AU3148693A - Improved developer systems for hydrazine containing films - Google Patents
Improved developer systems for hydrazine containing filmsInfo
- Publication number
- AU3148693A AU3148693A AU31486/93A AU3148693A AU3148693A AU 3148693 A AU3148693 A AU 3148693A AU 31486/93 A AU31486/93 A AU 31486/93A AU 3148693 A AU3148693 A AU 3148693A AU 3148693 A AU3148693 A AU 3148693A
- Authority
- AU
- Australia
- Prior art keywords
- ascorbic acid
- developer solution
- developing agent
- hydrazine
- silver halide
- 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims description 25
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 65
- -1 silver halide Chemical class 0.000 claims description 38
- 229960005070 ascorbic acid Drugs 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 235000010323 ascorbic acid Nutrition 0.000 claims description 25
- 239000011668 ascorbic acid Substances 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 17
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical group [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 7
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 5
- 239000002211 L-ascorbic acid Substances 0.000 claims description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 5
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 5
- 239000004320 sodium erythorbate Substances 0.000 claims description 5
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 5
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 239000000182 glucono-delta-lactone Substances 0.000 claims description 4
- 229960003681 gluconolactone Drugs 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-UHFFFAOYSA-N 0.000 claims description 3
- LTACQVCHVAUOKN-UHFFFAOYSA-N 3-(diethylamino)propane-1,2-diol Chemical compound CCN(CC)CC(O)CO LTACQVCHVAUOKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims 6
- 229960005055 sodium ascorbate Drugs 0.000 claims 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims 4
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 claims 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims 2
- QTLVFZFPYGQREC-UHFFFAOYSA-N 2-(4-phenylmethoxyphenyl)pyridine Chemical compound C=1C=CC=CC=1COC(C=C1)=CC=C1C1=CC=CC=N1 QTLVFZFPYGQREC-UHFFFAOYSA-N 0.000 claims 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 claims 1
- ALEZIZKXRBVZTQ-UHFFFAOYSA-N acetohydrazide;2-(4-phenylmethoxyphenyl)pyridin-1-ium;bromide Chemical compound [Br-].CC(=O)NN.C=1C=CC=CC=1COC(C=C1)=CC=C1C1=CC=CC=[NH+]1 ALEZIZKXRBVZTQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 32
- 235000002566 Capsicum Nutrition 0.000 description 8
- 239000006002 Pepper Substances 0.000 description 8
- 241000722363 Piper Species 0.000 description 8
- 235000016761 Piper aduncum Nutrition 0.000 description 8
- 235000017804 Piper guineense Nutrition 0.000 description 8
- 235000008184 Piper nigrum Nutrition 0.000 description 8
- 150000002429 hydrazines Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229940026239 isoascorbic acid Drugs 0.000 description 6
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 235000010350 erythorbic acid Nutrition 0.000 description 5
- 239000004318 erythorbic acid Chemical group 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 4
- 239000011755 sodium-L-ascorbate Substances 0.000 description 4
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 3
- 229940072107 ascorbate Drugs 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- VARKIGWTYBUWNT-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanol Chemical compound OCCN1CCN(CCO)CC1 VARKIGWTYBUWNT-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- BRIYEPMCMKMZLL-UHFFFAOYSA-N C(C)N(CC)C(C)O.OCCN1CCN(CC1)CCO.OCCN1CCNCC1 Chemical compound C(C)N(CC)C(C)O.OCCN1CCN(CC1)CCO.OCCN1CCNCC1 BRIYEPMCMKMZLL-UHFFFAOYSA-N 0.000 description 1
- LHMJLVBSHYEGMN-UHFFFAOYSA-N CC(NN)=O.Br Chemical compound CC(NN)=O.Br LHMJLVBSHYEGMN-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-MVHIGOERSA-N D-ascorbic acid Chemical compound OC[C@@H](O)[C@@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-MVHIGOERSA-N 0.000 description 1
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 description 1
- SBJKKFFYIZUCET-UHFFFAOYSA-N Dehydroascorbic acid Natural products OCC(O)C1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-UHFFFAOYSA-N 0.000 description 1
- DJKYUFCLHAMEQW-UHFFFAOYSA-L SC=1SC2=C(N1)C=CC=C2.C([O-])([O-])=O.[K+].[K+] Chemical compound SC=1SC2=C(N1)C=CC=C2.C([O-])([O-])=O.[K+].[K+] DJKYUFCLHAMEQW-UHFFFAOYSA-L 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- BTKOPDXMVKYSNL-UHFFFAOYSA-N [Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O Chemical compound [Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BTKOPDXMVKYSNL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 235000020960 dehydroascorbic acid Nutrition 0.000 description 1
- 239000011615 dehydroascorbic acid Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 231100000916 relative toxicity Toxicity 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- ZSOMPVKQDGLTOT-UHFFFAOYSA-J sodium green Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.COC=1C=C(NC(=O)C=2C=C(C(=CC=2)C2=C3C=C(Cl)C(=O)C=C3OC3=CC([O-])=C(Cl)C=C32)C([O-])=O)C(OC)=CC=1N(CCOCC1)CCOCCOCCN1C(C(=C1)OC)=CC(OC)=C1NC(=O)C1=CC=C(C2=C3C=C(Cl)C(=O)C=C3OC3=CC([O-])=C(Cl)C=C32)C(C([O-])=O)=C1 ZSOMPVKQDGLTOT-UHFFFAOYSA-J 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009736 wetting Methods 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
-
- 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
IΣΣ EL
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IMPROVED DEVELOPER SYSTEMS FOR HYDRAZINE CONTAINING FILMS 5
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the field of photographic
10 silver halide systems and more specifically to the processing of photographic silver halide elements. Still more specifically, this invention relates to rapid access photographic elements containing hydrazine compounds and to processing solutions related thereto.
15 2. Description of the Prior Art
Photographic silver halide elements have long been used to record images and are often preferred because they have excellent image reproduction characteristics and high speed. In the field of lithography, a host of
20 varied silver halide elements have been described for this method of reproduction, most of which have the high contrast and density needed to produce the good half-tone dots necessary for this reproduction method. However, most of these elements require a so-called
25 "induction period" during development, which means that there is an initial lag period during which processing is relatively slow prior to infectious development when the high contrast and density are achieved.
In an on-going effort to reduce the induction
30 period and thereby make a rapid access system, it has been observed that rapid access can be achieved, for example, by the addition of hydrazines and derivatives thereof to either the silver halide emulsion or to the developing solutions. It has been preferable to add the
hydrazine compounds to the emulsion, however, since the processing thereof can be better controlled. Research Disclosure 23510 (November 1983) presents a summary of the extensive literature on this subject. Although the use of hydrazine compounds reduced the induction period, these systems resulted in a loss of image quality such as lower dot quality, or the image may have a spotted appearance, or so-called "pepper". This is extremely undesirable and there have been numerous attempts in the prior art to reduce the propensity of the rapid access lithographic systems to produce pepper.
The developing solutions for elements containing hydrazine compounds typically contain conventional silver halide developing agents such as hydroquinone or derivatives of hydroquinone. It is sometimes necessary to add a super-additive developing agent such as phenidone or metol, for example. These developing solutions are necessarily kept at a fairly high pH which is deleterious to the life expectancy of the solution itself and to the processing equipment. Additionally, these prior art developing solutions tend to be environmentally hazardous and will produce sludge in the developing tanks. Ruger, U.S. Patent 4,937,160 teaches a novel group of hydrazides which can be used in a manner similar to the prior art hydrazines but with the advantage of somewhat lower processing pH. Silver halide elements containing these novel hydrazides, however, also suffer from the other disadvantages noted above, such as the appearance of "pepper" and the relative toxicity of the developer solutions.
The use of ascorbic acid or any of its derivatives as developing agents for silver halide elements, is
known in the prior art. For example, James, J. Amer. Che . Soc, Jan. 1944 (Communication No. 951 from the Kodak Research Laboratories) states that ascorbic and iso-ascorbic acid can be used as developing agents for silver halide elements. Similarly, James, U.S. Patent 2,688,549, teaches the use of a developer solution comprising 3-pyrazolidone and ascorbic acid or its sugar analogs. However, these prior art developing solutions were very slow and found little or no commercial success.
Recently, because ascorbic acid and its derivatives are environmentally safer than hydroquinone, there have been attempts to enhance conventional developing solutions by substituting ascorbic acid or erythorbic acid together with salts thereof for hydroquinone. For example, U.S. Appln. Ser. No. 07/472,803, filed Jan. 31, 1990, discloses a hydroquinone-free and alkali metal hydroxide-free developer solution wherein the developing agent consists of a salt of ascorbic or erythorbic acid either alone or in combination with ascorbic or erythorbic acid. In addition to the environmental advantage of removing hydroquinone from the developer solution, these developing agents are also environmentally advantageous because they tend to reduce the sludge commonly found in the developing tanks.
However, a shortcoming of the aforementioned ascorbate- containing developer solutions is that they cannot be used with hydrazine containing films to achieve satisfactory speed, contrast and image quality. The prior art ascorbate developer solutions are much lower in pH (e.g. 9.7-10) and are not formulated specifically for the rapid access processing of hydrazine films.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an improved system for rapid access processing of photographic silver halide elements comprising, in combination: a) a photographic silver halide element of the type containing a hydrazine compound; and b) a developer solution comprising at least one ascorbic acid developing agent selected from the group consisting of ascorbic acid, derivatives thereof, and salts of' either.
It is another object of the invention to provide an improved process of image formation comprising the step of developing an imagewise exposed photographic element of the type containing a hydrazine compound in a developer solution comprising at least one ascorbic acid developing agent selected from the group consisting of ascorbic acid, derivatives thereof, and salts of either. In is still another object of the invention to provide an improved rapid access developer solution for hydrazine containing films comprising an ascorbate developing agent, at least one alkanol amine and having a pH in the .range 10.65 to about 12.0. These and other objects of the invention will become apparent upon a further reading of the specification and the appended claims.
DETAILS OF THE INVENTION
The developing agents that are useful within the metes.and bounds of this invention include ascorbic acidr its derivatives, such as L- or D-ascorbic acid as well as erythorbic acid (also known as iso-erythorbic
acid) and the alkali salts of either, for example. These developing agents are effective when used alone or in combination with known hydroquinone developing agents. In the preferred embodiment, a mixture of sodium L-ascorbate and L-ascorbic acid or sodium erythorbate is the developing agent and no hydroquinone is present in the developer solution. The preferred embodiment also contains a small amount of a super- additive developer, such as l-phenyl-3-pyrazolidone or derivatives thereof, among others.
In addition to the above mentioned developing agents, the developer solutions of the present invention contain at least one alkanol amine in amounts suitable to effect the desired development rates. The alkanol amines suitable for use in the present developer solutions include those commonly employed by the prior art in the so-called wlith processing field," such as 1- piperidinethanol; 3-piperidino-l,2-propanediol; 1- methyl-2-piperidenemethanol; 1-(2-hydroxyethyl)- piperazine; 1,4-bis-(2-hydroxyethyl)-piperazine; diethanolamino ethanol; 3-(diethylamino)-1,2- propanediol; and N-butyl diethanol amine, among others. These compounds may be present in the developer solution in amounts of 5 to 50 grams per liter, and preferably in an amount of 20 grams per liter, of developer solution. Other developer adjuvants preferred for the developing solutions according to this invention include antioxidants (e.g. alkali metal sulfites) , sequestering agents (e.g. ethylene diamine tetraacetic acid, sodium salt), development accelerators (e.g. polyalkylene oxides) and the like. Buffers and pH adjusting compounds may also be mentioned here. Antifoggants and restrainers (KBr, Benzotriaizole PMT, etc.) may also be employed as is well known in the art.
Silver halide emulsions useful within the ambit of this invention include any of the commonly available silver halides such as silver bromide, silver chloride, silver iodide or mixtures of two or more of these halide salts. These emulsions may be precipitated by any of the conventional and well-know techniques such as splash or balanced double jet, for example. After precipitation of the grains in a small amount of gelatin, the grains are conventionally dispersed in a bulking amount of gelatin and then brought to their optimum sensitivity with gold and sulfur salts, as is well-known to those of normal skill in the art. Sensitizing dyes, antifoggants, dispersing agents, coating aids and hardeners may also be added if desired. Specifically, these emulsions will contain one of the prior art and known hydrazine compounds such as those previously described, with one of the hydrazides of the aforementioned Rϋger, U.S. Patent 4,937,160 preferably being used in accordance with the teachings of that patent. A most preferred silver halide emulsion will contain 98% bromide and 2% iodide, and will contain 80 g of gelatin per mole of silver halide present. This emulsion will be sensitized with sodium thiosulfate and green sensitizing dye and will contain 250 mg of 2-(4- Benzyloxyρhenyl)-l-Pyridinium acetyl-Hydrazine Bromide (BOP-HMP) per 1.5 moles of silver halide present. After full sensitization, standard antifoggants, coating aids, etc. are added and the emulsion coated on a 4 mil dimensionally stable, polyethylene terephthalate film support to about 4.4 g/m2 coating weight. Other useful supports such as cellulosic supports (e.g. cellulose acetate, etc.) and other common supports for the coating of silver halide elements which are well-known in the prior art may be used.
A typical and preferred developer solution of this invention will contain the following ingredients in the ranges shown.
Ingre ient Sodium Erythorbate Trisodium ethylenediamine- tetraacetic acid (Na3EDTA) Sodium Sulfite (Anhyr.) Potassium Bromide 45% KOH Soln. (aq.)
Dimezone S (4-Hydromethyl-4- methyl-l-phenyl-3-Pyrazoli- done) Benzotriazole Glucono delta Lactone l-Phenyl-5-Mercaptotetrazole Potassium Carbonate 2-Mercaptobenzothiazole 3-(Diethylamino)-1,2-
Propanediol N-butyl diethanol amine Water to
Adjust pH to at least 11.
This invention will now be illustrated by the following examples of which Example 2, using N-butyl diethanol amine is considered to be the best mode.
EXAMPLE 1
A standard control developer commonly used for the development of hydrazine containing films was prepared as follows:
Amount (g/liter of
Ingredient ork ng strength)
Na3EDTA 3.87 Sodium Bisulfite 62
Hydroquinone 25 Metol (N-Methyl-p-aminophenol sulfate) 1.5
KBr (Potassium Bromide) 3.0
3-(Diethylamino)-l,2-propanediol (DEAPD) 24.23 Benzotriazole 0.50 l-Phenyl-5-mercaptotetrazole (PMT) 0.05
Glucono Delta Lactone 1.0 45% Aq. KOH (Potassium Hydroxide
Solution) 105.6 Potassium Carbonate (anhy.) 53
Water to 1 liter
Another developer solution representative of this invention was prepared as follows:
Amount (g/liter of
Ingredient working strength)
Na3EDT 4 Sodium Sulfite 15
Sodium-L-Ascorbate 60
L-Ascorbic Acid 17
PMT 0.05
GDL 1.0 45% Aq. KOH 105
Potassium Carbonate 53
DEAPD 25
Dimezone S in Acetone 0.5 gm/25 ml
KBr 5.0 5-Methyl Benzotriazole 0.5
Water to 1 liter
The pH of both the control and developer of this invention were kept the same, e.g., 11.0 plus or minus 0.05 units. A film was prepared from an emulsion which comprised 98 mol % bromide and 2 mol % iodide dispersed in 80 gm of gelatin per mole of silver halide. This emulsion was brought to its optimum sensitivity by digestion with sodium thiosulfate (sulfur salt) and Green Sensitizing Dye for 40 minutes at a temperature of 130°F. After digestion, antifoggants, stabilizers, coating/wetting aids and hardeners were added as well- known to those of normal skill in the art along with 250 mg/1.5 mole of silver halide of a hydrazide such as that taught in the aforementioned Rϋger patent (BOP-HMP) . The emulsion was then coated to 4.4 g/m2 on a 4 mil biaxially oriented and heat-set polyethylene terephthalate film support having well-known resin and gel sub layers applied thereto. A thin layer of gelatin (e.g., 10 mg/dm2) was applied over the emulsion layer to act as a protective antiabrasion layer, as is well- known. Two samples of this film were taken and given an exposure (D. S. America Camera, halftone & continuous tone wedge targets, through a Beta GNE-MR Screen, 20 second exposure) and then developed 45 seconds at 95°F in a tray containing one of the above developers. Each developed sample was then fixed, washed and dried in the usual manner and the image analyzed for dot quality, speed, pepper, top density and contrast. The film developed in the developer of this invention had substantially equivalent speed, fog, contrast and density and had good dot quality as compared to the control. However, the film developed in the developer
of this invention had essentially no pepper as compared to that developed in the control developer.
EXAMPLE 2
The following ingredients were blended to make a stock solution representing the developer of this invention:
These ingredients were thoroughly mixed, diluted to 4,000 ml and the pH adjusted to 11.05. The following alkanol amines were tested at concentrations of 5,10,20 and 40 gm/liter for their efficacy in this developer solution:
1-piperidinethanol 3-piperidino-l,2-propandiol l-methyl-2-piperidenemethanol l-methyl-3-piperidenemethanol 1-(2-hydroxyethyl)-piperazine 1,4-bis-(2-hydroxyethyl)-piperazine Diethylamino ethanol
3-(Diethylamino)-1-2-propanediol N-butyl diethanol amine
All of the above developing solutions were tested with the film of Example 1 and gave excellent results as far as speed, contrast, dot quality and pepper. Additionally, the presence of the alkanol amine increased the developer activity as compared to the control developer. N-butyl diethanol amine is the preferred alkanol amine, not because of any superior results as compared to the other alkanol amines of this invention, but because it is less toxic and has a less objectionable odor.
EXAMPLE 3
To the standard control developer of Example 1, an addition of 5.0 gm/1 of sodium L-ascorbate was added and film prepared, exposed, developed for 60 seconds, fixed, washed and dried as in Example 1. A reading of the pepper- level on this film was made by examination with a 50X magnifier and compared to similarly treated film in the standard control developer. A very significant reduction in the size and frequency of the pepper spots was observed for the ascorbate-containing developer, without appreciable effect on sensitometry or deterioration in dot quality. Similar advantageous effects were observed when sodium D-isoascorbate, sodium erythorbate and dehydroascorbic acid were substituted for the sodium L-ascorbate.
EXAMPLE 4
In order to test a developer solution made according to this invention under machine processing conditions, the following solution was prepared:
These ingredients were thoroughly mixed and the solution diluted to 1 liter. The pH was adjusted to 11.4. Samples of this solution were placed in a desk-top. Convenience Processor® (E. I. du Pont de Nemours and Co., Wilmington, DE) and multiple strips of the same film described in Example 1 were processed through this machine over a period of several days. The developer functioned well and the sensitometric properties of the film were excellent. The pepper was low compared to controls "processed in an identical processor using a conventional, rapid access, hydroquinone-containing
developer. In addition, the life of the developer of this invention was considerably longer than the control developer. For example, a sample of standard, hydroquinone developer, left opened so that aerial oxidation could occur, darkened visibly and lost activity after a short period of time. Under the same conditions, the developer of this invention was much clearer and retained most of its activity.
Claims (22)
1. An improved system for rapid access processing of photographic silver halide elements comprising, in combination: a) a photographic silver halide element of the type containing a hydrazine compound; and b) a developer solution comprising at least one ascorbic acid developing agent selected from the group consisting of ascorbic acid, derivatives thereof, and salts of either.
2. The system of Claim 1, wherein said at least one ascorbic acid developing agent is sodium ascorbate.
3. The system of Claim 1, wherein said at least one ascorbic acid developing agent is a mixture of L- ascorbic acid and sodium ascorbate.
4. The system of Claim 1, wherein said developer solution further comprises a hydroquinone developing agent.
5. The system of Claim 1, wherein said photographic silver halide element comprises a gelatino, silver halide emulsion coated on a support.
6. The system of Claim 5, wherein said emulsion comprises 98 mol % Br and 2 mol % I and wherein said hydrazine compound is 2-(4-benzyl-oxyphenyl)-1- pyridinium acetyl)-Hydrazine Bromide.
7. The system of Claim 1, wherein said developer solution further comprises 5 to 50 gm/liter of an alkanol amine and has a pH in the range 10.7 to about 12.0
8. The system of Claim 1, wherein said developer solution comprises: Ingredient Amount Sodium Erythorbate 10-150 gm Trisodium Ethylenediamine- 1.0-10.0 gm tetraacetic acid (Na3ED A) Sodium Sulfite (Anhyr.) 10-150 gm Potassium Bromide 1.0-10.0 gm 45% KOH Soln. (aq.) 10-50 gm
Dimezone S (4-Hydromethyl-4-Methyl- 0.01-1.5 gm l-Phenyl-3-Pyrazolidone) Benzotriazole 0.1-1.5 gm
Glucono Delta Lactone 0.5-2.5 gm l-Phenyl-5-Mercaptotetrazole 0.01-0.20 gm Potassium Carbonate 10-100 gm 2-Mercaptobenzothiazole 0.01-20 gm 3-(Diethylamino)-1,2-Propanediol 5-50 gm 1-Piperidine ethanol 5-50 gm Water to 1 liter
9. A process of image formation comprising the step of developing an imagewise exposed photographic element of the type containing a hydrazine compound in a developer solution comprising at least one ascorbic acid developing agent selected from the group consisting of ascorbic acid, derivatives thereof, and salts of either.
10. The process of Claim 9, wherein said photographic element comprises a gelatino silver halide emulsion coated on a support and wherein said hydrazine compound is 2-(4-benzyl-oxyphenyl)-1-pyridinium acetyl- Hydrazine Bromide.
11. The process of Claim 9, wherein said at least one ascorbic acid developing agent is sodium ascorbate.
12. The process of Claim 9, wherein said developing agent is a mixture of sodium ascorbate and L- ascorbic acid.
13. The process of Claim 9, wherein said developer composition further comprises a hydroquinone developing agent.
14. The process of Claim 9, wherein said developer solution further comprises 5 to 50 gm/liter of an alkanol amine and has a pH in the range 10.7 to about 12.0.
15. An improved rapid access developer solution for hydrazine-containing films comprising at least one alkanol amine; at least one ascorbic acid developing agent selected from the group consisting of ascorbic acid, derivatives thereof, and salts -of either; and wherein said developing solution has a pH in the" range of 10.7 to about 12.0.
16. The developer solution of Claim 15, wherein said at least one ascorbic acid developing agent is sodium ascorbate.
17. The developer solution of Claim 15, wherein said at least one ascorbic acid developing agent is a mixture of L-ascorbic acid and sodium ascorbate.
18. The developer solution of Claim 15, further comprising a hydroquinone developing agent.
19. The developer solution of Claim 15, wherein said hydrazine-containing film comprises a gelatino, silver halide emulsion coated on a support.
20. The developer solution of Claim 19, wherein said emulsion comprises 98 mol % Br and 2 mol % I and wherein said hydrazine compound is 2-(4-benzyl- oxyphenyl)-1-pyridinium acteyl)-Hydrazine Bromide.
21. The developer solution of Claim 15, wherein said at least one alkanol amine comprises 5 to 50 gm/liter of N-butyl diethanol amine and said developer solution has a pH of about 11.0.
22. The developer solution of Claim 15, comprising:
Ingredient Amount
Sodium Erythorbate 10-150 gm Trisodium Ethylenediamine- 1.0-10.0 gm tetraacetic acid ( a3EDTA) Sodium Sulfite (Anhyr.) 10-150 gm
Potassium Bromide 1.0-10.0 gm
45% KOH Soln. (aq.) 10-50 gm Dimezone S (4-Hydromethyl-4-Methyl- 0.01-1.5 gm 1-Pheny1-3-Pyrazolidone) Benzotriazole 0.1-1.5 gm Glucono Delta Lactone 0.5-2.5 gm l-Phenyl-5-Mercaptotetrazole 0.01-0.20 gm Potassium Carbonate 10-100 gm
2-Mercaptobenzothiazole 0.01-20 gm
3-(Diethylamino)-1,2-Propanediol 5-50 gm
N-butyl ethanol amine 5-50 gm
Water to 1 liter
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US80134691A | 1991-12-02 | 1991-12-02 | |
US801346 | 1991-12-02 | ||
PCT/US1992/010219 WO1993011456A1 (en) | 1991-12-02 | 1992-12-02 | Improved developer systems for hydrazine containing films |
Publications (2)
Publication Number | Publication Date |
---|---|
AU3148693A true AU3148693A (en) | 1993-06-28 |
AU669142B2 AU669142B2 (en) | 1996-05-30 |
Family
ID=25180862
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU31486/93A Expired - Fee Related AU669142B2 (en) | 1991-12-02 | 1992-12-02 | Improved developer systems for hydrazine containing films |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0569580A1 (en) |
JP (1) | JPH06505574A (en) |
AU (1) | AU669142B2 (en) |
WO (1) | WO1993011456A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0585792B1 (en) * | 1992-09-04 | 1999-11-24 | Agfa-Gevaert N.V. | Process of recycling spent photographic developer and recycled photographic developer |
GB9226488D0 (en) * | 1992-12-19 | 1993-02-17 | Ilford Ltd | Photographic developing solution |
JP3148467B2 (en) * | 1993-06-18 | 2001-03-19 | 富士写真フイルム株式会社 | Image forming method |
AU689168C (en) * | 1993-06-18 | 2001-11-22 | Fuji Hunt Photographic Chemicals Pte Ltd | Non-hydroquinone photographic developer composition and processing method |
US5399457A (en) * | 1993-10-15 | 1995-03-21 | Minnesota Mining And Manufacturing Company | Process for reducing sludge in diffusion transfer printing plates |
US5925493A (en) * | 1994-05-09 | 1999-07-20 | Fuji Photo Film Co., Ltd. | Development processing method of silver halide photographic material and image forming method |
GB2290625B (en) * | 1994-06-22 | 1997-10-08 | Ilford Ltd | Concentrated photographic developing solution |
EP0690343B1 (en) * | 1994-06-27 | 2004-04-14 | FERRANIA S.p.A. | Photographic silver halide developer composition and process for forming photographic silver images |
DE69515776T2 (en) * | 1994-09-09 | 2000-07-27 | Konishiroku Photo Ind | Photographic processing method for processing a silver halide photographic light-sensitive material |
US5858611A (en) * | 1994-10-14 | 1999-01-12 | Fuji Photo Film Co., Ltd. | Development processing method of silver halide black-and-white photographic material |
JP3269929B2 (en) * | 1994-11-17 | 2002-04-02 | 富士写真フイルム株式会社 | Image forming method |
JP3508081B2 (en) * | 1995-10-30 | 2004-03-22 | コニカミノルタホールディングス株式会社 | Solid processing agent for silver halide photographic material and processing method |
US5589323A (en) * | 1996-01-23 | 1996-12-31 | Sun Chemical Corporation | Chemically stable ascorbate-based photographic developer and imaging process |
DE69702725T2 (en) * | 1996-03-04 | 2000-12-07 | Fuji Photo Film Co Ltd | Processing composition for silver halide photographic light-sensitive material, developer and processing method using the same |
EP0848287A1 (en) * | 1996-12-11 | 1998-06-17 | Imation Corp. | Photographic silver halide developer composition and process for forming photographic silver images |
DE102006026422A1 (en) | 2006-06-04 | 2007-12-06 | Orochemie Dürr + Pflug GmbH & Co.KG | developer concentrate |
CN104765244A (en) * | 2015-04-30 | 2015-07-08 | 石家庄太行科工有限公司 | Environment-friendly type developing solution and preparation method and application thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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BE770222A (en) * | 1970-07-20 | 1971-12-01 | Eastman Kodak Co | NEW DEVELOPERS FOR PHOTOGRAPHIC SILVER HALOGENIDE EMULSIONS IN INTERNAL OR SURFACE IMAGES |
IT1196972B (en) * | 1986-07-23 | 1988-11-25 | Minnesota Mining & Mfg | PHOTOGRAPHIC DEVELOPMENT COMPOSITIONS FOR SILVER HALIDES AND PROCEDURE FOR THE FORMATION OF SILVER PHOTOGRAPHIC IMAGES |
US4937160A (en) * | 1988-08-27 | 1990-06-26 | E. I. Du Pont De Nemours And Company | Photographic silver halide elements containing aryl hydrazides |
US4975354A (en) * | 1988-10-11 | 1990-12-04 | Eastman Kodak Company | Photographic element comprising an ethyleneoxy-substituted amino compound and process adapted to provide high constrast development |
US4988604A (en) * | 1990-05-24 | 1991-01-29 | Eastman Kodak Company | High contrast photographic element including an aryl sulfonamidophenyl hydrazide containing both thio and ethyleneoxy groups |
-
1992
- 1992-12-02 EP EP19920925425 patent/EP0569580A1/en not_active Withdrawn
- 1992-12-02 JP JP5510257A patent/JPH06505574A/en active Pending
- 1992-12-02 AU AU31486/93A patent/AU669142B2/en not_active Expired - Fee Related
- 1992-12-02 WO PCT/US1992/010219 patent/WO1993011456A1/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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JPH06505574A (en) | 1994-06-23 |
EP0569580A1 (en) | 1993-11-18 |
AU669142B2 (en) | 1996-05-30 |
WO1993011456A1 (en) | 1993-06-10 |
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