JPH05506727A - Silver removal from photographic products - Google Patents
Silver removal from photographic productsInfo
- Publication number
- JPH05506727A JPH05506727A JP91504601A JP50460191A JPH05506727A JP H05506727 A JPH05506727 A JP H05506727A JP 91504601 A JP91504601 A JP 91504601A JP 50460191 A JP50460191 A JP 50460191A JP H05506727 A JPH05506727 A JP H05506727A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- fixing agent
- accelerator
- bleach
- 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.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 34
- 239000004332 silver Substances 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000007844 bleaching agent Substances 0.000 claims abstract description 10
- -1 aliphatic thiol Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- 238000004061 bleaching Methods 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 8
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 7
- 229960003067 cystine Drugs 0.000 claims description 7
- 150000003573 thiols Chemical class 0.000 claims description 7
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 5
- 235000018417 cysteine Nutrition 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- OOTFVKOQINZBBF-UHFFFAOYSA-N cystamine Chemical compound CCSSCCN OOTFVKOQINZBBF-UHFFFAOYSA-N 0.000 claims description 3
- 229940099500 cystamine Drugs 0.000 claims description 3
- 239000000834 fixative Substances 0.000 claims description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000014509 gene expression Effects 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 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 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229940035024 thioglycerol Drugs 0.000 claims 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 230000007850 degeneration Effects 0.000 abstract 1
- 238000010186 staining Methods 0.000 abstract 1
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- PURYCGFBBYVQEQ-UHFFFAOYSA-N 1-(dimethylamino)ethanethiol Chemical compound CC(S)N(C)C PURYCGFBBYVQEQ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical group [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical group [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- KZTASAUPEDXWMQ-UHFFFAOYSA-N azane;iron(3+) Chemical compound N.[Fe+3] KZTASAUPEDXWMQ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004163 cytometry Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- 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
- G03C7/44—Regeneration; Replenishers
-
- 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
- G03C5/395—Regeneration of photographic processing agents other than developers; Replenishers therefor
- G03C5/3952—Chemical, mechanical or thermal methods, e.g. oxidation, precipitation, centrifugation
-
- 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
- G03C7/421—Additives other than bleaching or fixing agents
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
【発明の詳細な説明】 ０か゛のの、 ［ＩＬ星ＪＬ５ 本発明は、写真製品からの銀の除去における改良、特に漂白一定着工程中の好結 果での銀の除去を可能にするための現像された写真材料からの銀の除去における 改良に関する。[Detailed description of the invention] 0 or so, [IL Star JL5 The present invention provides improvements in the removal of silver from photographic products, particularly improved setting during the bleach-fixing process. in the removal of silver from developed photographic materials to enable the removal of silver in the final product. Regarding improvements.
ネガ写真製品の画像から銀を除去するためには、漂白工程に続いて定着工程を用 い、場合によっては両工程の間に洗浄工程を使用するのが普通である。カラー印 画紙のようなプリント材料については、漂白液を定着液と合わせて漂白一定着組 成物を得ることができる。しかしながら、この漂白一定着組成物の銀除去能カは 、カメラスピードの材料からすべての銀を除去するには不十分である。このこと は、現像された銀表面上に吸収された抑制物質によってひき起こされると考えら れる。A bleaching step followed by a fixing step is used to remove silver from images in negative photographic products. In some cases, it is common to use a washing step between the two steps. color stamp For printing materials such as paper, combine bleach with fixer to give a constant bleaching effect. can be obtained. However, the silver removal ability of this bleach-fixing composition is , camera speed is insufficient to remove all silver from the material. this thing is thought to be caused by inhibitors absorbed onto the developed silver surface. It will be done.
この結果、当技術分野における一つの問題は、ポジであろうとネガであろうと写 真製品の現像された銀表面から抑制する吸収物質を除去することである。As a result, one problem in the art is that photographs, whether positive or negative, The purpose is to remove inhibiting absorbing substances from the developed silver surface of the true product.
もう一つの問題は、銀回収のことである。使用済み写真試薬から銀を除去するこ とは通常のことである。これは、普通、別工程として化学的にあるいは電気分解 的に行なわれる。この回収の進行は、漂白一定着工程よりむしろ定着工程からよ り容易に達成され、さらに、もし銀の回収が、少なくとも大部分、別の除去処理 としてよりもむしろ写真材料からの錫除去処理の機能として達成されることがで きるならば、それは最も望ましいであろう。Another issue is that of silver recovery. Removing silver from used photographic reagents That is normal. This is usually done chemically or electrolytically as a separate process. It is carried out in a regular manner. This recovery progresses from the fixing step rather than the bleach-fixing step. furthermore, if silver recovery is at least in large part a separate removal process. can be achieved as a function of tin removal processing from photographic materials rather than as If possible, that would be most desirable.
これらの問題は、一部、ＵＳ−Ａ−３，８９３，８５８で言及された。この開示 においては、特定の脂肪族チオール類から選択される促進剤を、錫除去を助ける ためにｆ更用する。これらのチオールは１個以上の可溶化基と組み合わせたチオ ール基を含む化合物から選択することができる。These problems were mentioned in part in US-A-3,893,858. This disclosure In the present invention, accelerators selected from certain aliphatic thiols are used to aid in tin removal. Therefore, f is changed. These thiols are thiols in combination with one or more solubilizing groups. It can be selected from compounds containing a metal group.
しかしながら我々は今、促進剤が漂白一定着工程の前に前浴としてそれ自体使用 される場合には、それらの有効寿命は商業的に相当する価値のあるほど十分に長 くはなく、一方、もし促進剤が漂白一定着液に添加されるならば、この促進剤は 、放置すると漂白一定着液中で促進剤がそれ自体と反応する結果として汚染をひ き起こす傾向があることを発見した。これらの理由で、促進剤の使用は最近数年 間は当分野において一般的ではない。However we now know that the accelerator uses itself as a pre-bath before the bleach-fixing step. where their useful life is long enough to have commercial value On the other hand, if an accelerator is added to the bleach constant deposition solution, this accelerator If left unattended, the accelerator will react with itself in the bleaching solution, resulting in contamination. I discovered that there is a tendency to cause For these reasons, the use of accelerators has declined in recent years. time is not common in the field.
我々は今、これらの安定性の問題は、漂白一定着液を生成する定着液に促進剤を 添加することによって対処することができることを見出した。このことは２つの 効果を持ち；第一にはそれによって促進剤を安定化させてその活性寿命を増大さ せ、そして第二には、その安定化作用がその後のすべての汚染の問題を軽減する 。しかしながらさらに重要なことには、銀の除去を定着液段階で行なうことがで きる。We now address these stability issues by adding an accelerator to the fixing solution that produces a constant bleaching solution. We have found that this can be addressed by adding This means that there are two primarily by stabilizing the accelerator and increasing its active life. and secondly, its stabilizing action reduces all subsequent contamination problems. . More importantly, however, silver removal can be done at the fixer stage. Wear.
従って、定着液中に促進剤を包含することは、製品の品質を向上させ、一方で、 注意するとそれによって定着液段階からの有効な銀の除去が可能であり、以前に 必要とされた別の銀回収工程なしに銀の回収を可能にする、という効果を有する 。Therefore, the inclusion of accelerators in the fixer improves the quality of the product, while With care, effective silver removal from the fixer stage is possible and previously It has the effect of allowing silver recovery without a separate silver recovery step required. .
本発明に従う好ましい具体化においては、銀の回収は、促進剤と銀錯化合物との 相互作用の結果としての、容易に回収することができる銀生成物の沈殿により、 濾過のような通常の固体／液体分離法によって実施される。In a preferred embodiment according to the invention, the recovery of silver is carried out using a promoter and a silver complex compound. Due to the precipitation of silver products as a result of the interaction, which can be easily recovered, This is carried out by conventional solid/liquid separation methods such as filtration.
このため、本発明の第一の観点に従えば、定着剤組成物の一部として促進剤が存 在することを特徴とする、画像的に露光されカラー現像された写真要素を、漂白 一定着剤と接触させて金属銀を酸化してこれを要素から除去する前に、定着剤と 接触させ、このとき上記要素を漂白促進量のチオール〔このチオールは、モノチ オール−グリセロール、シスチン、シスタミン、システィンおよび式：（式中、 Ｒ’およびＲｔは各々別個にＨ，ＣＨ，またはＣ□Ｈ３であり、そしてｎは１か ら３までの値を有する整数である）のアミノアルキレンチオール類から選択され る〕またはその写真に有効な塩、から選択される促進剤とも接触させる、写真処 理法が提供される。Therefore, according to the first aspect of the invention, an accelerator is present as part of the fixer composition. Bleaching of imagewise exposed and color developed photographic elements characterized by A fixing agent and a fixing agent are used to oxidize the metallic silver and remove it from the element by contacting it with a fixing agent. The above elements are then brought into contact with a bleach-promoting amount of thiol [this thiol is a monothiol]. All-glycerol, cystine, cystamine, cystine and the formula: (wherein, R' and Rt are each independently H, CH, or C□H3, and n is 1 or is an integer having a value up to 3). or a photographically effective salt thereof. The logic is provided.
本発明の好ましい形においては、定着剤はチオ硫酸塩または化学的に類似した化 合物より成り、そして漂白一定着液には第二鉄アミノポリカルボン酸が含まれる 。In a preferred form of the invention, the fixing agent is a thiosulfate or chemically similar compound. The bleaching solution contains ferric aminopolycarboxylic acid. .
本発明の別の観点においては、画像的に露光されカラー現像された銀含有写真要 素を、漂白一定着液と接触させる前に定着剤と接触させる、写真処理から銀を回 収する方法が提供されるが； この回収方法は、定着剤にモノチオグリセロール、シスチン、シスタミン、シス ティン、および式 （式中、Ｒ１およびＲｔは各々にＨ，ＣＨ，またはＣ２Ｈ４であり、そしてｎは １から３までの値を有する整数である）のアミノアルキレンチオール類から選択 される促進剤を添加し、これによって銀を銀塩として沈殿させ、それにより漂白 一定着段階の前に反応媒質から事実上銀を除去することより成る。In another aspect of the invention, an imagewise exposed and color developed silver-containing photographic element is provided. The silver is removed from the photographic process by contacting the fixing agent before contacting the bleaching solution. Although a method is provided to collect; This recovery method uses fixatives such as monothioglycerol, cystine, cystamine, and ting, and expression (wherein R1 and Rt are each H, CH, or C2H4, and n is selected from aminoalkylenethiols (an integer having a value from 1 to 3) Adding an accelerator that precipitates the silver as a silver salt, thereby bleaching It consists in substantially removing silver from the reaction medium before the deposition step.
好ましくは、漂白一定着剤はチオ硫酸塩であり、そして銀は、硫化銀または銀チ オールの沈殿として除去される０本発明に従う好ましい促進剤は、ジメチルアミ ノエタン−チオール、（ＤＭＡＥＴ）およびそのチオウロニウム誘導体、チオグ リセロール、システィンおよびシスチンである。Preferably, the bleach-fixing agent is a thiosulfate and the silver is silver sulfide or silver sulfide. A preferred promoter according to the present invention is dimethylamino acid, which is removed as a precipitate of Noethane-thiol, (DMAET) and its thiouronium derivative, thiog These are lycerol, cysteine and cystine.
本発明は今、下記の実施例および添付されている図面を参照して、具体的記載の みによって説明されるであろう、添付図面中：図１は、標準のＣ−４１法によっ て処理されたコダカラー（Ｋｏｄａｃｏｌｏｒ） Ｖ Ｒ１００フイルムのセン シトメトリーのグラフを示す。これを、実施例の方法によって処理された同一フ ィルムと比較する。The invention will now be described in detail with reference to the following examples and the accompanying drawings. In the accompanying drawings, which may be explained by reference: FIG. Kodacolor V R100 film processed by A graph of cytometry is shown. This is the same file processed by the method of the example. Compare with film.
図２は、標準のＣ−４１法によって処理されたコダカラー（Ｋｏｄａｃｏｌｏｒ ） Ｖ Ｒ２００フイルムのセンシトメトリーのグラフを示す、これを、実施例 の方法によって処理された同一フィルムと比較する。Figure 2 shows Kodacolor processed by the standard C-41 method. ) V V R200 film sensitometry graph. Compare with the same film processed by the method.
図３は、標準のＣ−４１法によって処理されたコダカラー（Ｋｏｄａｃｏ Ｉｏ ｒ） Ｖ Ｒ４００フイルムのセンシトメトリーのグラフを示す、これを、実施 例の方法によって処理された同一フィルムと比較する。Figure 3 shows Kodacolor (Kodaco Io) processed by standard C-41 method. r) Shows the graph of sensitometry of V R400 film, which was carried out Compare with the same film processed by the example method.
図４は、標準のＣ−４１法によって処理されたコダカラー（Ｋｏｄａｃｏｌｏｒ ） Ｖ Ｒ１０００フイルムのセンシトメトリーのグラフを示す。これを、実施 例の方法によって処理された同一フィルムと比較する。Figure 4 shows Kodacolor processed by the standard C-41 method. ) V Shows a graph of sensitometry of R1000 film. Implement this Compare with the same film processed by the example method.
これらの図は、本方法が最終的なセンシトメトリーにはほとんど効果をもたない かまたは全く効果をもたない、すなわち対照法によって処理されたフィルムは、 画像の観点からは、標準のＣ−４１法において処理されたものと区別がつかない であろう、ことを証明している。These figures show that our method has little effect on the final sensitometry. or have no effect at all, i.e. films processed by the control method have From an image perspective, it is indistinguishable from that processed in the standard C-41 method. It proves that it is.
実施例 商業的に人手し得る物質を使用して、次の処方に従って定着液を製造した：実験 用促進性定着液 チオえヤア７エユウェ ３２０ｇ エチレンジアミン四酢酸（ＥＤＴＡ） ２ｇメタ重亜硫酸ナトリウム ８ｇ ジメチルアミノエタンチオール（ＤＭＡＥＴ） ５ｇ１リツトルにするだけの水 この溶液のＰＨを、酢酸の添加によって６．５に調整した。Example A fixer was prepared using commercially available materials according to the following recipe: Experimental accelerating fixer Chioeyaa7Eyuwe 320g Ethylenediaminetetraacetic acid (EDTA) 2g Sodium metabisulfite 8g Dimethylaminoethanethiol (DMAET) 5g Water to make 1 liter The pH of this solution was adjusted to 6.5 by addition of acetic acid.
商業的に入手できる物質を用いて、次の処方に従って漂白一定着液を製造した： 実験用漂白一定着液 １．５６Ｍ アンモニウム鉄（ＩＩＩ）ＥＤＴＡ溶液 ７５Ｍ１チオ硫酸アンモ ニウム ６０ｇ 亜硫酸ナトリウム ８ｇ １リツトルとする量の水 εの溶液のＰＨを、酢酸の添加によって６．０に調整した。A bleach constant solution was prepared using commercially available materials according to the following recipe: Experimental bleaching constant liquid 1.56M ammonium iron(III) EDTA solution 75M1 ammonium thiosulfate Nium 60g Sodium sulfite 8g 1 liter of water The pH of the solution of ε was adjusted to 6.0 by the addition of acetic acid.
現像液、漂白液および定着液を、コダック（Ｋｏｄａｋ）Ｃ−４１２０リツトル キツトを使用して、このキットボックスに封入された取扱説明書に従って、調合 した。The developer, bleach, and fixer were added to a Kodak C-4120 liter bottle. Use the kit and follow the instructions included in this kit box to prepare the mixture. did.
４稲のコダック（Ｋｏｄａｋ）カラ御名ガフィルム、ＶＲｌｏｏ、ＶＲ２００、 ＶＲ４００、ＶＲｌｏｏＯのストリップを、０．２対数露光量センシトメトリー ウエツジにより模倣の昼光に０．０１秒間露光させた。これらのストリップを２ ４時間保持した後、下記の方法によって処理した：Ｃ−４１現像液 ３７．８° Ｃ３’１５’実験用定着液 ３７，８°ｃ ｉ’ ｏｏ“実験用漂白一定着液 ３７．８°Ｃ２’００“洗浄 ３５．０℃ ３’００’ 乾燥 ２０゜ 同様の露光さね、時間のたったフィルムのストリップを、Ｃ−４１のマニュアル に記載された通りの標準のＣ−４１法で処理した。この処理されたストリップを 、マクベス（Ｍａｃｂｅｔｈ）濃度計を用いて測定し、比較した０図１−４は、 この４種の異なるフィルムについての結果を示している。すべでのストリップ中 の残留銀の水準Ｄｍａｘはすべて、Ｘ線蛍光スペクトロスコピーにより何らかの 信鯨をもって検出されることができる値、すなわち２５■／ｓｑ、ｍ、、よりも 小さかった。4Kodak Karaminaga film, VRloo, VR200, VR400 and VRlooO strips were subjected to 0.2 logarithmic exposure sensitometry. The wedge was exposed to simulated daylight for 0.01 seconds. 2 of these strips After holding for 4 hours, it was processed by the following method: C-41 developer 37.8° C3'15' experimental fixer 37,8°c i' oo' experimental bleach constant fixing solution 37.8°C 2’00” Washing 35.0°C 3’00’ Dry 20° A similar exposed and aged strip of film was prepared using the C-41 manual. The standard C-41 method was used as described in . This treated strip , measured using a Macbeth densitometer and compared. The results for these four different films are shown. Stripping in all directions The residual silver level Dmax of all than the value that can be detected with confidence, i.e., 25 ■/sq, m, It was small.
この実験を、実験用定着液中のＤＭＡＥＴの代りに多くの他の化合物をすべて濃 度５ｇ／ｌで使用してくり返した。下記の表１は、実験用の定着剤を使用し、す べての場合に２’００’間実験用漂白一定着液を使用して、異なる実験用定着液 を用いる実験法で処理された４種のフィルムの赤、緑および青Ｄｍａｘ濃度を示 す。This experiment can be repeated by adding a number of other compounds in place of DMAET in the experimental fixer. It was used repeatedly at 5 g/l. Table 1 below shows the results using experimental fixatives. Using the experimental bleach constant fixing solution for 2'00' in all cases, different experimental fixing solutions were used. The red, green and blue Dmax densities of four films processed by the experimental method using vinegar.
Ｆｌ（ｉ、 ７ 相対対数露光量 相対対数露光量 Ｆｌ５．２ ＦＩ５．３ ＦＩ５４ 浄書（内容に変更なし） 要 約 書 １′）”のの、 本発明は、画像的に露光さにカラー現像された写真要素を、漂白剤および定着剤 で処理することに存する。定着剤は、促進剤としての脂肪族チオールを包含する 。定着剤中に存在する促進剤は、商業的に使用することができるように定着剤と 安定させ、また同時に漂白定着浴中のチオールの退化の結果として起こる汚染を 予防する。Fl(i, 7 relative logarithmic exposure relative logarithmic exposure Fl5.2 FI5.3 FI54 Engraving (no changes to the content) Summary book 1') The present invention provides a method for preparing color developed photographic elements imagewise exposed to light using a bleaching agent and a fixing agent. It consists in processing. Fixing agents include aliphatic thiols as promoters . The accelerator present in the fixing agent is the same as the fixing agent so that it can be used commercially. Stabilizes and at the same time eliminates contamination that occurs as a result of thiol degradation in bleach-fix baths. Prevent.
本発明はまた、別の錫除去段階を除去する、定着浴からの有効な銀除去手段をも 提供する。The present invention also provides an effective means for removing silver from the fixing bath, eliminating a separate tin removal step. provide.
平成 ５年 ５月〉２日May 2nd, 1993
Claims (10)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9005130.1 | 1990-03-07 | ||
| GB909005130A GB9005130D0 (en) | 1990-03-07 | 1990-03-07 | Silver removal from photographic products |
| PCT/EP1991/000406 WO1991014205A1 (en) | 1990-03-07 | 1991-03-05 | Silver removal from photographic products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05506727A true JPH05506727A (en) | 1993-09-30 |
Family
ID=10672186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP91504601A Pending JPH05506727A (en) | 1990-03-07 | 1991-03-05 | Silver removal from photographic products |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0518905B1 (en) |
| JP (1) | JPH05506727A (en) |
| AT (1) | ATE108032T1 (en) |
| DE (1) | DE69102696T2 (en) |
| GB (1) | GB9005130D0 (en) |
| WO (1) | WO1991014205A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1290812B (en) * | 1965-06-11 | 1969-03-13 | Agfa Gevaert Ag | Process for bleach-fixing silver photographic images |
| GB1150466A (en) * | 1966-05-06 | 1969-04-30 | Fuji Photo Film Co Ltd | Improvements in Colour Photography Processes |
| GB1411985A (en) * | 1972-10-18 | 1975-10-29 | Ilford Ltd | Silver recovery process |
| JPS5946386B2 (en) * | 1979-05-09 | 1984-11-12 | 富士写真フイルム株式会社 | Bleaching composition for photographic processing |
| US4707434A (en) * | 1984-08-20 | 1987-11-17 | Konishiroku Photo Industry Co., Ltd. | Color image forming method comprising processing with a bleach-fixing solution |
| AU588898B2 (en) * | 1985-07-18 | 1989-09-28 | Konishiroku Photo Industry Co., Ltd. | Method of processing silver halide color photographic material |
-
1990
- 1990-03-07 GB GB909005130A patent/GB9005130D0/en active Pending
-
1991
- 1991-03-05 DE DE69102696T patent/DE69102696T2/en not_active Expired - Fee Related
- 1991-03-05 AT AT91904935T patent/ATE108032T1/en not_active IP Right Cessation
- 1991-03-05 WO PCT/EP1991/000406 patent/WO1991014205A1/en active IP Right Grant
- 1991-03-05 JP JP91504601A patent/JPH05506727A/en active Pending
- 1991-03-05 EP EP91904935A patent/EP0518905B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB9005130D0 (en) | 1990-05-02 |
| ATE108032T1 (en) | 1994-07-15 |
| WO1991014205A1 (en) | 1991-09-19 |
| DE69102696D1 (en) | 1994-08-04 |
| EP0518905B1 (en) | 1994-06-29 |
| EP0518905A1 (en) | 1992-12-23 |
| DE69102696T2 (en) | 1994-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS57144547A (en) | Silver halide color photosensitive material and its processing method | |
| JP2859965B2 (en) | How to stabilize photographic elements | |
| US6232052B1 (en) | Photographic processing compositions containing stain reducing agent | |
| JPS60123837A (en) | Photographic silver halide emulsion | |
| EP1109063A1 (en) | Photographic processing methods using compositions containing stain reducing agent | |
| US2203653A (en) | Integral mask for color film | |
| JPH06503183A (en) | Photographic silver halide development processing method, silver halide materials and solutions therefor | |
| JPH05506727A (en) | Silver removal from photographic products | |
| US2623822A (en) | Method of obtaining multicolored photographic images of increased color density | |
| US1966330A (en) | Process for making two-color subtractive photographic prints on double-coated film | |
| US2195419A (en) | Process for reducing the density of silver images and compositions therefor | |
| JP2634646B2 (en) | Stabilization of silver halide photographic images | |
| JPH07107599B2 (en) | Dot etching method for halftone silver halide images. | |
| JPH0126048B2 (en) | ||
| US3210189A (en) | Photographic reversal process | |
| USRE22977E (en) | Bleaching bath and process for | |
| US3664838A (en) | Treatment of and developing composition for photographic light-sensitive materials | |
| US2263009A (en) | Gold sound track in motion picture film | |
| US1552791A (en) | of bochester | |
| US2860978A (en) | Photographic washing accelerators | |
| US2541490A (en) | Tone control in photographic development | |
| US2218001A (en) | Process for making colored prints | |
| JPS5895342A (en) | Processing method for photosensitive material | |
| US1632740A (en) | Indttstrie axtiengesellschaft | |
| US3183087A (en) | Color reversal development process utilizing a preliminary development bath free of bromide ions |