US2748000A - Removing silver and silver halide from photographic elements - Google Patents
Removing silver and silver halide from photographic elements Download PDFInfo
- Publication number
- US2748000A US2748000A US420302A US42030254A US2748000A US 2748000 A US2748000 A US 2748000A US 420302 A US420302 A US 420302A US 42030254 A US42030254 A US 42030254A US 2748000 A US2748000 A US 2748000A
- Authority
- US
- United States
- Prior art keywords
- silver
- halide
- removal
- image
- fixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052709 silver Inorganic materials 0.000 title claims description 87
- 239000004332 silver Substances 0.000 title claims description 87
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 65
- -1 silver halide Chemical class 0.000 title description 34
- 238000000034 method Methods 0.000 claims description 32
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000084 colloidal system Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 29
- 239000000839 emulsion Substances 0.000 description 23
- 229910021607 Silver chloride Inorganic materials 0.000 description 19
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 19
- SUVZGLSQFGNBQI-UHFFFAOYSA-N 2,5-bis(sulfanyl)hexanedioic acid Chemical compound OC(=O)C(S)CCC(S)C(O)=O SUVZGLSQFGNBQI-UHFFFAOYSA-N 0.000 description 18
- 239000000975 dye Substances 0.000 description 16
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 16
- 239000007844 bleaching agent Substances 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 12
- 238000004061 bleaching Methods 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 3
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- CYXJEHCKVOQFOV-UHFFFAOYSA-N (4-amino-2-methylphenyl) hydrogen sulfate Chemical compound CC1=CC(N)=CC=C1OS(O)(=O)=O CYXJEHCKVOQFOV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- VAEMGHXAIBEXNI-UHFFFAOYSA-N 2-hydroxyethanedithioic acid Chemical compound OCC(S)=S VAEMGHXAIBEXNI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000006629 Prosopis spicigera Nutrition 0.000 description 1
- 240000000037 Prosopis spicigera Species 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- MPLZNPZPPXERDA-UHFFFAOYSA-N [4-(diethylamino)-2-methylphenyl]azanium;chloride Chemical compound [Cl-].CC[NH+](CC)C1=CC=C(N)C(C)=C1 MPLZNPZPPXERDA-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- BNOQSGWAWRCQRK-UHFFFAOYSA-L disodium;2-[2-[2-(carboxylatomethylsulfanyl)ethylsulfanyl]ethylsulfanyl]acetate Chemical compound [Na+].[Na+].[O-]C(=O)CSCCSCCSCC([O-])=O BNOQSGWAWRCQRK-UHFFFAOYSA-L 0.000 description 1
- NQTSMPMGYLBQMI-UHFFFAOYSA-L disodium;2-[2-[2-[2-(carboxylatomethylsulfanyl)ethylsulfanyl]ethylsulfanyl]ethylsulfanyl]acetate Chemical compound [Na+].[Na+].[O-]C(=O)CSCCSCCSCCSCC([O-])=O NQTSMPMGYLBQMI-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 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
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- G03C5/38—Fixing; Developing-fixing; Hardening-fixing
-
- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
Description
May 29. 1956 M MADER 2,
P. REMOVING SILVER AND SILVER HALIDE FROM PHOTOGRAPHIC ELEMENTS Filed April 1, 1954 EXPOSURE Ag G/, RED SENS/77VE CYAN COUPLE R MAGENTA COUPLER Ag 6/, GREEN 5EN5'/T/VE /NTERNAL LATENT lMAGE (Ag Br) BLUE SENS/T/VE SUPPORT STAGE l GOLOR DEVELOPER OYAN DYE, Ag, Ag G/ MAGENTA DYE,Ag, AgG/ LA TENT /MA6E 0F BLUE SENS/J r/0/v //v Ag Br SUPPORT l FIXING-BLEACH GYAN DYE MAGENTA DYE LATENT lMAGE 0F BLUE SENSAT/O/V /N Ag Br SUPPOR T l "50/. VEN 7"0EVELOPER /2 a a 0 0 0 0 0 o a o O o cyA/v DYE /0 fSUPPORT PAUL M. MA DE R IN V EN TOR.
ATTORNEY 8 AGE T United States Patent 2,748,000 -REMOVING SILVER AND SILVER HALIDE FROM PHOTOGRAPHIC ELEMENTS Paul M. Mader, Rochester, N. Y., assignor toEastman Kodak"Company,'Roehester, N. Y., a corporation of Application April 1, 1954, Serial No. 420,302 15 Claims. (Cl. 95-88) This invention relates to the removal of silver and silver 'halide from photographic elements. A'variety of agents for these-purposes are-known and theselection depends on the requirements of the particular *process'involved. Thus in conventional development of a silver'halide-latent image toablack silver image it is desired to remove residual silver halide without attacking developed silver. This can be done with thiosulfate or thiocyanate solutions. In other instances it is desired to remove a developed silver .imagewithout'aflecting residualundeveloped silver halide, :for example, in "direct positive development where negative metallic silver is removed "beforeth'e residual silver Jhalideis'developedto 'thesilverpositive image. The re- .rn'oval'is'etfectedwith 'an'oxidizingbath, such as potassium tdichromate=sulfurie 'acide, 'or potassium "permanganate- :sulfuric acid solution. These "bte'aches convert the silver to solublesi'lver salts which diffuse out of the emulsion layer, Without attacking the residual silver :halide.
.Instillrother case'siit may-'ibe desirable ttoremove both zsilver and :silvenhalideasis truein some .color processes. "-Tlihismayzbe .done .with.a..potassium cyanide solution or with .an oxidizing .bleach solution, .such .as idichromate,
ferricyanide, or .quinone, containing .or .followed by. a silver salt solvent .to sensurememoval .of both the oxidized iirnage silver andlhe. residual. silver. halide.
It is diflicult to find otherwise satisfactory silver halide solvents of suflicient stability for use in the presence of the strongly'oxidizing'bleach compounds. 'There are also instances where 'it'is advantageous tobe able to remove the image silver along with a distinct part of the residual silver halide, for example, the silver chloride, while 'leaving comparativelyunaifec'ted another portion-comprising,
. for example, silver 'bromide.
.l have discovered a group of related compounds which are silver-salt sol-vents and useful for the removal of silver h'alide from photographi'c layers. 'Some'of them compare favorably with alkali thiosulfates and 'thiocyamates in the orthodox fixing process and in addition have the unusual and beneficial properties of exceptional sta- -bility solutions not .only to acids and --alkalies but to -.the oxidizing agents commonly used in combination :bleaching and fixing baths for the removal of both silver and silver salts from photographic layers. Furthermore,
1 they show ase'lectivity-"or specificityin solvent activity for different silver salts commonly used in photographic layers.
These compounds are sulfur-containing diabasic acids f the-general formula:
in which n l, 2, or 3 alkali metal or ammonium salts These compounds are useful as fixing agents to remove silver halide from hydrophilic organic colloid layers of photographic elements. CompoundsZ and 3 are not very soluble in Water in'the acid form and are preferably used as .the salts, e. g.,the sodium salt. The ethylene-bis-thioglycolic acid may be used either in acid or salt form. It has the advantageous .property of dissolving silver chloride at a much faster rate than it dissolves silver bromide, so that it canbe usedfor the selectiveremoval of the chloride in thepresence of the bromide. Sodium chloride, sodium sulfite, and certain other silver halide solvents show a similar selective fixing action, but they have one or more shortcomings which make them impractical in many applications, e. g., slow rate of dissolving, instability in the presence of oxidizing agents, low activity, etc.
The 'Ihomologous compounds of ethylene-.bis-thioglycolic acid in which the ethylene .chain between the two sulfur atoms is replaced with methylene, propylene, tetramethylene, or higher alkylene groupings form considerably weaker complexes than does the ethylene derivative Coni- ".pound :1,: and:hence their potential value as'fixin'g agents -tdoes not approa'hihat of 1ethylene bis-thioglycolic acid.
The exceptional stability of the fixing agents, Compounds 1, :2,and 3,'becomes'apparentwhen they are used :inicombination bleaching *Jand fixing solutions for the 3removalof silverfrom'emulsions or other silver colloid layers, such'as colloidal silver ifilter layers in photo graphic "elements. This can, of course, be "done 'by the conven- 'tional method of firstoxidizing'th'e silver to a silver'halide 'by'itreatment withiferricyanide=bromide, or the like, and
' theirremoving'thesilver'halide thus'formed in a separate fixing :bath, suchas the conventionalshypo solution. it is .much more" convenient Ito "accomplish the oxidizing and bleaching operation and the solution of the silver salt in one step. A number of one :b'ath solutions for this :purpose are known, e. g., a reducer such as ferrocyanideilrypo solutiommight vbe used. Such baths, h0W6V6l','Zli
iusuallynot suificientlystable. .My compounds enable the preparation of .a combined bleaching and fixing-solution of good stability, excellent solvent properties for both silwer andsilverhalide, .and capable of formula and use modifications .to.permitremoval of the silver and all the residual .silverhalide or of the silver along with selective removal .of .the .silverchloride without appreciable attack "on .the .silver bromide.
Accordingly, -aqueous .solutionscontaining a mixture of a silver oxidizing agent such as guinone or an alkali metal ferricyanide and one of the "above sulfur-containing dibasic acids are very effective in the removal of silver from "hydrophiliccolloidlayers of photographic elements.
Aparticul'ar application of 'one of the dibasic sulfur compounds of the invention, ethylene-bis-thioglycolic jacid,"isin the simultaneous removal of a silver image and silverchloridefrom "a "system containing'both silver chloride "and "silver bromide as described in more detail in the following examples. In this case it is found that a *solutionof amixture'of an oxidizing agent, e. g., quinone, and the-dibasic sulfur'compound serves not only to dissolve the silver image but the ability of the ethylene-bisthioglycolic acid to selectively remove silver chloride from the system in the presence of silver bromide is not impaired by the presence of the oxidizing agent.
An important advantage of the mentioned bleachingfixing solutions containing oxidizing agent and one of the sulfur-containing dibasic acids lies in the high stability of the solutions. For example, a solution containing ethylene-bis-thioglycolic acid and quinone was found to lose none of its power for fixing silver chloride or removing silver from a colloid layer after standing for eight days although the solution had darkened appreciably. Similarly, a solution of ethylene-bis-thioglycolic acid and potassium ferricyanide at a pH of 6.5 which had been stored 50 days still fixed silver chloride and oxidized silver at the same rate as When the solution was first prepared. Also, the solution did not become discolored over this period of time.
The compositions of the invention containing a mixture of one of the dibasic sulfur compounds and an oxidizing agent, such as ethylene-bis-thioglycolic acid and potassium ferricyanide, find use as a reducer for removing metallic silver slowly from a photographic image in a manner similar to Farmers Reducer as shown in the following examples. In this case, when ferricyanide is used as the oxidizing agent, the concentration is maintained at a low level to prevent formation of silver ferrocyanide in the image.
The accompanying drawings illustrate in cross-sectional view the appearance of a color film at various stages in the formation of colored images in the film and the selective removal of silver and silver chloride from the film in the presence of an exposed silver bromide emulsion.
My invention is described in more detail in the following examples with reference to the accompanying drawings.
EXAMPLE I A two-layer color film was prepared as described in U. S. Patent 2,490,751 and shown in Stage 1 of the accompanying drawings as having a support 10 carrying a gelatino silver halide emulsion layer 11 containing a mixture of a green-sensitive silver chloride emulsion, magenta coupler and a blue-sensitive silver bromide emulsion of the internal latent image type. Coated thereon is a redsensitive silver chloride emulsion layer 12 containing a cyan coupler. The film was exposed to a colored subject and samples were processed in the following processes, Process A representing a process using the conventional bleaching and selective fixing steps and Process B incorporating the combined fixing-bleaching step of the invention.
Process A (70 F.)
Minutes Color develop 12 Stop 1 Wash 5 Bleach Wash 5 Selective fix 9 Wash 10 Develop (I) 5 Fix (I) Wash 10 Process B (70 F.)
Minutes Color develop 12 Stop 1 Wash 5 Fix-bleach 15 Wash 5 Develop (II) 5 Rinse Fix (II) 3 Wash 10 The processing solutions had the following compositions:
Color developer:
Sodium hexametaphosphate grams 1 NazSOa (10 12 2-amino-5-diethylaminotoluene hydrochloride do 3 NezCOs-HzO do 20 KBr do 2 H2O liter 1 Stop bath:
Acetic acid (glacial) grams 20 H2O liter 1 Bleach bath:
KzCrzOw "grams" 2 H2O liter 1 H2504 to make pH=1.9
Selective fix:
NazSOs grams H2O liter.. 1
Developer 1:
Monomethyl-p-aminophenol sulfate grams 2.2 NazSOa d0 96.0 Hydroquinone do 8.8 NazCOs d0 48.0 KBr do... 5.0 KI do 6.0 NaOH do 10.0 H2O liter.. 1
Developer II:
Monomethyl-p-aminophenol sulfate grams.. 2.2 Na2SO3 do 96.0 Hydroquinone do 8.8 Na2CO3 dO 48.0 KBr do 5.0 NazSzOa d0 5.0 H20 liter.. 1
Fix I:
(NH4)2S2O3 grams 250 NazSOs do 10 H2O to make 1 liter Fix II:
Water, about F. (50 C.) cc 600 Sodium thiosulfate, pentahydrate grams 240.0 Sodium sulfite, desiccated do 15.0 Acetic acid, 28% cc 48.0 Boric acid, crystals grams 7.5 Potassium alum do e 15.0 Cold water to make 1.0 liter Fix-bleach:
Ethylene-bis-thioglycolic acid grams 16 Quinone do 3.5 H20 liter.. 1
Accordingly, in Process A, color development forms silver and magenta and cyan dye images in layers 11 and 12 of the film, the bleach and selective fixing steps removing the silver images and residual silver chloride from the film, leaving the dye images and exposed silver bromide emulsion in the film. Subsequent development with the developer I yields a silver image of the blue sensation in layer 11. This developer can, of course, be replaced by a solvent type of yellow image-forming color developer such as shown in U. S. Patent 2,490,791 to yield a yellow dye image in layer 11 together with the previously developed magenta dye image and the cyan image in layer 12.
Process B embodying the combined fixing-bleaching step of the invention is illustrated in the accompanying drawings wherein the exposed element of Stage 1 of the drawings described above is shown in Stage 2 of the drawings following color development, stop bath and washing steps, ascontaining magenta"an'd"cyan dye-images 'in layer 11.
Following development of the element of the third stage 'of'the drawings with the 'black-and-white Tsolvent developer II, or a solvent typeof yellow color-forming developer, such'as shown in U. S/Patent 2,490,751, the element contains a silver, or silver and yellow dye image and the magenta dye image in layer 11 as Wellas a cyan dye image in layer .12 as describedin Stage 4 of .the drawings. In case a solvent type of color developer has been used in the last development step, the resultant silver image can be removed with the fixing-bleach bath of the invention or by conventional methods, leaving only cyan, magenta and yellow dye images in the film.
When sensitometric curves of the subtractively colored dye images formed in the conventional Process A were compared with the curves of the dye images formed in Process B of the invention, it was found that the comparable dye images of the two processes had the same contrast, and other sensitometric characteristics of the element of Process B were favorable. In particular, the desired contrast and other characteristics were obtained in Process B in the image corresponding to the blue light exposure.
A fixing-bleaching bath containing about 2 to grams of potassium ferricyanide and about 16 grams of ethylenebis-thioglycolic acid per liter at a pH of about 6.5 can be used for the removal of silver images in processes such as that described in the above example. However, the rate of removal of silver is somewhat lower than when the quinone-containing fixing-bleaching solution is used.
In those processes such as present-day color development processes, in the final stages of which it is desired to remove silver images and all residual silver halide in the presence of color-developed dye images, very satisfactory results will be obtained with a fixing-bleach bath containing an alkali salt of Compound 3 above in conjunction with ferricyanide.
EXAMPLE 2 The mentioned use of the sulfur-containing dibasic acids in conjunction with an oxidizing agent as a reducer for the slow removal of silver from silver images in a manner similar to Formers reducer is demonstrated by first forming a silver image in a light-sensitive film or paper product followed by fixing in the usual manner. The film is then treated in a solution of the following composition:
Ethylene-bis-thioglycolic acid grams 4.0 Water cc 250.0 Sodium hydroxide to bring pH to 6.5
Potassium ferricyanide grams 0.75
Treatment of a silver image developed in a high-speed negative film with this solution at 70 C. for seconds, 1 minute, 3 minutes and 8 minutes, gave silver densities as follows:
1. Untreated image 1.85 2. 30-second treatment 1.76 3. l-minute treatment 1.65 4. 3-minute treatment 1.42 5. 8-minute treatment 0.8
After holding the above solution for 49 days, the solution gave a silver density of 0.94 at Log E 3.6 when the same silver image was reduced.
The activity "of i'the reducer solution appears to be intermediate "between a proportional and a subtractive reducer solution.
"Thefollowingexampleillustrates the use of Compound '3'-for-the removal of silver-and silver halide'fromphotographic elements.
EXAMPLE 3 A multilayer .product having blue, greenand red- -sensitive,gelatin emulsionlayers superposed in that order on a paperbase was provided. The emulsion layers con- .tained dispersions of color-forming couplers for forming subtractively colored dye images of colors complementary 'to the-sensitivity of the .respective emulsion layers. .The
..paper wasexposed in.the usual manner to a color negative and developed 8 :minutes in a conventional color developing solution containinga primary aromatic amino silver halide developing agent to obtain silver and dye images in the emulsion. layers.
After color development the .paper was treated 1 /2 .minutes with a 1 aaceticacid .stop bath followed'by a 4 .minute wash and .10 .minutes with a fix-bleach bath :0.'05 .molar in sodium-3,6,9,12-tetrathiatetradecanedioate wherein n represents a positive integer of from 1 to 3 and alkali metal and ammonium salts thereof.
2. A fixing-bleach composition for silver halide emulsion layers, comprising an aqueous solution of a mixture of quinone and ethylene-bis-thioglycolic acid.
3. A fixing-bleach composition for silver halide emulsion layers, comprising an aqueous solution of a mixture of potassium ferricyanide and ethylene-bis-thioglycolic acid.
4. A fixing-bleach composition for silver halide emulsion layers, comprising an aqueous solution of a mixture of potassium ferricyanide and sodium 3,6,9,l2-tetrathiatetradecanedioate.
5. A process for the removal of silver from photographic elements which comprises treating a supported hydrophilic organic colloid layer containing silver with an aqueous solution of a mixture of (1) a member of the class consisting of quinone and an alkali metal ferricyanide, and (2) a compound having the general formula wherein n represents a positive integer of from 1 to 3 and alkali metal and ammonium salts thereof.
6. A process for the removal of silver from photo graphic elements which comprises treating a supported hydrophilic organic colloid layer containing silver with an aqueous solution of a mixture of quinone and ethylenebis-thioglycolic acid.
7. A process for the removal of silver from photographic elements which comprises treating a supported hydrophilic organic colloid layer containing silver with an aqueous solution of a mixture of potassium fern'cyanide and ethylene-bis-thioglycolic acid.
8. A process for the removal of silver from photographic elements which comprises treating a supported hydrophilic organic colloid layer containing silver with an aqueous solution of a mixture of potassium ferricyanide and sodium 3,6,9,l2-tetrathiatetradecanedioate.
9. A process for the selective removal of silver chloride from a photographic emulsion layer in the presence of an emulsion layer containing silver bromide, which comprises treating the silver chloride in the presence of the silver bromide with an aqueous solution of ethylenebis-thioglycolic acid, until the silver chloride has been removed leaving silver bromide in an emulsion layer.
16. A process for the removal of silver from a photographic element containing a silver image, silver chloride and silver bromide which comprises treating said element with an aqueous solution of a mixture of quinone and ethylene-bis-thioglycolic acid until the silver and silver chloride have been removed leaving silver bromide in the element.
11. A process for the removal of a silver image from a photographic element containing a silver image, silver chloride and silver bromide which comprises treating said element with an aqueous solution of a mixture of quinone and ethylene-bis-thioglycolic acid until the silver and silver chloride have been removed leaving silver bromide in the element.
12. A process for the removal of silver halide from a hydrophilic-organic colloid photographic emulsion layer containing silver halide which comprises treating said layer with an aqueous solution of a compound having the general formula wherein n represents a positive integer of from 1 to 3 and alkali metal and ammonium salts thereof.
13. A process for the removal of silver halide from a hydrophilic organic colloid photographic emulsion layer containing silver halide which comprises treating said layer with an aqueous solution of sodium 3,6,9-trithiahendecanedioate.
14. A process for the removal of silver halide from a hydrophilic organic colloid photographic emulsion layer containing silver halide which comprises treating said layer with an aqueous solution of sodium 3,6,9,l2-tetrathiatetracanedioate.
15. A process for the removal of silver chloride from a hydrophilic organic colloid photographic emulsion layer containing silver halide which comprises treating said layer with an aqueous solution of ethylene-bis-thioglycolic acid.
References Cited in the file of this patent UNITED STATES PATENTS 2,331,678 Hanson Oct. 12, 1943
Claims (1)
- 5. A PROCESS FOR THE REMOVAL OF SILVER FROM PHOTOGRAPHIC ELEMENTS WHICH COMPRISES TREATING A SUPPORTED HYDROPHILIC ORGANIC COLLOID LAYER CONTAINING SILVER WITH AN AQUEOUS SOLUTION OF A MIXTURE OF (1) A MEMBER OF THE CLASS CONSISTING OF QUINONE AND AN ALKALI METAL FERRICYAMIDE, AND (2) A COMPOUND HAVING THE GENERAL FORMULA
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US420302A US2748000A (en) | 1954-04-01 | 1954-04-01 | Removing silver and silver halide from photographic elements |
| GB8962/55A GB765053A (en) | 1954-04-01 | 1955-03-28 | Improvements in photographic processing |
| FR1131908D FR1131908A (en) | 1954-04-01 | 1955-04-01 | Process for the elimination of silver or silver halides present in photographic layers and produced for the implementation of this process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US420302A US2748000A (en) | 1954-04-01 | 1954-04-01 | Removing silver and silver halide from photographic elements |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2748000A true US2748000A (en) | 1956-05-29 |
Family
ID=23665914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US420302A Expired - Lifetime US2748000A (en) | 1954-04-01 | 1954-04-01 | Removing silver and silver halide from photographic elements |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US2748000A (en) |
| FR (1) | FR1131908A (en) |
| GB (1) | GB765053A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3156562A (en) * | 1960-10-14 | 1964-11-10 | Murray N Gladstone | Reproduction of photographic images on ceramic surfaces |
| US3210189A (en) * | 1961-12-20 | 1965-10-05 | Ciba Ltd | Photographic reversal process |
| US3716362A (en) * | 1969-07-30 | 1973-02-13 | Ciba Geigy Ag | Process for the removal of metallic silver from photographic material |
| EP0458277A2 (en) * | 1990-05-21 | 1991-11-27 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
| US5162106A (en) * | 1989-10-12 | 1992-11-10 | The Governors Of The University Of Alberta | Photographic fixer regeneration |
| US5171658A (en) * | 1989-04-26 | 1992-12-15 | Eastman Kodak Company | Method of photographic processing |
| EP0652477A1 (en) * | 1993-11-09 | 1995-05-10 | Eastman Kodak Company | Acceleration of silver removal by thioether compounds in sulfite fixer |
| US5633124A (en) * | 1992-05-08 | 1997-05-27 | Eastman Kodak Company | Acceleration of silver removal by thioether compounds |
| JP2890272B2 (en) | 1991-04-16 | 1999-05-10 | 富士写真フイルム株式会社 | Photo-bleach-fixing composition and method for processing color photographic light-sensitive material using the same |
| JP2890271B2 (en) | 1990-05-21 | 1999-05-10 | 富士写真フイルム株式会社 | Photo-fixing composition and method for processing photographic light-sensitive material using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2331678A (en) * | 1941-01-09 | 1943-10-12 | Eastman Kodak Co | Differential fixing solution |
-
1954
- 1954-04-01 US US420302A patent/US2748000A/en not_active Expired - Lifetime
-
1955
- 1955-03-28 GB GB8962/55A patent/GB765053A/en not_active Expired
- 1955-04-01 FR FR1131908D patent/FR1131908A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2331678A (en) * | 1941-01-09 | 1943-10-12 | Eastman Kodak Co | Differential fixing solution |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3156562A (en) * | 1960-10-14 | 1964-11-10 | Murray N Gladstone | Reproduction of photographic images on ceramic surfaces |
| US3210189A (en) * | 1961-12-20 | 1965-10-05 | Ciba Ltd | Photographic reversal process |
| US3716362A (en) * | 1969-07-30 | 1973-02-13 | Ciba Geigy Ag | Process for the removal of metallic silver from photographic material |
| US5171658A (en) * | 1989-04-26 | 1992-12-15 | Eastman Kodak Company | Method of photographic processing |
| US5162106A (en) * | 1989-10-12 | 1992-11-10 | The Governors Of The University Of Alberta | Photographic fixer regeneration |
| EP0458277A2 (en) * | 1990-05-21 | 1991-11-27 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
| EP0458277A3 (en) * | 1990-05-21 | 1991-12-18 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
| US5429914A (en) * | 1990-05-21 | 1995-07-04 | Fuji Photo Film Co., Ltd. | Composition having a fixing ability for photography and method for processing photographic materials with the same |
| JP2890271B2 (en) | 1990-05-21 | 1999-05-10 | 富士写真フイルム株式会社 | Photo-fixing composition and method for processing photographic light-sensitive material using the same |
| JP2890272B2 (en) | 1991-04-16 | 1999-05-10 | 富士写真フイルム株式会社 | Photo-bleach-fixing composition and method for processing color photographic light-sensitive material using the same |
| US5633124A (en) * | 1992-05-08 | 1997-05-27 | Eastman Kodak Company | Acceleration of silver removal by thioether compounds |
| EP0652477A1 (en) * | 1993-11-09 | 1995-05-10 | Eastman Kodak Company | Acceleration of silver removal by thioether compounds in sulfite fixer |
| US5424176A (en) * | 1993-11-09 | 1995-06-13 | Eastman Kodak Company | Acceleration of silver removal by thioether compounds in sulfite fixer |
Also Published As
| Publication number | Publication date |
|---|---|
| GB765053A (en) | 1957-01-02 |
| FR1131908A (en) | 1957-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2748000A (en) | Removing silver and silver halide from photographic elements | |
| JP3045311B2 (en) | Photo color processing method | |
| US3770437A (en) | Photographic bleach compositions | |
| JPS6146820B2 (en) | ||
| JPH03253853A (en) | Stabilization of photographic factor | |
| JP2622839B2 (en) | Bleaching parts composition | |
| US2515121A (en) | Process for preventing stains in photographic color material by treatment with basic acids immediately prior to drying | |
| US6156488A (en) | Photographic bleach compositions | |
| US4040837A (en) | Photographic bleach-fixer | |
| DE2411249A1 (en) | METHOD FOR TREATMENT OF COLOR PHOTOGRAPHIC MATERIALS | |
| US5445925A (en) | Method of forming a photographic color image | |
| US4153459A (en) | Hybrid color photographic elements and processes for developing same | |
| US2657139A (en) | Process of removing color developer stain in azine dye images | |
| US3259497A (en) | Photographic color reversal process | |
| GB2216677A (en) | Two stage process for the rapid development of colour materials. | |
| US5246822A (en) | Method of photographic processing | |
| US3761262A (en) | Photographic color developing process | |
| US2706687A (en) | Preventing formation of prussian blue stain in color developed photographic prints | |
| US3942984A (en) | Process for bleach-fixing chromogenically color photographic silver halide material | |
| DE2101344A1 (en) | Process for the production of color copy material | |
| US2483971A (en) | Antistain baths for sensitive color photographic material | |
| US3664838A (en) | Treatment of and developing composition for photographic light-sensitive materials | |
| US2515122A (en) | Process for preventing stains in photographic color material by the use of a fixing bath-consisting of water, an alkali sulfite, and a fixing agent | |
| US4194911A (en) | Inhibitor removing bath for direct positive color photographic development | |
| JPS5811617B2 (en) | Silver halide color photographic material processing method |