JPS62215261A - Photographic silver halide emulsion - Google Patents
Photographic silver halide emulsionInfo
- Publication number
- JPS62215261A JPS62215261A JP5790186A JP5790186A JPS62215261A JP S62215261 A JPS62215261 A JP S62215261A JP 5790186 A JP5790186 A JP 5790186A JP 5790186 A JP5790186 A JP 5790186A JP S62215261 A JPS62215261 A JP S62215261A
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- water
- silver halide
- dye
- nucleus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 39
- 239000000839 emulsion Substances 0.000 title claims abstract description 38
- 239000004332 silver Substances 0.000 title claims abstract description 38
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 35
- 230000003595 spectral effect Effects 0.000 claims abstract description 32
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 23
- 150000002170 ethers Chemical class 0.000 claims description 11
- 239000012736 aqueous medium Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 12
- 206010070834 Sensitisation Diseases 0.000 abstract description 12
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 230000008313 sensitization Effects 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 7
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 abstract description 3
- 229960003237 betaine Drugs 0.000 abstract description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 abstract 1
- 241000047703 Nonion Species 0.000 abstract 1
- 230000029936 alkylation Effects 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 62
- 238000000034 method Methods 0.000 description 34
- 239000000463 material Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 108010010803 Gelatin Proteins 0.000 description 10
- 229920000159 gelatin Polymers 0.000 description 10
- 239000008273 gelatin Substances 0.000 description 10
- 235000019322 gelatine Nutrition 0.000 description 10
- 235000011852 gelatine desserts Nutrition 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 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 6
- 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 5
- 239000001116 FEMA 4028 Substances 0.000 description 5
- 229960004853 betadex Drugs 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003839 salts Chemical class 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229930092411 Swietenocoumarin D Natural products 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 description 1
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- 150000001473 2,4-thiazolidinediones Chemical class 0.000 description 1
- FWBHETKCLVMNFS-UHFFFAOYSA-N 4',6-Diamino-2-phenylindol Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC2=CC=C(C(N)=N)C=C2N1 FWBHETKCLVMNFS-UHFFFAOYSA-N 0.000 description 1
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は分光増感に有用な色素(分光増感色素)を、シ
クロデキストリンのエーテル誘導体を利用して水性媒体
中に溶解させたハロゲン化銀写真乳剤に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is a halogenated dye that is useful for spectral sensitization (spectral sensitizing dye) dissolved in an aqueous medium using an ether derivative of cyclodextrin. Regarding silver photographic emulsions.
(従来の技術)
写真感光材料の製造にとって、分光増感技術すなわち感
光材料の感光波長域を可視域さらには赤外域まで充分に
長波長光に感光させるよう拡大せしめる方法か重要であ
ること、特にカラー感光材料にとって必須の技術である
ことはよく知られている。(Prior Art) In the production of photographic light-sensitive materials, spectral sensitization technology, that is, a method of expanding the sensitive wavelength range of light-sensitive materials to the visible range and even the infrared range, is important, especially in the production of photographic light-sensitive materials. It is well known that this technology is essential for color photosensitive materials.
分光増感色素かハロゲン化銀写真乳剤に添加される場合
、添加される条件の変化によってハロゲン化銀微結晶表
面における吸着状態か著しく異り、これか写真作用例え
ばカフリ作用、感度、分光感度分布、減感作用、感度の
安定性などに重大な影響を与える。このことはシー、イ
ー、ケー。When a spectral sensitizing dye is added to a silver halide photographic emulsion, the state of adsorption on the surface of silver halide microcrystals varies significantly depending on the conditions under which it is added, resulting in photographic effects such as cuffing, sensitivity, and spectral sensitivity distribution. , which has a significant effect on desensitization and sensitivity stability. This is sh, e, k.
ミース(C,E、に、Mees)著、ザ セオリー オ
フ ザフオトクラフィック プロセス (The Th
eory ofthe Photographic P
rocess)第2版(1954年マクミラン社刊)の
第12章430頁から500頁に詳しく記載されている
。The Theory of the Technical Process by C.E. Mees
eory of the Photographic P
rocess) 2nd edition (published by Macmillan in 1954), Chapter 12, pages 430 to 500.
一般に、ハロゲン化銀写真乳剤の分光増感色素の多くは
実質的に水に不溶である。このため、分光増感色素をハ
ロゲン化銀写真乳剤に添加するために通常用いられてい
る方法は、第1に水に自由に混合てきる有機溶剤、例え
ばアセトン、メタノール、エタノール、プロパツール、
メチルセロソルフやピリジンなどに色素を溶解させて、
乳剤に添加する方法である。この有機溶剤に一部水を混
合して添加する場合もある。特公昭44−23389号
公報に記載されている如く、アミジニウムイオン発色団
を有する増感色素に強酸を加えてプロトン化して水溶液
として添加する方法、また特公昭44−22948号公
報に記載されている如く、実質的に水に不溶性の増感色
素を揮発性溶剤のコロイドに添加混合し、それを加熱し
て溶剤を除去することによって親木コロイド中に色素を
分散させる方法がある。Generally, many of the spectral sensitizing dyes in silver halide photographic emulsions are substantially insoluble in water. For this reason, the commonly used method for adding spectral sensitizing dyes to silver halide photographic emulsions is to first add organic solvents that are freely miscible with water, such as acetone, methanol, ethanol, propatool,
Dissolve the dye in methyl cellosol, pyridine, etc.
This is a method of adding it to an emulsion. A portion of water may be mixed and added to this organic solvent. As described in Japanese Patent Publication No. 44-23389, a method of adding a strong acid to a sensitizing dye having an amidinium ion chromophore to protonate it and adding it as an aqueous solution, and as described in Japanese Patent Publication No. 44-22948, There is a method of dispersing the dye in the parent wood colloid by adding and mixing a substantially water-insoluble sensitizing dye to a colloid of a volatile solvent and heating it to remove the solvent.
(発明が解決しようとする問題点)
しかしなから、これらの方法は多くの欠陥をもっている
。まず通常用いられている、水に自由に混合てきる有機
溶剤に溶解して添加する方法は、用いる有機溶剤が共存
する塗布助剤の界面活性を低下させたり、バインダーを
凝固させたり、またカラー感材の場合には共存するカプ
ラーを固塊したりするので、高速塗布例えば1分間当り
100m以上の塗布を著しく困難にする。他方、添加さ
れたとき、用いられている有機溶剤が直ちに水に混合す
るため増感色素かハロゲン化銀結晶に吸着する以前にバ
インダーに吸着してしまったり、それ自身凝集してしま
ったりするために弱い分光感度しか与えないことがある
。また有機溶剤を用いる方法は防爆上の点て好ましくな
い。次に特公昭44−23389号公報に記載されてい
る方法では水溶液を強酸性にするため、色素の安定性の
点て好ましくない場合が多い。また特公昭44−229
48号公報に記載の親木コロイド中に色素を分散させる
方法は、有機溶剤を必要とし、したがって前記有機溶剤
を用いる場合と同様の欠点がある。(Problems to be Solved by the Invention) However, these methods have many deficiencies. First, the commonly used method of adding the organic solvent by dissolving it in an organic solvent that is freely miscible with water reduces the surface activity of the coating aid coexisting with the organic solvent, coagulates the binder, and adds color. In the case of photosensitive materials, coexisting couplers are solidified, making high-speed coating, for example, coating over 100 m per minute, extremely difficult. On the other hand, when added, the organic solvent used immediately mixes with water, so it may adsorb to the binder or aggregate itself before adsorbing to the sensitizing dye or silver halide crystals. may provide only weak spectral sensitivity. Furthermore, methods using organic solvents are not preferred from the viewpoint of explosion protection. Next, the method described in Japanese Patent Publication No. 44-23389 makes the aqueous solution strongly acidic, which is often unfavorable from the viewpoint of dye stability. Also, the special public official public interest rate was 44-229.
The method of dispersing a pigment in parent wood colloid described in Japanese Patent No. 48 requires an organic solvent, and therefore has the same drawbacks as the case using the organic solvent.
したかって本発明の目的は、有機溶剤や強酸を用いるこ
となく分光増感色素を水溶液としたハロゲン化銀写真乳
剤を提供することである。Therefore, an object of the present invention is to provide a silver halide photographic emulsion in which a spectral sensitizing dye is made into an aqueous solution without using an organic solvent or a strong acid.
(問題点を解決するための手段)
本発明者らは上記問題点を克服するため鋭意研究を重ね
た結果、分光増感色素をシクロデキストリンのエーテル
誘導体の存在下て水溶液とすることにより、従来水には
実質的に不溶てあった分光増感色素を水に可溶にして、
所望のハロゲン化銀写真乳剤を調製しうることを見い出
し、この知見に基づき本発明をなすに至った。(Means for Solving the Problems) The present inventors have conducted extensive research to overcome the above problems, and have found that by making a spectral sensitizing dye into an aqueous solution in the presence of an ether derivative of cyclodextrin, By making the spectral sensitizing dye, which was virtually insoluble in water, soluble in water,
It has been discovered that a desired silver halide photographic emulsion can be prepared, and the present invention has been completed based on this knowledge.
すなわち本発明は、シクロデキストリンのエーテル誘導
体の存在下に水性媒体中に溶解した分光増感色素を含有
させてなることを特徴とするハロゲン化銀写真乳剤を提
供するものである。That is, the present invention provides a silver halide photographic emulsion characterized by containing a spectral sensitizing dye dissolved in an aqueous medium in the presence of an ether derivative of cyclodextrin.
シクロデキストリンとは多数のD(+)−グルコビラノ
ース単位がα−1,4=結合により環を形成した化合物
てあり、1分子を構成するグルコース単位の数により、
α(6単位)、β(7単位)、γ(8単位)・・・なる
接頭文字がつけられ、それぞれα−シクロデキストリン
、β−シクロデキストリン、γ−シクロデキストリン・
・・と呼ばれている(一般式(I)参照)。このうち、
α、β、γの三種がよく知られており市販されている。Cyclodextrin is a compound in which many D(+)-glucobylanose units form a ring through α-1,4= bonds, and depending on the number of glucose units constituting one molecule,
α (6 units), β (7 units), γ (8 units), etc. are prefixed with α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, etc., respectively.
... (see general formula (I)). this house,
Three types, α, β, and γ, are well known and commercially available.
これらはまた別の呼び方として、シクロへキサアミロー
ス、シクロへブタアミロース、シクロオクタアミロース
などと呼ばれることもある。また、これらシクロデキス
トリンの水酸基をエーテル、エステル、アミノ基などに
した誘導体も知られている。これらシフロブキトリンに
関しては、M、 L、ベンダー、 M、コミャマ著、シ
クロデキストリン・ケミストリー(Cyclodext
rinChemistry)スブリンゲルーフエルラー
グ社、1978年刊に詳しく記載されている。These are also sometimes called cyclohexaamylose, cyclohexaamylose, cyclooctaamylose, etc. Also known are derivatives in which the hydroxyl group of these cyclodextrins is replaced by an ether, ester, amino group, or the like. Regarding these siphrobuchytrins, see Cyclodextrin Chemistry, M. L., Bender, M. Komyama.
rinChemistry) Sbringerfuerlag, published in 1978.
本発明に用いられる、シクロデキストリンのエーテル誘
導体とは、上記一般式(I)で表わされる化合物の水酸
基がアルキル化されてエーテルになったものをいう。種
々のエーテル誘導体のうちで特に2位および6位の2ケ
所がエーテル化されたものか好ましい。この例としては
、ヘプタキス−2,6−シメチルーβ−シクロデキス1
〜リン、ヘキサキス−2,6−シメチルーα−シクロデ
キス1へリン、オクタキス−2,6−シメチルーγ−シ
クロデキストリンなどかあけられる。例えばヘプタキス
−2,6−ラメチル−β−シクロデキストリンは、水に
溶けにくい(1,85g/100m文)β−シクロデギ
ストリンに較べ水に対する溶解度が著しく増大し、10
倍以」−に達する。従って、濃厚な水溶液を調製するこ
とか可能になり、β−シクロデギストリンに対し多くの
利点か期待される。The ether derivative of cyclodextrin used in the present invention refers to one in which the hydroxyl group of the compound represented by the above general formula (I) is alkylated to become an ether. Among various ether derivatives, those in which two positions, the 2-position and the 6-position, are etherified are particularly preferred. An example of this is heptakis-2,6-dimethyl-β-cyclodex1
~ Phosphorus, hexakis-2,6-dimethyl-α-cyclodextrin, octakis-2,6-dimethyl-γ-cyclodextrin, etc. are available. For example, heptakis-2,6-ramethyl-β-cyclodextrin has significantly increased solubility in water compared to β-cyclodextrin, which is less soluble in water (1.85g/100m).
Reach more than double. Therefore, it becomes possible to prepare concentrated aqueous solutions, which is expected to have many advantages over β-cyclodextrin.
また、本発明に用いられる増感色素としては、シアニン
色素、メロシアニン色素、複合シアニン色素、複合メロ
シアニン色素、ホロポーラ−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ギソノール色素か包
含される。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など
かあけられる。また、好ましく用いられる増感色素とし
てはノニオン、ベタイン、カチオンタイプのものかある
。これらの色素類には、塩基性異部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、ピリジン核、オキサゾリジン、チアンリン核、
ビロール核、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
など;これらの核に脂環式炭化水素環か縮合した核、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、ペンズイミタゾール核、ナフトオキサゾ
ール核、キノリン核イミタン[4,5−b]キノキザリ
ン核などが適用てきる。これらの核は炭素原子上に置換
されていてもよい。The sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemiogisonol dyes. Particularly useful dyes include those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes. Preferably used sensitizing dyes include nonionic, betaine, and cationic sensitizing dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyridine nucleus, oxazolidine, thianrin nucleus,
Virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus condensed with an alicyclic hydrocarbon ring to these nuclei, and an aromatic hydrocarbon ring condensed to these nuclei Nuclei, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, penzimitazole nucleus, naphthoxazole nucleus, quinoline nucleus imitane [4,5-b] quinoxaline nucleus etc. can be applied. These nuclei may be substituted on carbon atoms.
メロシアニン色素または複合メロシアニン色素にはケ1
〜メチレン構造を有する核として、ピラゾリン−5−オ
ン核、チオヒタントイン核、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、チオバルビッール酸根、2−チオセレナ
ゾリジン−2,4−ジオン核、ピラゾロ[1,5−a]
ペンズイミタゾール核、ピラゾロ[5,1−b]キナソ
ロン核などの5〜6員異節環核を適用することがてきる
。さらにはF、 M、ハマー著”へテロ環化合物−シア
ニン染料と関連化合物−”、ションウィレー アント
サンズにューヨーク、ロンドン)社、1964年刊に記
載されている色素が用いられる。For merocyanine dyes or complex merocyanine dyes,
- As a nucleus having a methylene structure, pyrazolin-5-one nucleus, thiohytantoin nucleus, 2-thioxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
Rhodanine nucleus, thiobarbyl acid group, 2-thioselenazolidine-2,4-dione nucleus, pyrazolo[1,5-a]
A 5- to 6-membered heterocyclic nucleus such as a penzimitazole nucleus or a pyrazolo[5,1-b]quinasolone nucleus can be applied. Furthermore, F., M. Hammer, “Heterocyclic Compounds - Cyanine Dyes and Related Compounds”, Schonwille Ant.
The dyes described in Sands (New York, London), 1964 are used.
本発明に用いられるシフロブキス1〜リンのエーテル誘
導体の量は、分光増感色素を溶解させるに必要な量てあ
り、これは分光増感色素の種類濃度等により異なるか、
分光増感色素に対し、モル比て通常1〜10000倍の
範囲てあり、好ましくは10〜1000倍の範囲であり
、より好ましくは10〜100倍の範囲である。The amount of the ether derivative of Sifurobukis 1 to Phosphorus used in the present invention is the amount necessary to dissolve the spectral sensitizing dye, and this may vary depending on the type and concentration of the spectral sensitizing dye.
The molar ratio is usually 1 to 10,000 times, preferably 10 to 1,000 times, and more preferably 10 to 100 times the molar ratio of the spectral sensitizing dye.
本発明において、ハロゲン化銀写真乳剤中の分光増感色
素の使用量は、従来とは特に異ならない。In the present invention, the amount of spectral sensitizing dye used in the silver halide photographic emulsion is not particularly different from the conventional method.
木発朋のハロゲン化銀写真乳剤の調製は通常、シフロブ
キス1〜リンのエーテル1誘導体の水溶液中に分光増感
色素を溶解し、この水溶液とハロゲン化銀写真乳剤とを
混合することにより行われる。The preparation of Kibatomo's silver halide photographic emulsion is usually carried out by dissolving a spectral sensitizing dye in an aqueous solution of an ether 1 derivative of Schiflovkis 1 to Phosphorus, and mixing this aqueous solution with a silver halide photographic emulsion. .
本発明に用いられる分光増感色素水溶液の調製は、次の
ような方法にて可能である。例えば(1)シクロデキス
トリンのニーデル誘導体の水溶液を調製しておきこれに
、分光増感色素の粉末を添加する。The aqueous spectral sensitizing dye solution used in the present invention can be prepared by the following method. For example, (1) an aqueous solution of a needle derivative of cyclodextrin is prepared and a powder of a spectral sensitizing dye is added thereto.
(2)シクロデキストリンのエーテル誘導体および分光
増感色素を同時に水に加える。あるいは逆に水を後から
加える
などである。(2) Add the ether derivative of cyclodextrin and the spectral sensitizing dye to water simultaneously. Alternatively, you can add water later.
このとき、分光増感色素のぬれ性を良くするだめの処理
(例えば、少量の水溶性の有機溶剤てぬらしておくなど
)を施しておいても良い。At this time, a treatment to improve the wettability of the spectral sensitizing dye (for example, wetting it with a small amount of water-soluble organic solvent) may be applied.
ここて得られた水溶液をハロゲン化銀乳剤に添加する時
期は、ハロゲン化銀粒子の形成中、形成後、化学熟成開
始時、終了後、水洗工程前あるいこのいずれの時期に添
加した写真乳剤も包含する。この際、用いた分光増感色
素よりも、シクロデキストリンのエーテル誘導体に包接
され易い化合物を用いてもよい(例えば、色素水溶液添
加後に加える。予め乳剤中に添加しておくなど)。The aqueous solution obtained here can be added to the silver halide emulsion during or after the formation of silver halide grains, at the beginning or end of chemical ripening, before the water washing step, or at any time during the formation of silver halide grains. Also includes. At this time, a compound that is more easily included in the ether derivative of cyclodextrin than the spectral sensitizing dye used may be used (eg, added after addition of the dye aqueous solution, added to the emulsion in advance, etc.).
本発明に用いられるハロゲン化銀乳剤は、通常水溶性銀
塩(例えば硝酸銀)溶液と水溶性ハロゲン塩(例えば臭
化カリウム)溶液とをゼラチンの如き水溶性高分子溶液
の存在下で混合してつくられる。このハロゲン化銀とし
ては、塩化銀、臭化銀のほかに、混合ハロゲン化銀、例
えば塩臭化銀、沃臭化銀、塩沃臭化銀等を用いることが
できる。ハロゲン化銀粒子の平均粒子サイズ(球状また
は球に近似の粒子の場合は、粒子直径、立方体粒子の場
合は、稜長を粒子サイズとし、投影面積にもとすく平均
て表す)は、4JLm以下が好ましい。粒子サイズ分布
は狭くても(いわゆる「単分散」)広くてもいずれでも
よい。The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. able to make. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. The average grain size of silver halide grains (in the case of spherical or approximately spherical grains, the grain size is taken as the grain diameter; in the case of cubic grains, the grain size is expressed as the ridge length, and the average is expressed in terms of the projected area) is 4 JLm or less is preferred. The particle size distribution may be narrow (so-called "monodisperse") or broad.
これらのハロゲン化銀粒子の形は立方晶形、14面体、
菱12面体、八面体、その混合晶形等または球状、板状
等どれでもよい。The shapes of these silver halide grains are cubic, tetradecahedral,
Any rhombic dodecahedral, octahedral, mixed crystal shape, spherical shape, plate shape, etc. may be used.
また粒子の直径がその厚みの5倍以上の超平板のハロゲ
ン化銀粒子が全投影面積の50%以上を占めるような乳
剤を使用してもよい。詳しくは特開昭58−12792
1、同58−113927などの明細書に記載されてい
る。Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. For details, see JP-A-58-12792.
1, No. 58-113927, etc.
また、別々に形成した2種以上のハロゲン化銀写真乳剤
を混合してもよい。さらに、ハロゲン化銀粒子の結晶構
造は内部まで一様なものであっても、また内部と外部の
ハロゲン組成が異なった層状構造をしたものや、英国特
許635,841号、米国特許3,622,318号に
記載されているような、いわゆるコンバージョン型のも
のてあってもよい。また、潜像を主として表面に形成す
る形のもの、粒子内部に形成する内部潜像型のもののい
ずれでもよい。Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of silver halide grains is uniform inside, there are also grains with a layered structure in which the halogen composition inside and outside differs, and those described in British Patent No. 635,841 and US Patent No. 3,622. There may also be a so-called conversion type as described in , No. 318. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used.
これらの写真乳剤はジェムス著、「ザ・セオリー・オブ
・フォトグラフィック・プロセス」第4版 マツクミラ
ン社刊(1976年);p、 グラフキデ著“シミー・
工・フィジーク・フォトグラフィーク″(ポール・モン
テル社刊、1967年)、G、F、ダアフィン著“フォ
トグラフィック・エマルジョン・ケミストリー” (フ
ォー力Jレプレス刊、1966年)、V、L、ツェリク
マンら著“メイキング・アンド・コーティング・フォト
グラフィック・エマフレジョン” ()オーカルレフ。These photographic emulsions are described in James James, "The Theory of Photographic Process", 4th edition, Matsukumiran Publishing (1976); p. Grafkide, "Simmy".
``Photographic Emulsion Chemistry'' by G. F. Daaffin (Published by Four Power J.Repress, 1966), V. L. Zelikman et al. Author: “Making and Coating Photographic Emergence” () Ocalref.
レス刊、1964年) (James r The T
heory ofthe Photographic
ProcessJ The 4th edition、
Mac Millan(1976)、 P、 Glaf
kides、 ”Chimie etPhysique
Photographique″(Paul Mon
tel、1967)、 G、 F、 Duffin、P
hotographic EmulsionChemi
stry″(The Focal Press、 19
66)、 V。James r The T
theory of the Photographic
ProcessJ The 4th edition,
Mac Millan (1976), P. Glaf
kids, “Chimie et Physique
Photographique'' (Paul Mon
tel, 1967), G., F., Duffin, P.
photographic Emulsion Chemi
try'' (The Focal Press, 19
66), V.
L、 Zelika+an et al、”Maki
ng and CoatingPhotographi
c Emulsion″(The Focal Pre
ss。L, Zelika+an et al, “Maki
ng and coatingphotography
c Emulsion'' (The Focal Pre
ss.
1964) )などに記載された方法を用いて調製する
ことができる。すなわち、酸性法、中性法、アンモニア
法等のいずれでもよく、また可溶性銀塩と可溶性ハロゲ
ン塩を反応させる形式としては、片側混合法、同時混合
法、それらの組合せなどのいずれを用いてもよい。1964)). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.
粒子を銀イオン過剰の下において形成させる方法(いわ
ゆる逆混合法)を用いることもできる。It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
同時混合法の一つの形式としてハロゲン化銀の生成され
る液相中のp、Agを一定に保つ方法、すなわち、いわ
ゆるコンドロールド、ダブルジェット法を用いることも
できる。この方法によると、結晶形が規則的で粒子サイ
ズが均一に近いハロゲン化銀乳剤が得られる。As one form of the simultaneous mixing method, a method in which p and Ag in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald or double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.
別々に形成した2種以上のハロゲン化銀乳剤を混合して
用いてもよい。Two or more types of silver halide emulsions formed separately may be mixed and used.
ハロゲン化銀乳剤は、化学増感を行わない、いわゆる末
後熟乳剤(プリミティブ乳剤)を用いることもできるが
、通常は化学増感される。化学増感のためには、前記グ
ラフィキデまたはツエリクマンらの著書、あるいはH,
フリーゼル編、[ディー・グルンドラーゲン・デル・ホ
トグラフィッシェン・ブロツェセ・ミツト・ジルベルハ
ロゲニデン]アカデミッシエ フエルラーグスゲゼルシ
ャフト(1968)(DieGrundlagen d
er Photographischen Proze
ssemit Silbcrbalogeniden
” AkademischeVcrlagsgese
llschaft (1968))に記載の方法を用い
ることかてきる。The silver halide emulsion may be a so-called primitive emulsion which is not chemically sensitized, but it is usually chemically sensitized. For chemical sensitization, the above-mentioned book by Grafkide or Zerikman et al., or by H.
Friesel ed.
er Photography Proze
ssemit Silbcrbalogeniden
” AkademischeVcrlagsgese
llschaft (1968)).
すなわち、活性ゼラチンや銀と反応しつる硫黄を含む化
合物(例えばチオ硫酸塩、チオ尿素類、メルカプト化合
物、ロータニジ類)を用いる硫黄増感法、還元性物質(
例えば第一スズ塩、アミン類、ヒドラジン誘導体、ホル
ムアミジンスルフィン酸、シラン化合物)を用いる還元
増感法、貴金属化合物(例えば金化合物の他、白金、イ
リジウム、パラジウムなどの周期律表第■族金属の錯塩
)を用いる貴金属増感法などを単独あるいは組み合わせ
て実施することかできる。In other words, sulfur sensitization using active gelatin and compounds containing sulfur that react with silver (e.g. thiosulfates, thioureas, mercapto compounds, rotanidines), reducing substances (
For example, reduction sensitization using stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal compounds (for example, gold compounds, as well as metals from group Ⅰ of the periodic table such as platinum, iridium, palladium, etc.) A noble metal sensitization method using complex salts of 1,2,2, etc. can be carried out alone or in combination.
感光材料に用いる結合剤または保護コロイドとしては、
ゼラチンを用いるのが有利であるが、それ以外の親水性
コロイドも用いることかてきる。Binders or protective colloids used in photosensitive materials include:
Although it is advantageous to use gelatin, other hydrophilic colloids may also be used.
ゼラチンとしては、石灰処理ゼラチン、酸処理ゼラチン
、ゼラチン誘導体などを用いることかてきる。As the gelatin, lime-treated gelatin, acid-treated gelatin, gelatin derivatives, etc. can be used.
また、その他の種々の添加剤か用いられる。例えば、発
色剤(例えばイエローカプラー、マゼンタカプラー、シ
アンカプラーなど)、蛍光増白剤(スチルベン系など)
、カプラ防止剤、安定剤(1−フェニル−5−メルカプ
トテトラゾール、4−ヒドロキシ置換(1,3,3a、
7)テトラアザインデンなど)、減感剤、硬膜剤(例え
ば1.3.5−トリアクリロイル−へキサヒトロー5−
t−リアジン、2,4−ジクロル−6−ヒトロキシーs
−)リアジンなど)、塗布助剤、帯電防止剤、可塑剤、
スベリ剤、マット剤、現像促進剤、オイル(例えばフタ
ール酸アルキルエステル、リン酸エステルなど)、媒染
剤、紫外線吸収剤、退色防止剤(ハイドロキノン誘導体
など)、色カプラ防止剤(ハイドロキノン誘導体など)
、防パイ剤(2−チアゾリルベンズイシタゾール類、イ
ンチアゾロン類など)などがあげられる。Also, various other additives may be used. For example, color formers (e.g. yellow couplers, magenta couplers, cyan couplers, etc.), optical brighteners (stilbenes, etc.)
, anti-coupler, stabilizer (1-phenyl-5-mercaptotetrazole, 4-hydroxy substituted (1,3,3a,
7) Tetraazaindene, etc.), desensitizers, hardeners (e.g. 1.3.5-triacryloyl-hexahythroyl-5-
t-Ryazine, 2,4-dichloro-6-hydroxys
-) riazine, etc.), coating aids, antistatic agents, plasticizers,
Slip agents, matting agents, development accelerators, oils (e.g. phthalate alkyl esters, phosphate esters, etc.), mordants, ultraviolet absorbers, anti-fading agents (hydroquinone derivatives, etc.), color coupler inhibitors (hydroquinone derivatives, etc.)
, anti-piping agents (2-thiazolylbenzicitazoles, intiazolones, etc.).
これらの添加剤について、具体的にはリサーチ・ディス
クローシャー(RESEARCHDISCLO3URE
)176号、第22〜31頁(RD−17643)(D
ec、1978)などに記載されたものを用いることか
できる。For more information on these additives, please refer to Research Disclosure (RESEARCH DISCLO3URE).
) No. 176, pp. 22-31 (RD-17643) (D
EC, 1978) can be used.
完成(finished)乳剤は、適切な支持体、例え
ばバライタ紙、レジンコート紙、合成紙、トリアセテー
トフィルム、ポリエチレンテレフタレートフィルム、そ
の他のプラスチックベースまたはガラス板の上に塗布さ
れる。すなわち、ディップコート、エアーナイフコート
、カーテンコート、あるいは米国特許第2,681,2
94号に記載のホッパーを使用するエクストルージョン
コートを含む種々の塗布法によって塗布することによっ
て写真感光材料とすることができる。The finished emulsion is coated onto a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates. i.e. dip coat, air knife coat, curtain coat, or U.S. Pat. No. 2,681,2
A photographic light-sensitive material can be obtained by coating by various coating methods including extrusion coating using a hopper as described in No. 94.
本発明の写真乳剤を用いることのてきる写真感光材料と
しては、種々のカラー及び黒白感光材料を挙げることが
できる。Photographic materials in which the photographic emulsion of the present invention can be used include various color and black-and-white light-sensitive materials.
例えば撮影用カラーネガフィルム(一般用、映画用等)
、カラー反転フィルム(スライド用、映画用等、またカ
プラーを含有しない場合もする場合もある)、カラー印
画紙、カラーポジフィルム(映画用等)、カラー反転印
画紙、熱現像用カラー感光材料、銀色素漂白法を用いた
カラー感光材料、製版用写真感光材料(リスフィルム、
スキャナーフィルム等)、Xレイ写真感光材料(直接・
間接医療用、工業用等)、撮影用黒白ネガフィルム、黒
白印画紙、マイクロ用感光材料(C0M用、マイクロフ
ィルム等)、カラー拡散転写感光材料(DTR)、銀塩
拡散転写感光材料、プリントアウト感光材料などを挙げ
ることができる。For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, etc., and may or may not contain couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, color photosensitive materials for heat development, silver Color light-sensitive materials using the bare bleaching method, photographic light-sensitive materials for plate making (lith film,
scanner film, etc.), X-ray photosensitive materials (direct,
(indirect medical use, industrial use, etc.), black and white negative film for photography, black and white photographic paper, microphotosensitive materials (for C0M, microfilm, etc.), color diffusion transfer photosensitive materials (DTR), silver salt diffusion transfer photosensitive materials, printouts Examples include photosensitive materials.
本発明の光応答性材料が感光材料の場合、その写真処理
には、公知の方法のいずれをも用いることができるし処
理液には公知のものを用いることかできる。また、処理
温度は通常、18°Cから50°Cの間に選ばれるか、
18°Cより低い温度または50°Cをこえる温度とし
てもよい。目的に応し、録画像を形成する現像処理(黒
白写真処理)、あるいは、色素像を形成すべき現像処理
から成るカラー写真処理のいずれをも適用することか出
来る。When the photoresponsive material of the present invention is a photosensitive material, any known method can be used for its photographic processing, and known processing solutions can be used. Also, the processing temperature is usually chosen between 18°C and 50°C;
The temperature may be lower than 18°C or above 50°C. Depending on the purpose, either a developing process for forming a recorded image (black and white photographic process) or a color photographic process consisting of a developing process for forming a dye image can be applied.
現像処理方法に関しては、詳しくはリサーチ・ディスク
ローシャ−176号第28頁〜第30頁(RD−176
43)(Dec、1978)に記載されている。For details regarding the development processing method, see Research Disclosure No. 176, pages 28 to 30 (RD-176
43) (Dec, 1978).
(発明の効果)
本発明によれば、シクロデキストリンのエーテル誘導体
を用いることにより、従来水には実質的に不溶であった
分光増感色素を水に可溶にすることかてきる。したがっ
て、水溶液中ての分光増感色素の安定性が高く、色増感
感度の高いハロゲン化銀写真乳剤として優れた効果を奏
する。なお、これらの効果はシクロデキストリンのエー
テル誘導体の包接によるものと推定される。このような
本発明のハロゲン化銀写真乳剤は有機溶剤を用いずに含
有成分の分散安定性を高めたものであり、高速塗布適性
等、塗布性の優れるものである。(Effects of the Invention) According to the present invention, by using an ether derivative of cyclodextrin, a spectral sensitizing dye, which has conventionally been substantially insoluble in water, can be made soluble in water. Therefore, the stability of the spectral sensitizing dye in an aqueous solution is high, and it exhibits excellent effects as a silver halide photographic emulsion with high color sensitization sensitivity. It is assumed that these effects are due to the inclusion of the ether derivative of cyclodextrin. Such a silver halide photographic emulsion of the present invention has improved dispersion stability of the contained components without using an organic solvent, and has excellent coating properties such as suitability for high-speed coating.
(実施例) 次に本発明を実施例に基づきさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail based on examples.
参考例1
下記の2種の分光増感色素について、ヘプタキス−2,
6−ジメチル−β−シクロデキストリン(DMCD)の
有無による水への溶解性の差な測定した。結果を表1に
示した。Reference Example 1 Regarding the following two types of spectral sensitizing dyes, heptakis-2,
The difference in water solubility between the presence and absence of 6-dimethyl-β-cyclodextrin (DMCD) was measured. The results are shown in Table 1.
色素1
色素2
表1
上記の結果から明らかなように、DMCDを添加するこ
とにより分光増感色素の水への溶解性を高めることがで
きる。Dye 1 Dye 2 Table 1 As is clear from the above results, the solubility of the spectral sensitizing dye in water can be increased by adding DMCD.
実施例1
色素lを、5%DMCD水溶液を用いてI X 10’
mo l/lの溶液とし、ハロゲン化銀乳剤に添加した
。このハロゲン化銀乳剤について分光増感の実験を行な
った。詳細は下記の通りである。Example 1 Dye 1 was prepared using 5% DMCD aqueous solution.
A mol/l solution was prepared and added to a silver halide emulsion. Spectral sensitization experiments were conducted on this silver halide emulsion. Details are as below.
臭化カリウムと塩化ナトリウムをモル比7:3て含む水
溶液と硝酸銀水溶液を激しい攪拌の下で塩化ナトリウム
を含むゼラチン水溶液に添加し、同時混合法にて塩臭化
銀乳剤(臭化銀含量70モル%、平均粒径0.45ルm
、変動係数15%)を調製した。さらに上記乳剤にハロ
ゲン化銀1モル当りチオ硫酸ナトリウムを2.0X10
−5モル、増感色素lを1.0X10−4モル添加し、
最高感度を得るべく、最適に増感を施した。なお、上記
色素を添加する際に5%へブタキス−2,6−ジメチル
−β−シクロデキストリン(商品名:セルデックス二日
本食品化工製)の前記水溶液を溶媒として添加したもの
と、比較として増感色素1を添加しないものを調製し、
得られた赤感性塩臭化銀乳剤をそれぞれイ及び口とした
。An aqueous solution containing potassium bromide and sodium chloride at a molar ratio of 7:3 and an aqueous silver nitrate solution were added to an aqueous gelatin solution containing sodium chloride under vigorous stirring, and a silver chlorobromide emulsion (silver bromide content: 70%) was prepared by simultaneous mixing. Mol%, average particle size 0.45 lm
, coefficient of variation 15%) were prepared. Furthermore, 2.0×10 sodium thiosulfate was added to the above emulsion per mole of silver halide.
-5 mol, 1.0X10-4 mol of sensitizing dye l was added,
Optimal sensitization was performed to obtain the highest sensitivity. In addition, when adding the above-mentioned dye, the above-mentioned aqueous solution of 5% hebutakis-2,6-dimethyl-β-cyclodextrin (trade name: Seldex Nippon Foods Chemical Co., Ltd.) was added as a solvent, and for comparison. Prepare one without adding sensitive dye 1,
The resulting red-sensitive silver chlorobromide emulsions were designated as A and A, respectively.
次にシアンカプラー*aと*bを、退色防止剤*C1紫
外線吸収剤*d、*e、*fと共にジブチルフタレート
(DBP)および酢酸エチルの混合液に溶解し、ドデシ
ルベンゼンスルホン酸ナトリウムを含む10%ゼラチン
水溶液に乳化分散させた。(各薬品量は表2参照)
この乳化分散物を前記乳剤イ、口と混合して塗布液を調
製し、両面ポリエチレンラミネート紙に塗布し、それぞ
れ試料No、101.102を作成した。塗布した側の
ポリエチレンは二酸化チタンを白色顔料として、また微
量の群青を含有する。保護層としてはゼラチンを塗布し
た。各層の硬膜剤としては2.4−ジクロロ−6−ヒト
ロキシー5−)−リアジンナトリウム塩を用いた。塗布
試料の内容および塗布量を表2に示した。Next, cyan couplers *a and *b are dissolved in a mixture of dibutyl phthalate (DBP) and ethyl acetate, along with anti-fade agent *C1 ultraviolet absorber *d, *e, *f, containing sodium dodecylbenzenesulfonate. It was emulsified and dispersed in a 10% aqueous gelatin solution. (See Table 2 for the amount of each chemical.) This emulsified dispersion was mixed with the emulsions A and I to prepare a coating solution, which was coated on double-sided polyethylene laminated paper to prepare samples No. 101 and 102, respectively. The polyethylene on the coated side contains titanium dioxide as a white pigment and a trace amount of ultramarine blue. Gelatin was applied as a protective layer. As a hardening agent for each layer, 2,4-dichloro-6-hydroxy-5-)-lyazine sodium salt was used. Table 2 shows the contents and coating amount of the coating sample.
なお比較のためにシクロデキストリンを用いないて増感
色素1.0xlO−4モルを添加したところ、溶解する
に必要な水の量が多くなり、良好な塗布はできなかった
。For comparison, when 1.0xlO-4 mole of sensitizing dye was added without using cyclodextrin, the amount of water required for dissolution was large and good coating could not be achieved.
(*a)シアンカプラー
(*b)シアンカプラー
しW
(*C)退色防止剤
(*d)紫外線吸収剤
H
(*e)紫外線吸収剤
(*f)紫外線吸収剤
R
に4H9[tl
これらの試料に引き伸ばし機(富士写真フィルム社製フ
シカラーヘット609)て赤フィルターを介し、センシ
トメトリー用の階調露光を与えた後、以下の処理工程の
現像処理を行った。(*a) Cyan coupler (*b) Cyan coupler W (*C) Anti-fading agent (*d) Ultraviolet absorber H (*e) Ultraviolet absorber (*f) Ultraviolet absorber R 4H9 [tl These The sample was subjected to gradation exposure for sensitometry through a red filter using an enlarger (Fushicolor Head 609 manufactured by Fuji Photo Film Co., Ltd.), and then subjected to the following processing steps.
処理工程 温 度 時 間現像液
33°C3,5分
漂白定着液 33°C1,5分
水洗 24〜35°C3,0分
叉奪薫
ジエチレントリアミン五酢酢・5Na 2.0gベン
ジルアルコール 15m文ジエチレング
リコール 10m文Naz so3
2.OgKBr
0.5gヒドロキシルアミン硫酸塩
3.0g4−アミノ−3−メチル−N−
エチル−N−(β−(メタン
スルホンアミド)エチル〕−p−
フェニレンシアミン・硫酸塩 5.OgN a 2
CO3(−水塩) 30.0g蛍光増白剤
(スチルベン系) 1.0g水を加えてlリッ
ターにする (pH10,1)漂白定着液
チオ硫酸アンモニウム(54w t%)50nlj
Naz so3 15.0gNH4
(Fe (EDTA)) 55.OgEDTA・
2Na 4.0g水を加えてlリッ
ターにする (pH6,9)得られた結果を表3に示
した。感度は試料No。Processing process Temperature Time Developer
Bleach-fix solution for 3.5 minutes at 33°C Wash with water for 1.5 minutes at 33°C Wash for 3.0 minutes at 24-35°C Diethylenetriaminepentavinegar vinegar/5Na 2.0g Benzyl alcohol 15m diethylene glycol 10m Naz so3
2. OgKBr
0.5g hydroxylamine sulfate
3.0g4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl]-p-phenylenecyamine sulfate 5.OgN a 2
CO3 (-water salt) 30.0g Fluorescent brightener (stilbene type) 1.0g Add water to make 1 liter (pH 10,1) Bleach-fix ammonium thiosulfate (54wt%) 50nlj Naz so3 15.0gNH4
(Fe (EDTA)) 55. OgEDTA・
Add 4.0 g of 2Na to make up to 1 liter (pH 6,9) The results obtained are shown in Table 3. Sensitivity is sample no.
101の感度を便宜上100とした。感度は最小濃度に
0.5を加えた濃度を与えるのに必要な露光量の逆数の
相対値で表わした。表3に示すように本発明の溶媒を用
いた系で色増感感度が得られていることがわかる。また
二つの試料の乳剤が、はぼ同等の固有感度を有している
ことも露光フィルターを変えた同様の実験で確認した。The sensitivity of 101 was set to 100 for convenience. Sensitivity was expressed as a relative value of the reciprocal of the exposure amount required to provide the minimum density plus 0.5. As shown in Table 3, it can be seen that color sensitization sensitivity was obtained in the system using the solvent of the present invention. It was also confirmed in a similar experiment using different exposure filters that the two sample emulsions had similar intrinsic sensitivities.
表3
実施例2
色素1の水溶液の安定性を評価した。5%のDMCDを
含む試料(A)と含まない試料(B)(それぞれ色素濃
度は2X 10−4mol/見)を室温暗所に保存し、
調液直後のものと1週間経過したものについて、吸光度
を比較した。結果を表4に示した。Table 3 Example 2 The stability of an aqueous solution of Dye 1 was evaluated. A sample containing 5% DMCD (A) and a sample without DMCD (B) (each dye concentration 2X 10-4 mol/view) were stored at room temperature in the dark.
The absorbance was compared between the sample immediately after preparation and the sample after one week. The results are shown in Table 4.
表4
表中の値は各試料をメタノールにて20倍に稀釈したの
ち測定した吸光度の相対値である。Table 4 The values in the table are relative values of absorbance measured after each sample was diluted 20 times with methanol.
以上の実施例から明らかなように、本発明の方法により
、水に難溶の増感色素を水に可溶にし且つ分光増感可能
にして、さらに水溶液の安定化が可能なことが明らかで
ある。As is clear from the above examples, it is clear that the method of the present invention makes it possible to make sensitizing dyes that are poorly soluble in water soluble in water, enable spectral sensitization, and further stabilize the aqueous solution. be.
Claims (1)
体中に溶解した分光増感色素を含有させてなることを特
徴とするハロゲン化銀写真乳剤。A silver halide photographic emulsion comprising a spectral sensitizing dye dissolved in an aqueous medium in the presence of an ether derivative of cyclodextrin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5790186A JPS62215261A (en) | 1986-03-15 | 1986-03-15 | Photographic silver halide emulsion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5790186A JPS62215261A (en) | 1986-03-15 | 1986-03-15 | Photographic silver halide emulsion |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS62215261A true JPS62215261A (en) | 1987-09-21 |
Family
ID=13068897
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5790186A Pending JPS62215261A (en) | 1986-03-15 | 1986-03-15 | Photographic silver halide emulsion |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62215261A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0666496A1 (en) * | 1994-02-08 | 1995-08-09 | Minnesota Mining And Manufacturing Company | Photographic silver halide elements comprising infrared sensitizing dyes |
EP0675403A1 (en) * | 1994-03-22 | 1995-10-04 | Agfa-Gevaert N.V. | Photograhic material with effeciently used non-sensitizing dyes |
CN109329588A (en) * | 2018-10-24 | 2019-02-15 | 浙江海洋大学 | Compound feed for marine fish for deep-water cage culture |
-
1986
- 1986-03-15 JP JP5790186A patent/JPS62215261A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0666496A1 (en) * | 1994-02-08 | 1995-08-09 | Minnesota Mining And Manufacturing Company | Photographic silver halide elements comprising infrared sensitizing dyes |
EP0675403A1 (en) * | 1994-03-22 | 1995-10-04 | Agfa-Gevaert N.V. | Photograhic material with effeciently used non-sensitizing dyes |
CN109329588A (en) * | 2018-10-24 | 2019-02-15 | 浙江海洋大学 | Compound feed for marine fish for deep-water cage culture |
CN109329588B (en) * | 2018-10-24 | 2022-02-08 | 浙江海洋大学 | Compound feed for marine fish for deep-water cage culture |
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