酢酸溶液を14ml添加した。引き続いて硝酸銀153
gの水溶液と臭化カリウムの水溶液をpAg8.1に保
ちながらコントロールダブルジェット法で55分かけて
添加した。次に2Nのチオシアン酸カリウム溶液15ml
を添加した。5分間そのままの温度で物理熟成したのち
35℃に温度を下げた。a1 =15%、平均投影面積直
径a3 =1.30μm 、厚みa4 =0.29μm 、平均
アスペクト比a2 =4.5、直径変動係数17.0%の
単分散純臭化銀平板状粒子を得た。Emulsion C: low aspect ratio (111) AgB
r Preparation of tabular grains 6.0 g of potassium bromide in 1 liter of water, average molecular weight 1
An aqueous solution containing 37 ml of an aqueous silver nitrate solution (4.00 g of silver nitrate) and 5.9 g of potassium bromide while stirring into a vessel kept at 55 ° C., adding 7.0 g of 15,000 low molecular weight gelatin.
ml was added by the double jet method in 37 seconds. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C., and 89 ml of an aqueous silver nitrate solution (9.80 g of silver nitrate) was added over 22 minutes. Here, 15 ml of a 25% aqueous ammonia solution was added, and the mixture was physically aged for 15 minutes at the same temperature, and then 100 ml.
14 ml of a 10% acetic acid solution were added. Followed by silver nitrate 153
g of an aqueous solution of potassium bromide and an aqueous solution of potassium bromide were added by a control double jet method over 55 minutes while maintaining the pAg at 8.1. Next, 15 ml of 2N potassium thiocyanate solution
Was added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. a 1 = 15%, average projected area diameter a 3 = 1.30μm, thickness a 4 = 0.29μm, an average aspect ratio a 2 = 4.5, the diameter variation coefficient 17.0 percent of monodispersed pure silver bromide tabular Particles were obtained.
【0163】この後、沈降法により可溶性塩類を除去し
た。再び40℃に昇温してゼラチン30gとフェノキシ
エタノール2.35gおよび増粘剤としてポリスチレン
スルホン酸ナトリウム0.8gを添加し、苛性ソーダと
硝酸銀溶液でpH5.90、pAg8.00に調整し
た。Thereafter, the soluble salts were removed by the sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrenesulfonate as a thickener were added, and the mixture was adjusted to pH 5.90 and pAg 8.00 with sodium hydroxide and silver nitrate solution.
【0164】(化学増感)以上のように調製した乳剤A
を攪拌しながら57℃に保った状態で化学増感を施し
た。まず、下記のチオスルホン酸化合物−Iをハロゲン
化銀1モル当たり10-4モル添加し、次に直径0.03
μm のAgI微粒子を全銀量に対して0.15モル%添
加した。3分後に二酸化チオ尿素を1×10-6モル/モ
ルAg添加し、22分間そのまま保持して還元増感を施
した。次に4−ヒドロキシ−6−メチル−1,3,3
a,7−テトラアザインデンをハロゲン化銀1モル当た
り3×10-4モル相当を添加し、増感色素−1の分散物
を増感色素−1の量としてハロゲン化銀1モル当たり
1.0×10-3モル相当と、増感色素−2の分散物を増
感色素−2の量としてハロゲン化銀1モル当たり1.2
×10-5モル相当、増感色素−3の分散物を増感色素−
3の量としてハロゲン化銀1モル当たり2.4×10-4
モル相当を同時に添加し、さらに塩化カルシウムを添加
した。(Chemical sensitization) Emulsion A prepared as described above
Was subjected to chemical sensitization while maintaining the temperature at 57 ° C. while stirring. First, 10 -4 mol of the following thiosulfonic acid compound-I was added per mol of silver halide, and
0.1 μmol% of AgI fine particles was added to the total silver amount. Three minutes later, 1 × 10 −6 mol / mol Ag of thiourea dioxide was added, and the mixture was kept for 22 minutes to perform reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetraazaindene was added in an amount of 3 × 10 -4 mol per mol of silver halide, and the dispersion of sensitizing dye-1 was used as sensitizing dye-1 in an amount of 1.times.1 mol per mol of silver halide. 0 × 10 -3 mole equivalent, and the dispersion of sensitizing dye-2 was used as sensitizing dye-2 in an amount of 1.2 per mole of silver halide.
× 10 −5 mole equivalent, dispersion of sensitizing dye-3 was converted to sensitizing dye−
As an amount of 3, 2.4 × 10 -4 per mol of silver halide
A molar equivalent was added at the same time, and further calcium chloride was added.
【0165】引き続きチオ硫酸ナトリウムをハロゲン化
銀1モル当たり6×10-6モル相当とセレン化合物−1
をハロゲン化銀1モル当たり4×10-6モル相当加えた
後、塩化金酸をハロゲン化銀1モル当たり1×10-5モ
ル相当およびチオシアン酸カリウムをハロゲン化銀1モ
ル当たり2×10-3モル相当添加した。さらに核酸(山
陽国策パルプ社製:商品名RNA−F)をハロゲン化銀
1モル当たり67mg相当添加した。40分後に水溶性メ
ルカプト化合物−1をハロゲン化銀1モル当たり1×1
0-4モル相当添加し35℃に冷却した。こうして乳剤の
化学増感を終了した。乳剤B、Cも同様にして最適に化
学増感を行った。Subsequently, sodium thiosulfate was added to the selenium compound-1 in an amount of 6 × 10 -6 mol per mol of silver halide.
After the addition corresponding 4 × 10 -6 mol per mol of silver halide, of chloroauric acid per mol of silver halide 1 × 10 -5 mol equivalent and potassium thiocyanate per mol of silver halide per 2 × 10 - 3 moles were added. Further, nucleic acid (manufactured by Sanyo Kokusaku Pulp Co., Ltd., trade name: RNA-F) was added in an amount of 67 mg per mol of silver halide. After 40 minutes, 1 × 1 of water-soluble mercapto compound-1 was added per mole of silver halide.
It was added in an amount corresponding to 0-4 mol and cooled to 35 ° C. Thus, the chemical sensitization of the emulsion was completed. Emulsions B and C were similarly optimally subjected to chemical sensitization.
【0166】[0166]
【化9】 Embedded image
【0167】《増感色素−1,2,3の分散物の調製》
水50mlに対し、各増感色素1gをpH7.0±0.
5、50〜65℃で、ディゾルバーを用いて2000〜
2500rpmにて機械的に1μm 以下の固体微粒子に
分散し、10%ゼラチン50gを加え、混合後冷却し
た。<< Preparation of Dispersion of Sensitizing Dye-1, 2, 3 >>
1 g of each sensitizing dye was added to 50 ml of water at pH 7.0 ± 0.
5, at 2000 to 2000 using a dissolver at 50 to 65 ° C.
The mixture was mechanically dispersed at 2,500 rpm into solid fine particles of 1 μm or less, 50 g of 10% gelatin was added, and the mixture was cooled after cooling.
【0168】《顔料分散物A,B,Cの調製》チバガイ
ギー社製のマイクロリスブルーA3R-K(C.I.Pigment Blue
60)、マイクロリスブルー4G-K(C.I.Pigment Blue 15:
3)、マイクロリスバイオレットB-K(C.I.Pigment Violet
37)の分散物を順にA,B,Cとして、それぞれ以下の
ように調製した。各顔料1.8g、酢酸エチル48.8
g、下記高沸点有機溶媒−I1.8g、ドデシルベンゼ
ンスルホン酸ナトリウムの72%水溶液1.44gを5
0℃で超音波分散した。ついで、ゼラチン7.2g、プ
ロキセルの3.5%水溶液0.72gと水104.4c
cを添加し、ホモジナイザーにて50℃、12000r
pmで8分間乳化分散した。次に、ロータリーエバポレ
ーターにて酢酸エチルを脱溶媒した後、全量が180g
になるように水を加えて降温し、顔料の分散物を得た。<< Preparation of Pigment Dispersions A, B, C >> Microlith Blue A3R-K (CIPigment Blue) manufactured by Ciba-Geigy
60), Microlith Blue 4G-K (CIPigment Blue 15:
3), Microlith Violet BK (CIPigment Violet
The dispersion of 37) was sequentially prepared as A, B, and C as follows. 1.8 g of each pigment, 48.8 ethyl acetate
g, the following high-boiling organic solvent-I 1.8 g, and a 72% aqueous solution of sodium dodecylbenzenesulfonate 1.44 g in 5 parts
Ultrasonic dispersion was performed at 0 ° C. Then, 7.2 g of gelatin, 0.72 g of a 3.5% aqueous solution of proxel and 104.4 c of water were used.
c at 50 ° C. and 12000 r with a homogenizer.
The mixture was emulsified and dispersed at pm for 8 minutes. Next, after removing the ethyl acetate by a rotary evaporator, the total amount was 180 g.
Was added to the mixture and the temperature was lowered to obtain a pigment dispersion.
【0169】[0169]
【化10】 Embedded image
【0170】《顔料分散物D,E,Fの調製》C.I.Pigm
ent Blue 60、C.I.Pigment Blue 15、C.I.Pigment Viol
et 23をそれぞれ20wt%、分散剤として花王アトラ
ス社製デモールNを10wt%を含む溶液をサンドミル
にて分散し、平均粒子径0.15μm の顔料の水分散物
を得、それぞれ顔料分散物D,E,Fとした。<< Preparation of Pigment Dispersions D, E, and F >>
ent Blue 60, CI Pigment Blue 15, CI Pigment Viol
A solution containing 20 wt% of each of et 23 and 10 wt% of Demol N manufactured by Kao Atlas Co. as a dispersant was dispersed in a sand mill to obtain an aqueous dispersion of a pigment having an average particle diameter of 0.15 μm. E and F.
【0171】(染料乳化物aの調製)下記の染料−I6
0g、2,4−ジアミノフェノール62.8g、ジシク
ロヘキシルフタレート62.8gおよび酢酸エチル33
3gを60℃で溶解した。つぎにドデシルベンゼンスル
ホン酸ナトリウムの5%水溶液65mlとゼラチン94
g、水581mlを添加し、ディゾルバーにて60℃、
30分間乳化分散した。つぎにp−ヒドロキシ安息香酸
メチル2gおよび水6リットルを加え、40℃に降温し
た。つぎに旭化成製限外濾過ラボモジュールACP10
50を用いて、全量が2kgとなるまで濃縮し、p−ヒド
ロキシ安息香酸メチルを1g加えて染料乳化物aとし
た。(Preparation of Dye Emulsion a) The following Dye-I6
0 g, 2,2.8 g of 2,4-diaminophenol, 62.8 g of dicyclohexyl phthalate and 33 of ethyl acetate
3 g were melted at 60 ° C. Next, 65 ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate and gelatin 94
g and water (581 ml) were added, and the mixture was dissolved at 60 ° C. with a dissolver.
The mixture was emulsified and dispersed for 30 minutes. Next, 2 g of methyl p-hydroxybenzoate and 6 l of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei ultrafiltration lab module ACP10
Using 50, the mixture was concentrated until the total amount became 2 kg, and 1 g of methyl p-hydroxybenzoate was added to obtain a dye emulsion a.
【0172】[0172]
【化11】 Embedded image
【0173】《乳剤塗布液の調製》化学増感を施した乳
剤に対してハロゲン化銀1モル当たり下記の薬品を添加
して乳剤塗布液とした。 ・ゼラチン(乳剤中のゼラチンも含めて) 80.6g ・デキストラン(平均分子量3.9万) 21.5g ・ポリアクリル酸ナトリウム(平均分子量40万) 5.1g ・ポリスチレンスルホン酸ナトリウム(平均分子量60万) 1.2g ・沃化カリウム 78mg ・硬膜剤 1,2−ビス(ビニルスルホニルアセトアミド)エタン(膨潤率が1 40%の値となるように添加量を調整)<< Preparation of Emulsion Coating Solution >> The following chemicals were added per mole of silver halide to the chemically sensitized emulsion to prepare an emulsion coating solution. 80.6 g of gelatin (including gelatin in the emulsion) 21.5 g of dextran (average molecular weight 39,000) 5.1 g of sodium polyacrylate (average molecular weight 400,000) 5.1 g of sodium polystyrene sulfonate (average molecular weight 60) 10,000 g 1.2 g Potassium iodide 78 mg Hardener 1,2-bis (vinylsulfonylacetamide) ethane (addition amount is adjusted so that the swelling ratio becomes a value of 140%)
【0174】さらに下記の化合物−I〜VIIを下記の量
で添加した。 化合物−I 70mg 化合物−II 5.0g 化合物−III 0.58g 化合物−IV 30mg 化合物−V 6.0mg 化合物−VI 0.1g 化合物−VII 0.1gFurther, the following compounds-I to VII were added in the following amounts. Compound-I 70 mg Compound-II 5.0 g Compound-III 0.58 g Compound-IV 30 mg Compound-V 6.0 mg Compound-VI 0.1 g Compound-VII 0.1 g
【0175】[0175]
【化12】 Embedded image
【0176】活性メチレン基を有する下記ポリマーラテ
ックスを塗布量0.8g/m2になるように、添加量を
調整。 コア:スチレン/ブタジエン共重合体(37/63) シェル:スチレン/2−アセトアセトキシエチルメタク
リレート(84/16) コア/シェル=50/50(数値はいずれも重量百分
率) (NaOHでpH6.1に調整)The addition amount of the following polymer latex having an active methylene group was adjusted so that the coating amount was 0.8 g / m 2 . Core: Styrene / butadiene copolymer (37/63) Shell: Styrene / 2-acetoacetoxyethyl methacrylate (84/16) Core / shell = 50/50 (all numerical values are weight percentages) (to pH 6.1 with NaOH) Adjustment)
【0177】《染料層塗布液の調製》乳剤下層として塗
設する染料層の各成分が、下記の塗布量となるように塗
布液を調製した。 ・ゼラチン 0.25g/m2 ・添加剤D(下記) 1.4mg/m2 ・ポリスチレンスルホン酸ナトリウム(平均分子量60万) 5.9mg/m2 ・染料分散物i(染料固形分として) 20mg/m2 染料分散物iは以下のようにして調製した。<< Preparation of Dye Layer Coating Solution >> A coating solution was prepared so that each component of the dye layer to be coated as the lower layer of the emulsion had the following coating amount.・ Gelatin 0.25 g / m 2・ Additive D (described below) 1.4 mg / m 2・ Sodium polystyrene sulfonate (average molecular weight: 600,000) 5.9 mg / m 2・ Dye dispersion i (as dye solid content) 20 mg / M 2 dye dispersion i was prepared as follows.
【0178】《染料分散物iの調製》下記の染料−IIを
乾燥させないでウェットケーキとして取り扱い、乾燥固
形分で6.3gになるように秤量した。下記の分散助剤
Vは、25wt%の水溶液として扱い、乾燥固形分で染
料固形分に対し30wt%になるように添加した。水を
加えて全量を63.3gとし、よく混合してスラリーと
した。平均直径0.5mmのジルコニア製ビーズを100
ml用意し、スラリーと一緒にベッセルに入れ、分散機
(1/16Gサンドグラインダーミル:アイメックス
(株)製)で6時間分散し、染料濃度が8wt%となる
よう水を加えて染料分散液を得た。<< Preparation of Dye Dispersion i >> The following Dye-II was treated as a wet cake without drying, and weighed to a dry solid content of 6.3 g. The following Dispersing Aid V was treated as a 25 wt% aqueous solution, and was added so that the dry solid content was 30 wt% with respect to the dye solid content. Water was added to make a total amount of 63.3 g, and mixed well to form a slurry. 100 zirconia beads with an average diameter of 0.5 mm
ml, put it in a vessel together with the slurry, disperse it for 6 hours with a disperser (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.), add water so that the dye concentration becomes 8 wt%, and prepare the dye dispersion. Obtained.
【0179】得られた分散剤は、染料固形分が5wt
%、写真用ゼラチンが染料固形分と等重量%となるよう
に混合し、防腐剤として下記の添加剤Dがゼラチンに対
して2000ppm となるように水溶液を添加して冷蔵
し、ゼリー状にて保存した。The resulting dispersant had a dye solid content of 5 wt.
% And photographic gelatin are mixed so as to be equal to the dye solid content by weight, and an aqueous solution is added as an antiseptic so that the following additive D is 2,000 ppm relative to the gelatin, refrigerated, and refrigerated. saved.
【0180】このようにして915nmに光吸収極大をも
つ非溶出性の固体微粒子分散状の染料として染料分散物
iを得た。染料分散物iの固体微粒子の平均粒子径は
0.4μm であった。Thus, a dye dispersion i was obtained as a non-elutable solid fine particle dispersed dye having a light absorption maximum at 915 nm. The average particle diameter of the solid fine particles of the dye dispersion i was 0.4 μm.
【0181】[0181]
【化13】 Embedded image
【0182】[0182]
【化14】 Embedded image
【0183】《表面保護層塗布液の調製》表面保護層の
各成分が、支持体の片側当たり下記の塗布量となるよう
に表面保護層の塗布液を調製した。 ・ゼラチン 0.33g/m2 ・添加剤D 1.4mg/m2 ・ポリアクリル酸ナトリウム(平均分子量4.1万) 34mg/m2 ・添加剤−1 40mg/m2 ・添加剤−2 5.4mg/m2 ・添加剤−3 22.5mg/m2 ・添加剤−4 0.5mg/m2 ・マット剤−1(平均粒子径3.7μm ) 72.5mg/m2 ・化合物−IX 4.4mg/m2 ・化合物−X 1.3mg/m2 上記において用いた添加剤等は下記に示すとおりであ
る。<< Preparation of Coating Solution for Surface Protective Layer >> A coating solution for the surface protective layer was prepared such that each component of the surface protective layer was applied in the following amount per one side of the support.・ Gelatin 0.33 g / m 2・ Additive D 1.4 mg / m 2・ Sodium polyacrylate (average molecular weight 41,000) 34 mg / m 2・ Additive-1 40 mg / m 2・ Additive-25 .4mg / m 2 · additives -3 22.5mg / m 2 · additives -4 0.5mg / m 2 · matting agent-1 (average particle size 3.7μm) 72.5mg / m 2 · compound -IX 4.4 mg / m 2 · Compound-X 1.3 mg / m 2 Additives and the like used in the above are as follows.
【0184】[0184]
【化15】 Embedded image
【0185】[0185]
【化16】 Embedded image
【0186】《中間層塗布液の調製》中間層の各成分
が、支持体の片側当たり下記の塗布量となるように中間
層の塗布液を調製した。 ・ゼラチン 0.33mg/m2 ・ポリスチレンスルホン酸カリウム 20mg/m2 << Preparation of Coating Solution for Intermediate Layer >> A coating solution for the intermediate layer was prepared such that each component of the intermediate layer had the following coating amount per one side of the support.・ Gelatin 0.33mg / m 2・ Potassium polystyrene sulfonate 20mg / m 2
【0187】《支持体−1,2の作製》二軸延伸された
厚さ175μm のポリエチレンテレフタレートフィルム
上にコロナ放電処理を行い、疎水性ポリマー層が下記の
塗布量になるようにワイヤーバーコーターにより両面塗
布し、185℃にて1分間乾燥した。使用したポリエチ
レンテレフタレートフィルムは、無着色のものと前記染
料−Iで青色着色したものであり、無着色のものを支持
体−1、前記染料−Iで青色着色したものを支持体−2
とした。それぞれの透過白色光濃度は0.03、0.14であっ
た。<< Preparation of Supports-1 and 2 >> A corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the hydrophobic polymer layer was coated with a wire bar coater so as to have the following coating amount. It was coated on both sides and dried at 185 ° C. for 1 minute. The polyethylene terephthalate film used was an uncolored film and a blue-colored film with the dye-I. The uncolored film was a support-1 and a blue-colored film with the dye-I was a support-2.
And The respective transmitted white light densities were 0.03 and 0.14.
【0188】 《疎水性ポリマー層》 ・ブタジエン−スチレン共重合体ラテックス ブタジエン/スチレン重量比=31/69 0.32g/m2 ・2,4−ジクロロ−6−ヒドロキシ−s−トリアジンナトリウム塩 8.4mg/m2 *ラテックス溶液中には、下記の乳化分散剤−Aをラテックス固形分に対し0. 4wt% 含有。[0188] "hydrophobic polymer layer" Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio = 31/69 0.32g / m 2 · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 8. In the 4 mg / m 2 * latex solution, the following emulsifying dispersant-A was added in an amount of 0. Contains 4wt%.
【0189】[0189]
【化17】 Embedded image
【0190】《親水性コロイド層》次に、親水性コロイ
ド層が下記の塗布量になるようにワイヤーバーコーター
により両面塗布し、155℃にて1分間乾燥した。 ・ゼラチン 80mg/m2 ・ポリエチルアクリレート 20mg/m2 ・塗布助剤−B(下記) 1.8mg/m2 ・染料−III (下記) 40mg/m2 ・添加剤D(下記) 0.27mg/m2 << Hydrophilic Colloid Layer >> Next, the hydrophilic colloid layer was coated on both sides with a wire bar coater so as to have the following coating amount, and dried at 155 ° C. for 1 minute.・ Gelatin 80 mg / m 2・ Polyethyl acrylate 20 mg / m 2・ Coating aid-B (described below) 1.8 mg / m 2・ Dye-III (described below) 40 mg / m 2・ Additive D (described below) 0.27 mg / M 2
【0191】《染料−III の調製方法》下記の染料−II
I 20gとカルボキシメチルセルロース1%水溶液20
0g、H2 O 287gを混合し、直径2mmの酸化ジル
コニウム(ZrO2 )のビーズを用いたアイガーミル
(アイガー・ジャパン(株))にて5,000rpm の条
件で8時間処理した。得られた混合物を濾過してZrO
2 ビーズを除去した。これをゼラチン水溶液中に分散し
て染料−III の固体微粒子状の染料分散物を得た。染料
濃度は12wt%であり、染料の固体微粒子の平均粒子
径は0.37μm であった。上記において用いた化合物
は以下に示すものである。<< Method for Preparing Dye-III >> The following Dye-II
I 20 g and carboxymethyl cellulose 1% aqueous solution 20
0 g and 287 g of H 2 O were mixed and treated at 5,000 rpm for 8 hours in an Eiger mill (Eiger Japan KK) using zirconium oxide (ZrO 2 ) beads having a diameter of 2 mm. The resulting mixture is filtered and ZrO
Two beads were removed. This was dispersed in an aqueous gelatin solution to obtain a dye dispersion in the form of solid fine particles of Dye-III. The dye concentration was 12% by weight, and the average particle size of the solid fine particles of the dye was 0.37 μm. The compounds used in the above are shown below.
【0192】[0192]
【化18】 Embedded image
【0193】《感光材料の調製》前述のように準備した
支持体上に、先の染料層、乳剤層、中間層および表面保
護層を組み合わせ、同時押し出し法により両面に塗布し
た。片面当たりの塗布銀量は1.3g/m2とした。このと
き、表1に示すように顔料の分散物A〜F、染料乳化物
aをそれぞれ添加位置と添加量を変化させて塗布試料を
得た。<< Preparation of Photosensitive Material >> On the support prepared as described above, the dye layer, emulsion layer, intermediate layer and surface protective layer were combined and coated on both sides by a simultaneous extrusion method. The amount of silver applied per side was 1.3 g / m 2 . At this time, as shown in Table 1, coating samples were obtained by changing the addition positions and amounts of the pigment dispersions A to F and the dye emulsion a, respectively.
【0194】(写真性能の評価)写真材料を富士フイル
ム(株)社製のXレイオルソスクリーンHGMを使用し
て、両側に密着させ、両側から0.05秒の露光を与
え、X線センシトメトリーを行った。(Evaluation of photographic performance) The photographic material was brought into close contact with both sides using an X-ray orthoscreen HGM manufactured by FUJIFILM Corporation, exposed for 0.05 seconds from both sides, and subjected to X-ray sensitizing. The metrology was performed.
【0195】露光量の調整は、X線管球とカセッテとの
距離を変化させることにより行った。露光後、下記現像
液と定着液にて自動現像機処理を行った。The adjustment of the exposure amount was performed by changing the distance between the X-ray tube and the cassette. After the exposure, the film was subjected to automatic developing machine processing using the following developing solution and fixing solution.
【0196】(処理)自動現像機・・・富士フイルム
(株)社製CEPROS−30 濃縮液の調製(Processing) Automatic developing machine: Preparation of a concentrate of CEPROS-30 manufactured by FUJIFILM Corporation
【0197】 <現像液> パーツ剤A 水酸化カリウム 330 g 亜硫酸カリウム 630 g 亜硫酸ナトリウム 255 g 炭酸カリウム 90 g ホウ酸 45 g ジエチレングリコール 180 g ジエチレントリアミン五酢酸 30 g 1−(N,N−ジエチルアミン)エチル−5−メルカプト テトラゾール 0.75g ハイドロキノン 450 g 4−ヒドロキシメチル−4−メチル−1−フェニル−3− ピラゾリドン 60 g 水を加えて 4125 ml パーツ剤B ジエチレングリコール 525 g 3,3′ジチオビスヒドロ桂皮酸 3 g 氷酢酸 102.6g 2−ニトロインダゾール 3.75g 1−フェニル−3−ピラゾリドン 34.5 g 水を加えて 750 ml パーツ剤C グルタールアルデヒド(50wt/wt%) 150 g 臭化カリウム 15 g メタ重亜硫酸カリウム 105 g 水を加えて 750 ml<Developer> Parts agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine) ethyl- 5-mercaptotetrazole 0.75 g Hydroquinone 450 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Water 4125 ml Parts B Diethylene glycol 525 g 3,3'dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 2-Nitroindazole 3.75 g 1-phenyl-3-pyrazolidone 34.5 g Add water 750 ml Parts C glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g 750 ml with water
【0198】 <定着液> チオ硫酸アンモニウム(70wt/vol %) 3000 ml エチレンジアミン四酢酸・二ナトリウム・二水塩 0.45 g 亜硫酸ナトリウム 225 g ホウ酸 60 g 1−(N,N−ジエチルアミン)−エチル−5−メルカプ トテトラゾール 15 g 酒石酸 48 g 氷酢酸 675 g 水酸化ナトリウム 225 g 硫酸(36N) 58.5 g 硫酸アルミニウム 150 g 水を加えて 6000 ml pH 4.68<Fixing Solution> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid disodium dihydrate 0.45 g sodium sulfite 225 g boric acid 60 g 1- (N, N-diethylamine) -ethyl-5 -Mercaptotetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Add water 6000 ml pH 4.68
【0199】(処理液の調製)上記現像液濃縮液を下記
の容器に各パーツ剤毎に充填した。この容器はパーツ剤
A、B、Cの各部分容器が容器自身によって一つに連結
されているものである。また、上記定着液濃縮液も同種
の容器に充填した。(Preparation of Processing Solution) The above-mentioned concentrated solution of the developing solution was filled in the following containers for each part. In this container, the respective partial containers of the parts agents A, B, and C are connected together by the container itself. The above-mentioned fixer concentrate was also filled in the same type of container.
【0200】まず、現像槽内にスターターとして、酢酸
54gと臭化カリウム55.5gを含む水溶液300ml
を添加した。First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was placed in a developing tank as a starter.
Was added.
【0201】上記処理剤入容器を逆さにして自現機の側
面に装着されている処理液ストックタンクの穿孔刃にさ
しこんで、キャップの封止膜を破り、容器内の各処理剤
をストックタンクに充填した。The treatment agent container is turned upside down and inserted into the perforation blade of the treatment liquid stock tank mounted on the side surface of the automatic processing machine to break the sealing film of the cap and to remove each treatment agent in the container. Filled the stock tank.
【0202】これらの各処理剤を下記の割合で自現機の
現像槽、定着槽に、それぞれ自現機に設置されているポ
ンプを作動して満たした。Each of these processing agents was filled in the developing tank and the fixing tank of the automatic processing machine at the following ratios by operating pumps provided in the automatic processing machine.
【0203】また、感材が4切サイズ換算で8枚処理さ
れる毎にも、この割合で、処理剤原液と水とを混合して
自現機の処理槽に補充した。In addition, every time the photosensitive material was processed into 8 pieces in terms of a 4-cut size, the stock solution of the processing agent and water were mixed at this ratio and replenished into the processing tank of the automatic processing machine.
【0204】現像液 パーツ剤A 51 ml パーツ剤B 10 ml パーツ剤C 10 ml 水 125 ml pH 10.50 定着液 濃縮液 80 ml 水 120 ml pH 4.62 水洗槽には水道水を満たした。Developing solution Parts A 51 ml Parts B 10 ml Parts C 10 ml Water 125 ml pH 10.50 Fixer Concentrate 80 ml water 120 ml pH 4.62 The washing tank was filled with tap water.
【0205】また、水あか防止剤として、放線菌を平均
粒径100μm、平均孔径3μmのパーライトに担持さ
せたもの0.4gをポリエチレン製のビン(ビン開口部
を300メッシュのナイロン布で覆い、この布より水お
よび菌の流通が可能)に充填したものを3個用意し、そ
のうちの2個を水洗槽の底部に、1個を水洗水のストッ
クタンク(液量0.2リットル)の底部にそれぞれ沈め
た。Further, as a scale inhibitor, 0.4 g of actinobacteria supported on perlite having an average particle diameter of 100 μm and an average pore diameter of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. 3 pieces of water and bacteria can be distributed from the cloth), two of them are placed at the bottom of the washing tank and one is placed at the bottom of the washing tank (0.2 liter). Each sunk.
【0206】 [0206]
【0207】(未露光部白色光透過濃度寄与の評価)未
露光の試料を前述の定着、水洗のみ行った後、さらに、
現像、定着、水洗を行い、乾燥させた。白色光透過濃度
をマクベス濃度計TD-904のビジュアルフィルターを用い
て測定した。また、支持体の白色光透過濃度も同様に測
定し、前記試料と支持体の白色光透過濃度との差を顔料
および/または染料の白色光透過濃度とし、この濃度が
現像処理後の未露光部白色光透過濃度のうちに占める割
合を濃度寄与として計算した。結果を表1に示す。(Evaluation of Unexposed Area White Light Transmission Density Contribution) The unexposed sample was subjected to only the above-mentioned fixing and washing, and further,
The film was developed, fixed, washed with water and dried. The white light transmission density was measured using a visual filter of Macbeth densitometer TD-904. The white light transmission density of the support was also measured in the same manner, and the difference between the white light transmission density of the sample and the support was defined as the white light transmission density of the pigment and / or dye. The percentage of the white light transmission density was calculated as the density contribution. Table 1 shows the results.
【0208】(感度の評価)感度はカブリ+0.3の濃
度を得るのに必要な露光量の逆数の常用対数として求
め、試料No.16を1.0として相対値表示した。結果
を表2に示す。(Evaluation of Sensitivity) The sensitivity was determined as a common logarithm of the reciprocal of the exposure amount required to obtain a density of fog + 0.3, and the relative value was indicated by setting Sample No. 16 to 1.0. Table 2 shows the results.
【0209】(現像銀の銀色調の評価)現像処理を行っ
た試料を反射光における現像銀の銀色調を観察し、官能
評価で5〜1の評点をつけた。評点は1〜5の順で好ま
しい色調を与える。結果を表2に示す。(Evaluation of Silver Tone of Developed Silver) The silver tone of the developed silver in the reflected light was observed on the sample subjected to the development treatment, and a sensory evaluation gave a score of 5-1. Scores are given in the order of 1 to 5 to give favorable color tones. Table 2 shows the results.
【0210】(増感紙汚れ試験) <スクリーンクリーナーテスト>富士フイルム(株)社
製のXレイオルソスクリーンHGMに富士フイルム
(株)社製のスクリーンクリーナーを適量塗りつけ、現
像処理前の試料に密着させて、40℃で3日間10Kg
の荷重をかけた。その後、スクリーン表面をスクリーン
クリーナーで湿らした脱脂綿でふきとり、その汚れ具合
を目視により評価した。結果を表2に示す。増感紙に対
するスクリーン汚染性の評価は以下の通りである。(Screen dirt test) Screen cleaner test A suitable amount of a screen cleaner manufactured by FUJIFILM Corporation was applied to an X-ray orthoscreen HGM manufactured by FUJIFILM Corporation, and adhered to the sample before development processing. Let 10kg at 40 ° C for 3 days
Was applied. Thereafter, the screen surface was wiped with absorbent cotton moistened with a screen cleaner, and the degree of dirt was visually evaluated. Table 2 shows the results. The evaluation of the screen staining property for the intensifying screen is as follows.
【0211】汚染性評価 ◎:付着なし。 ○:ほぼ付着なし。 ×:付着あり。Evaluation of contamination ◎: No adhesion. :: Almost no adhesion. X: There is adhesion.
【0212】残色の評価 感光材料を30.5cm×25.4cmに裁断し、水洗水を
5℃にしてdry to dryで30秒の上述のよう
な処理を行い、感材の残色の度合いを目視にて下記の基
準で評価した。結果を表2に示す。 ◎:ほとんど残色しない。 ○:微かに残色しているが気にならない。 △:残色しているが実用的に許容される。 ×:残色が多く不可。Evaluation of Residual Color The photosensitive material was cut into a size of 30.5 cm × 25.4 cm, and the above-mentioned treatment was carried out for 30 seconds with a washing water of 5 ° C. and a dry to dry process. Was visually evaluated according to the following criteria. Table 2 shows the results. A: Almost no residual color. :: Slight residual color but not bothersome. Δ: Remains color but practically acceptable. ×: Many residual colors are not possible.
【0213】[0213]
【表1】 [Table 1]
【0214】[0214]
【表2】 [Table 2]
【0215】表2より、本発明の感光材料は、現像銀の
反射銀色調の点で優れていることがわかる。また、残色
がなく、スクリーンクリーナーテストにおいても染料や
顔料の添加位置やその化合物種などを選択することによ
って改善が可能であることがわかる。これに対し、染料
や顔料を添加しない試料、あるいは染料や顔料による白
色光透過濃度の寄与が本発明の範囲外の試料では銀色調
が劣るものとなる。また、ハロゲン化銀組成が本発明外
の試料では残色が生じ、平板化度が本発明外の試料では
感度の低下が著しい。なお、本発明の試料のうち、試料
No.1〜7、No.17〜22は、試料No.13〜15に比
べて現像処理後の画像の認識性が優れていた。Table 2 shows that the light-sensitive material of the present invention is excellent in the reflection silver tone of developed silver. In addition, there is no residual color, and it can be seen that improvement can be achieved in a screen cleaner test by selecting the addition positions of dyes and pigments and the types of the compounds. In contrast, a sample to which no dye or pigment is added, or a sample in which the contribution of the white light transmission density by the dye or pigment is out of the range of the present invention, has a poor silver tone. Samples having a silver halide composition outside the scope of the present invention have a residual color, and samples having a tabularization degree outside the scope of the invention have a remarkable decrease in sensitivity. In addition, among the samples of the present invention, the sample
Nos. 1 to 7 and Nos. 17 to 22 were more excellent in the recognizability of the image after the development processing than the samples Nos. 13 to 15.
【0216】実施例2 実施例1の試料を用いて、下記の現像処理条件としたこ
と以外は、実施例1と同様に評価したところ、試料の構
成に応じ同様の傾向を示し、実施例1と同様に本発明の
感光材料は現像の反射銀色調の点で優れていることがわ
かった。Example 2 An evaluation was conducted in the same manner as in Example 1 except that the development processing conditions described below were used using the sample of Example 1, and the same tendency was shown according to the structure of the sample. Similarly to the above, it was found that the light-sensitive material of the present invention was excellent in the development reflection silver tone.
【0217】(濃縮現像液の調製)下記処方のエリソル
ビン酸ナトリウムを現像主薬とする濃縮現像液Aを調製
した。 ジエチレントリアミン五酢酸 8.0g 亜硫酸ナトリウム 20.0g 炭酸ナトリウム・1水塩 52.0g 炭酸カリウム 55.0g エリソルビン酸ナトリウム 60.0g 4−ヒドロキシメチル−4−メチル−1−フェニル−3−ピラゾリドン 13.2g 3,3’−ジフェニル−3,3’−ジチオプロピオン酸 1.44g ジエチレングリコール 50.0g 下記の化合物を下記の量(Preparation of Concentrated Developing Solution) Concentrated developing solution A having the following formulation and using sodium erythorbate as a developing agent was prepared. Diethylenetriaminepentaacetic acid 8.0 g Sodium sulfite 20.0 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Sodium erythorbate 60.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 13.2 g 3,3'-diphenyl-3,3'-dithiopropionic acid 1.44 g diethylene glycol 50.0 g
【0218】[0218]
【化19】 Embedded image
【0219】水を加えて1リットルとする。水酸化ナト
リウムでpH10.1に調整する。Add water to make 1 liter. Adjust to pH 10.1 with sodium hydroxide.
【0220】(現像補充液の調製)上記濃縮現像液を2
倍希釈し、現像補充液として使用した。(Preparation of developer replenisher)
It was diluted twice and used as a developing replenisher.
【0221】(現像母液の調製)上記濃縮現像液2リッ
トルを水で希釈して4リットルとし、下記組成のスター
タ液を希釈した現像液1リットル当たり55ml添加し
た、pH9.5の現像液を現像母液とした。 スタータ液 臭化カリウム 11.1g 酢酸 10.8g 水を加えて55mlとする。(Preparation of developing mother liquor) A developing solution having a pH of 9.5 was prepared by diluting 2 liters of the above concentrated developing solution to 4 liters with water and adding 55 ml per liter of a diluted developing solution of a starter solution having the following composition. Used as mother liquor. Starter liquid Potassium bromide 11.1 g Acetic acid 10.8 g Add water to make up to 55 ml.
【0222】(濃縮定着液の調製)以下の処方の濃縮定
着液を調製した。 水 0.5リットル エチレンジアミンテトラ酢酸・2水塩 0.05g チオ硫酸ナトリウム 200g 重亜硫酸ナトリウム 98.0g 水酸化ナトリウム 2.9g NaOHでpH5.2に調整し、水を加えて1リットルとする。(Preparation of concentrated fixing solution) A concentrated fixing solution having the following formulation was prepared. Water 0.5 L Ethylenediaminetetraacetic acid dihydrate 0.05 g Sodium thiosulfate 200 g Sodium bisulfite 98.0 g Sodium hydroxide 2.9 g Adjust the pH to 5.2 with NaOH, and add water to make 1 L.
【0223】(定着補充液の調製)上記濃縮定着液を2
倍希釈し、定着補充液として使用した。(Preparation of Fixing Replenisher)
It was diluted twice and used as a fixing replenisher.
【0224】(定着母液の調製)上記濃縮定着液2リッ
トルを水で希釈して4リットルとした。pHは5.4で
あった。(Preparation of fixing mother liquor) 2 L of the above concentrated fixing solution was diluted with water to 4 L. pH was 5.4.
【0225】(感光材料の処理工程)上記現像母液およ
び定着母液を用いて、現像補充液および定着補充液を感
光材料1m2当たり65ml補充しながら処理した。なお、
水洗水は水道水を用いた。 工 程 温度 処理時間 現 像 35℃ 8秒 定 着 35℃ 8秒 水 洗 25℃ 7秒 乾 燥 55℃ 7秒 合 計 30秒[0225] Using the above developer mother liquor and fixing the mother liquor (processing step of the photosensitive material), and the developer replenisher and the fixing replenisher to the processing photosensitive material 1 m 2 per 65ml supplemented with. In addition,
Tap water was used as washing water. Process Temperature Processing time Current image 35 ° C 8 seconds Fixed 35 ° C 8 seconds Rinse 25 ° C 7 seconds Dry 55 ° C 7 seconds Total 30 seconds
【0226】実施例3 実施例1において、化学増感時に下記テルル化合物−1
をハロゲン化銀1モル当たり4×10-6モル相当をセレ
ン化合物−1とともに添加した以外は同様にて各試料を
作成し、実施例1と同じ評価をしたところ、同様の結果
が得られ、本発明の感材が現像銀の反射銀色調等につい
て優れていることが確認された。Example 3 In Example 1, the following tellurium compound-1 was used during chemical sensitization.
Was prepared in the same manner as above except that 4 × 10 −6 mol per mol of silver halide was added together with the selenium compound-1, and the same evaluation as in Example 1 was carried out. It was confirmed that the light-sensitive material of the present invention was excellent in the reflection silver tone of developed silver and the like.
【0227】[0227]
【化20】 Embedded image
【0228】[0228]
【発明の効果】本発明により、画像銀の透過および反射
の黒色度が改良され、残色が少なく、高感度で高い銀被
覆力を有し、ケイ光増感紙等に対する汚染性が改善可能
であり、さらには画像の認識性を向上させることができ
るハロゲン化銀写真感光材料を提供できる。According to the present invention, the blackness of transmission and reflection of image silver is improved, the residual color is small, the sensitivity is high and the silver covering power is high, and the stainability on fluorescent intensifying screens and the like can be improved. In addition, it is possible to provide a silver halide photographic material capable of improving the recognizability of an image.
Claims (6)
銀乳剤層を有する青色染色された医療用ハロゲン化銀写
真感光材料であって、 前記ハロゲン化銀乳剤層に含有されるハロゲン化銀粒子
の全投影面積の50%以上がアスペクト比が5以上の平
板状粒子で占められており、 前記平板状粒子が平均ヨウ化銀含有率1モル%以下のヨ
ウ臭化銀または臭化銀の組成を有し、かつセレン化合物
および/またはテルル化合物により化学増感されてお
り、 前記ハロゲン化銀乳剤層および/または前記ハロゲン化
銀乳剤層よりも上層の親水性コロイド層中に、570〜
650nmの間に極大吸収波長を有する顔料および/ま
たは染料が含有されており、かつ前記顔料および/また
は染料の含有量が、現像処理後の未露光部白色透過濃度
のうち、前記顔料および/または染料の寄与が50%以
上である量であることを特徴とするハロゲン化銀写真感
光材料。Claims 1. A blue-dyed medical silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide grains contained in the silver halide emulsion layer are 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 5 or more, and the tabular grains have a composition of silver iodobromide or silver bromide having an average silver iodide content of 1 mol% or less. Sensitized with a selenium compound and / or a tellurium compound, and in the silver halide emulsion layer and / or in a hydrophilic colloid layer above the silver halide emulsion layer,
The pigment and / or dye having a maximum absorption wavelength between 650 nm is contained, and the content of the pigment and / or dye is the pigment and / or dye in the unexposed portion white transmission density after the development processing. A silver halide photographic light-sensitive material characterized in that the dye contributes 50% or more.
請求項1のハロゲン化銀写真感光材料。2. The silver halide photographic material according to claim 1, wherein said pigment contains an anthraquinone pigment.
ジオキサジン系顔料とを含む請求項1または2のハロゲ
ン化銀写真感光材料。3. A silver halide photographic material according to claim 1, wherein said pigment contains a metal phthalocyanine pigment and a dioxazine pigment.
ロゲン化銀乳剤層よりも上層で表面保護層よりも下層に
ある親水性コロイド層中に含有される請求項1〜3のい
ずれかのハロゲン化銀写真感光材料。4. The halogen according to claim 1, wherein the pigment and / or dye is contained in a hydrophilic colloid layer above the silver halide emulsion layer and below the surface protective layer. Silver halide photographic material.
うち、前記顔料および/または染料の寄与が80%以上
である請求項1〜4のいずれかのハロゲン化銀写真感光
材料。5. The silver halide photographic light-sensitive material according to claim 1, wherein the contribution of said pigment and / or dye is at least 80% of the unexposed area white light transmission density after development processing.
持体に下塗層が存在するときは、この下塗層も染色され
ていない請求項1〜5のいずれかのハロゲン化銀写真感
光材料。6. The silver halide photograph according to claim 1, wherein the support is not dyed, and when an undercoat layer is present on the support, the undercoat layer is not dyed. Photosensitive material.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35410597A JP3682158B2 (en) | 1997-12-08 | 1997-12-08 | Silver halide photographic material |
US09/185,618 US6027866A (en) | 1997-11-07 | 1998-11-04 | Silver halide photographic element |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35410597A JP3682158B2 (en) | 1997-12-08 | 1997-12-08 | Silver halide photographic material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11174619A true JPH11174619A (en) | 1999-07-02 |
JP3682158B2 JP3682158B2 (en) | 2005-08-10 |
Family
ID=18435333
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP35410597A Expired - Fee Related JP3682158B2 (en) | 1997-11-07 | 1997-12-08 | Silver halide photographic material |
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Country | Link |
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JP (1) | JP3682158B2 (en) |
-
1997
- 1997-12-08 JP JP35410597A patent/JP3682158B2/en not_active Expired - Fee Related
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JP3682158B2 (en) | 2005-08-10 |
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