WO2005054947A1 - Photographic bleach composition - Google Patents
Photographic bleach composition Download PDFInfo
- Publication number
- WO2005054947A1 WO2005054947A1 PCT/GB2004/004233 GB2004004233W WO2005054947A1 WO 2005054947 A1 WO2005054947 A1 WO 2005054947A1 GB 2004004233 W GB2004004233 W GB 2004004233W WO 2005054947 A1 WO2005054947 A1 WO 2005054947A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- iron
- optionally substituted
- agent
- iii
- Prior art date
Links
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000008139 complexing agent Substances 0.000 claims abstract description 49
- 229910052709 silver Inorganic materials 0.000 claims abstract description 33
- 239000004332 silver Substances 0.000 claims abstract description 33
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 230000002140 halogenating effect Effects 0.000 claims abstract description 21
- 230000000536 complexating effect Effects 0.000 claims abstract description 18
- 230000001376 precipitating effect Effects 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 90
- 229910052742 iron Inorganic materials 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 29
- -1 silver ions Chemical class 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 15
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical class CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- WWVBXWRCQNSAKA-UHFFFAOYSA-N 2-[butyl(carboxymethyl)amino]acetic acid Chemical compound CCCCN(CC(O)=O)CC(O)=O WWVBXWRCQNSAKA-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 2
- AQFJPHAVWFBQQY-UHFFFAOYSA-N 2-[carboxymethyl(propyl)amino]acetic acid Chemical compound CCCN(CC(O)=O)CC(O)=O AQFJPHAVWFBQQY-UHFFFAOYSA-N 0.000 claims 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 4
- 229910001626 barium chloride Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 3
- QHHFAXFIUXRVSI-UHFFFAOYSA-N 2-[carboxymethyl(ethyl)amino]acetic acid Chemical compound OC(=O)CN(CC)CC(O)=O QHHFAXFIUXRVSI-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 150000001649 bromium compounds Chemical group 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 1
- 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 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical group CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- MSFPLIAKTHOCQP-UHFFFAOYSA-M silver iodide Chemical class I[Ag] MSFPLIAKTHOCQP-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000010626 work up procedure 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
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A photographic bleach composition comprising an iron (III) complex as an oxidising agent and a silver precipitating or complexing agent, preferably a halogenating agent, is prepared by treating an iron (III) source a solution of an iron (III) complexing agent, which solution is the product mixture in the preparation of the iron (III) complexing agent in which the silver precipitating or complexing agent, preferably halogenating agent, is formed as a by-product. The resultant composition may be used as a bleach composition, preferably a rehalogenating bleach composition, without the addition of bromide ions or other silver precipitating or complexing moiety.
Description
Photographic Bleach Composition
FIELD OF THE INVENTION The present invention relates to the field of photographic bleach compositions and, in particular, to a method of making photographic bleach compositions that are biodegradable. More particularly, the present invention is concerned with a method of making a photographic bleach composition comprising ailjAlirrnnodiacetic acid complexed iron (III) as the major oxidant and a method of maldng the alkylim odiacetic acid for use in a bleach composition.
BACKGROUND OF THE INVENTION
Photographic bleaches axe used to remove silver from photographic material carrying developed images during photographic processing so that only image dye remains in the photographic material. The bleaches typically comprise an oxidizing agent, for oxidizing metallic silver particles to silver (I) ions, and a halogenating agent, for converting the silver ions to silver halide, which is then soluble in the bleach solution and can be removed from the photographic material. A bleach composition may also consist of other components for modifying pH, or for scavenging other metal ions that may be present and may also be combined with a fixing agent, such as arnmonium thiosulphate, to form a bleach-fix composition. The halogenating agent is typically a bromide, such as potassium bromide. The halogenating agent, and any other components are typically added to an aqueous solution of the oxidizing agent.
Conventionally, bleach baths have often been based on alkali metal ferricyanide as the oxidizing agent, because it gives fast and effective bleaching. For the most part, this has been superceded in commercially used bleach or bleach-fix baths by iron (III) ions complexed with a suitable iron-complexing
agent, which is typically ethylenediarnine tet aacetic acid (EDTA), 1,3- prσpyleneάiamine tetraacetic acid (1,3 PDTA) or mtrilotriacetic acid (NTA).
A number of alternative, biodegradable ligands (or complexing agents) have been developed, such, as
acid derived ligands. Memyli inodiacetic acid (MID A), for example, does not have the same toxicity obj ections as the ferrocyanide bleach and even the EDTA and PDTA ligands.
MIDA can be made by reaction of hydrogen cyanide, formaldehyde and an aliylamine via a cyanohydrin intermediate and can be prepared such that the product can be used in preparing a bleach solution without further purification.
An alternative preparation for MIDA is described by Berchet (Organic Syntheses, Combined Volume 2, 397) and utilised in US-A-4294914 (see Example 2) as a ligand m. a photographic bleach solution by complexing with1 iron (III), to which was added ammoniu i bromide as a rehalogenating agent in the bleach. According to this method of preparing MIDA, methylarni e is added to an aqueous solution of two equivalents of chloroacetic acid in the presence of a base. In the preparation of commercial bleaches, it is necessary to remove the chloride by-product to prevent corrosion of equipment. The chloride is removed using barium chloride.
The two described methods of preparing MIDA are not ideal for use in the preparation of commercial rehalogenating bleach compositions because formaldehyde and hydrogen cyanide used in the cyanohydrin route described above are hazardous materials, which are preferably avoided, and because barium chloride, which is involved in the necessary removal of chloride from the reaction mixture in the chloroacetic acid route to prevent corrosion of equipment, is toxic.
PROBLEM TO BE SOLVED BY THE INVENTION
It is desirable to improve the process for preparing biodegradable photographic bleach compositions comprising complexed iron (III) as the bleach by avoiding the use of hydrogen cyanide, formaldehyde and barium chloride. It is also desirable to prepare bleach compositions without the necessity to isolate intermediate ligands so that the bleach composition may be prepared in a one-pot reaction. There is, therefore, a need for an improved process for preparing iron (III) bleach compositions and for preparing biodegradable ligands for use in such iron(III) bleach compositions, which processes avoid the use of toxic materials and at the same time provides a more efficient process. ' SUMMARY OF THE INVENTION
According to a first aspect of the invention, there is provided a process for the preparation of a photographic bleach composition, the process comprising freating a solution of an iron complexing agent, which solution further comprises a silver precipitating or complexing moiety for precipitating or complexing silver ions, with an iron (III) source to form an iron (III) oxidising agent, characterized in that the silver precipitating or complexing moiety is a by-product in the preparation of the iron complexing agent. Generally, the silver precipitating or complexing moiety according the first aspect of the invention is preferably a halogenating agent. It is preferable that the halogenating agent is a bromide. It is also preferable that the iron complexing agent is an optionally substituted
acid. According to a second aspect of the invention, there is provided a process for the preparation of an optionally substituted alj linunodiacetic acid iron
complexing agent, comprising reacting an optionally substituted bromoacetic acid with an optionally substituted allcylamine in the presence of a base.
In a triird aspect of the invention, there is provided the use of an optionally substituted bromoacetic acid in the preparation of an alkylirrn'norliacetic acid complexing agent for use in a rehalogenating photographic bleach.
ADVANTAGEOUS EFFECT OF THE INVENTION The preparation of an iron complexing agent, such as optionally substituted aDcyliminocftacetic acid, for use in a photographic bleach composition in such a way that as a by-product of that preparation a silver precipitating or complexing moiety, especially a halogenating agent (such as a bromide) is provided, enables the preparation of the iron complexing agent and subsequently the photographic bleach composition to be carried out in a one-pot synthesis without the necessity of adding a silver precipitating or complexing moiety, for example a bromide, or other rehalogenating agent, to the bleach solution to provide precipitation or complexing of silver ions, by for example rehalo enation. Furthermore, where the iron complexing agent is a substituted ah yliminodiacetic acid, the process of preparing that agent whereby a bromide is a by-product of the reaction enables the product mixture to be used in preparing a bleach solution without purification, and avoids the use of undesirable components such as barium chloride, hydrogen cyanide and formaldehyde.
DETAILED DESCRIPTION OF THE INVENTION
In the general sense, the present invention is concerned with a process for preparing a bleach solution by treating a solution of an iron complexing agent with an iron (Til) source to form an iron (ffi) oxidising agent, where the. solution of the iron complexing agent comprises, as a by-product in its preparation, a silver ion precipitating or complexing moiety, which when it precipitates or complexes silver
ions to form a silver compound or complex, is soluble in the fix solution to be used so that the silver can be washed form the photographic material.
The by-product from the reaction in which the iron complexing agent is formed could be a fhiosulphate, for example, whereby a bleach-fix solution would be formed on treatment with an iron (III) source. In this embodiment, the thiosulphate would be a silver complexing moiety which would be capable of forming a complex with silver and the silver complex formed would be soluble in the bleach-fix solution and would then be washed from the photographic material.
The by-product as a silver precipitating or complexing moiety according to the invention could be any silver ion precipitating or complexing moiety, such as halides or phosphates, for example, but is preferably a halide. • The embodiments of the invention described herein with reference to a halide as the silver precipitating or comlexing moiety may alternatively be applied to any silver precipitating or complexing moiety, in a more general sense.
More particularly, therefore, the invention provides a process of preparing a photographic bleach composition where a solution of an iron complexing agent and a halogenating agent is treated with an iron (III) source to form an oxidizing agent as a complex between iron (III) and the iron complexing agent. The halogenating agent, which is suitable for rehalogenating silver ions (for example, those oxidized from silver by the oxidizing agent) is a by-product of the reaction in which the iron complexing agent is formed.
Preferably, the iron complexing agent intermediate used for forming the iron (TJT) oxidizing agent is not isolated prior to use in the process for preparing the photographic bleach composition. For example, the product mixture in the iron complexing agent preparation may be used without significant work up procedures or without undertaking a purification procedure.
This enables the photographic bleach composition to be prepared in a simple and efficient manner, for example, in a "one-pot" synthesis whereby the reaction to prepare the iron complexing agent is carried out, then the product mixtur© treated with a source of iron HTD to produce a rehaloσenatin<τ bleach solution comprising an iron (Til) oxidizing agent and a halogenating agent without the necessity of adding further halogenating agent to the bleach solution.
The invention is particularly applicable to commercial bleach solutions where it is normally necessary to ensure any chloride ions are absent or njirrirnised to prevent corrosion of equipment. Such a commercial bleach solution would be required, for example,' for use in commercial photographic mini-labs.
The source of iron (ILT) for use in the present invention may be any suitable iron (111) source that allows iron (III) to complex with the iron complexing agent in ! aqueous solution. Examples of iron (331) sources according to the invention include iron (III) nitrate, sulfate and acetate, preferably as hexahydrate salts. Preferably, iron (LU) nitrate is utilised. One advantage of using iron (111) nitrate is that it provides an anti-corrosive effect. The halogenating agent can be any material that facilitates the halogenation of silver or silver ions to silver halide. Examples of suitable halogenating agents include alkali metal halides, preferably chlorides, bromides or iodides, preferably sodium bromide or potassium bromide. In any case the preferred halogenating agent is a bro inating agent, because in the photographic processing of colour negative film, the fix solution is less effective if silver iodides are formed and it is more difficult to form silver chlorides during the rehalog ating bleaching step unless a particularly strong bleach is utilised. The halogenating agent is typically formed by loss of a bromine anion from one of the starting materials in the preparation of the iron complexing agent, e.g. from bromoacetic acid in the formation of an alkylirrrinodiacetic acid, which may be picked up by a counter-ion available in the reaction mή ture, which may be, for example, potassium from potassium hydroxide if used as a base.
The iron complexing agent (or ligand) according to the present invention may be any compound capable of forming a complex with iron (Til) so as to be capable of oxidizing silver to silver (I). The complexing agent may be mono-, di- or tri-dentate, for example, and there may be required one or more- complexing agents to form an effective complex with iron (111).
Preferably, the complexing agent is an optionally substituted alkylmrinodiacetic acid. The complexing agent (or ligand) should be soluble in the bleach solution. The alJAlirninodiacetic acid may have a straight chain or branched alkyl group, which may be substituted or unsubstituted. Preferably, the alkyl group is a substituted or unsubstituted C1-C12 straight chain or branched alkyl group, more preferably a substituted or unsubstituted Cι-C6 straight chain or branched alkyl group, still more preferably a substituted or unsubstituted methyl, ethyl, (iso)propyl or butyl group and most preferably a methyl or ethyl group. The alkylirninodiacetic may also be substituted on the α-carbon of one or both of the acetic acid groups, for example with a hydroxy group, a fluorine or a methyl group. Suitable substituents on the alkyl group of the alkyljniinodiacetic acid may include, for example, a carboxylic acid group (i.e. CO H), hydroxy, methylamido, sulphonate or methylsulphonarnido, at any point on the alkyl chain. For example, the alkyl group may be a propanoic acid group (e.g. -CH2-CH2-CO2H). As another example, for a C12 alkyl group, the substituent may be a solubilizing group such as a carboxylic acid group or sulphonate.
Preferred optionally substituted alkylirninodiacetic acid include melnyliminodiacetic acid (MIDA), ethyliminodiacetic acid (EIDA), propyljmjinodiacetic acid (PLOA) and butyliminodiacetic acid (BID A), most preferably MTD A or EIDA.
The optionally substituted alVyh'τnirιorK acetic acid, as the complexing agent, is prepared, according to the invention, by treating an optionally substituted bromoacetic acid with optionally substituted a∑ ylaniine in ύie presence of a base. The base may be, for example, any strong base having a pKb of less than one, may „be an organic or inorganic base, but is preferably an alkah metal hydroxide such as sodium hydroxide or potassium hydroxide. In order to achieve the stoichiometry of the desired aH yljrninodiacetic acid, it is necessary to employ 2 moles of bromoacetic acid per mole of the alq amine. However, excess alkylamine not directly involved in the reaction can be used. Preferably, at least 4 molar equivalents of base are utilized.
The reaction of the alkylamine with bromoacetic acid in the presence of a base is exothermic. The reaction temperature should be controlled so as to minimise the formation of glycolic acid as a by-product. Where the base is a strong base such as potassium hydroxide, it is preferable that the temperature should be kept below 50° C, more preferably below 30°C, during addition of the base to bromoacetic acid solution. The temperature of the reaction during and following addition of the alkylamine should be maintained at or below 50°C, preferably at or below 30°C, to minimise the formation of side products. •
As mentioned above, in a preferred embodiment of the present invention, the product mixture formed in the preparation of the iron (III) complexing agent is utilised directly in the preparation of the bleach composition. Addition of an iron (III) source, such as iron (ffl) nitrate, yields a rehalogenating bleach composition comprising an iron (III) oxidizing agent and a halogenating agent, without the necessity to add a halogenating agent.
Typically the preparation of the bleach composition involves adding an iron (III) source to a well-stirred iron (III) complexing agent solution. Optionally, a calcium ion scavenger, such as Dequest ™ 2000 (50% a ino tris(methylene phosphonic acid) solution), available from Monsanto, may be added to the bleach
composition. Glacial acetic acid may also be added. The pH may be adjusted as desired, for example by addition of potassium hydroxide or acetic acid.
There m ^ also bs added to the bleach composition one or more additional iron (III) complexing agents, such as EDTA, 1,3-PDTA and a second complexing agent according to the invention.
There may be a wide variation in the proportion of iron (III) ions present in the composition to iron (III) complexing agent. For example, where an allςylrniinodiacetic acid is the complexing agent, there may be a ratio of aljAliminodiacetic acid to iron (III) ions of from 1:1.5 to 15:1, preferably 1:2 to 5:1, more preferably 1:2 to 1:4 and most preferably about 1:3. The proportion of iron (III) ions to (one or more) iron (III) complexing agent may be adjusted as desired.
In a most preferred embodiment of the present invention, a bleach composition is prepared by treating an aqueous solution of bromoacetic acid with methylamine in the presence of an alkali metal hydroxide as base, under controlled temperature conditions as described above; to the completed reaction mixture adding a second iron (III) complexing agent, preferably 1,3-PDTA and adding iron (111) nitrate without adding any additional bromide. The second complexing agent is preferably the minor component, present in a ratio of MLDA to 1,3-PDTA of, for example, 5:1 to 40:1, preferably 10:1 to 30:1, most preferably 10:1 to 20:1. The invention will now be further illustrated without limitation by the following specific examples.
EXAMPLES
Example 1 Preparation of MIDA
279 g (2 mol) bromoacetic acid was placed in 150 ml water in a 2 L flask provided with a mechanical stirrer, separating funnel and thermometer. The flask was cooled in ice water and a cold solution of 224 g (4 mol) potassium hydroxide in 500 ml water was added, with stirring, from the separating funnel at such a rate as to maintain the temperature at 30" C or below. Following addition of the alkali solution, the cooling bath was removed and an aqueous solution containing 3 Ig (1 mol) was slowly added to the reaction mixture. The resulting reaction is exothermic and the temperature of the reaction nήxture was maintained below 50° C by controlling the rate of addition of the melnylamine solution and by occasional immersion of the flask in ice water. Following addition of the methylarnine, the reaction mixture was allowed to stand for 2 hours to allow completion of the reaction to form methylinrinodiacetic acid (MIDA).
Preparation of rehalogenating bleach composition
To this mixture was added 1 L demineralised water and 19 g glacial acetic acid. 35g Dequest ™ 2000 (50% amino tris(methylene phosphonic acid)) was added to the mixture. 225 g 42% iron (III) nitrate solution was then added with vigorous stirring. The pH of the solution was adjusted to 4.64 with 10% potassium hydroxide solution. The total volume was made up to 2.5 L to give a biodegradable rehalogenating bleach without the addition of bromide.
Example 2
MIDA was prepared as per Example 1, and used in the form of the product mixture.
Prep oration of rehalogenating bleach composition
To the IvQDA solution was added 1 L demineralised water, 20 ml glacial acPtir aciH anr) 19 σ 1 -PTVTΔ T i<= as fn]1r.w<=>rl hv 36 5 ml T rme< f ™ 2000 To this was added 237 g 42% iron (HI) nitrate solution with vigorous stirring. The pH of the solution was adjusted to 4.64 with 10% potassium hydroxide solution. The total volume was made up to 2.5 L to give a biodegradable rehalogenating bleach without the addition of bromide. The present invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims
1. A process for the preparation of a photographic bleach composition, said process comprising treating a solution of an iron complexing agent, which solution further comprises a silver precipitating or complexing moiety for precipitating or complexing silver ions, with an iron (III) source to form an iron (III) oxidising agent, characterized in that the silver precipitating or complexing moiety is a by-product in the preparation of the iron complexmg agent.
2. A process as claimed in Claim 1, wherein the photographic bleach is prepared without isolating the intermediate iron complexing agent.
3. A process as claimed in Claim 1 or Claim 2, wherein the silver precipitating or complexing moiety is a halogenating agent for halogenating silver ions.
4. A process, as claimed in Claim 3, wherein the halogenating agent is a bromide ion.
5. A process as claimed in any one of the preceding claims, wherein the iron complexing agent is an optionally substituted ajJAliπύnodiacetic acid.
6. A process as claimed in Claim 5, wherein the optionally substituted alkylirninodiacetic acid is selected from optionally substituted straight chain or branched Cι-C12 alkylirninodiacetic acids.
7. A process as claimed in Claim 5, wherein the optionally substituted ajlkyliminodiacetic acid is selected from optionally substituted straight chain or branched Cι-C6 alkyhminodiacetic acids.
8. A process as claimed in Claim 5, wherein the optionally substituted all<yliminodiacetic acid is selected from methyliminodiacetic acid, ethylirninodiacetic acid, propyliminodiacetic acid and butyliminodiacetic acid.
5 9. A process as claimed in Claim 8, wherein the optionally substituted alkylim odiacetic acid is me yliminodiacetic acid or emylirriinodiacetic acid
10. A process as claimed in any one of Claims 5 to 9, wherein the optionally substituted auylirninodiacetic acid iron (III) complexing agent is 10 prepared by reacting an optionally substituted bromoacetic acid with an optionally substituted alkylamine in the presence of a base.
11. A process as claimed in Claim 10, wherein the base is an alkali metal hydroxide.
15 ' 12. A process as claimed in any one of the preceding claims, which further comprises adding a second iron (III) complexing agent prior to the treatment with the iron (III) source.
20 13. A process as claimed in Claim 12, wherein the second iron (III) complexing agent is selected from EDTA and 1,2 -PDTA.
14. A process as claimed in any one of the preceding claims, which comprises the addition of iron (111) nitrate.
25 15. A process for the preparation of an optionally substituted aH ylinjinodiacetic acid iron complexing agent, comprising reacting an optionally substituted bromoacetic acid with an optionally substituted alkylamine in the presence of a base.
30 16. A process as claimed in Claim 15, wherein the alkylamine is selected from methylamine and ethylaniine.
17. Use of -an optionally substituted bromoacetic acid in the preparation of an ajkyliminodiacetic acid complexing agent for use in a rehalogenating photo raphic bleach.
18. A use as claimed in Claim 17, wherein the optionally substituted
• bromoacetic acid is bromoacetic acid.
19. A use as claimed in Claim 1 or Claim 18 , wherein the alkyliniinodiacetic acid complexing agent is methyliminodiacetic acid or e yliminodiacetic acid.
20. A process as claimed in any one of Claims 1 to 14 substantially as hereinbefore described with reference to the Examples.
21. A process as claimed in Claim 15 or Claim 16 substantially as hereinbefore described with reference to the Examples.
22. A use as claimed in any one of Claims 17 to 19 substantially as hereinbefore described with reference to the Examples.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0325762.3 | 2003-11-05 | ||
| GB0325762A GB0325762D0 (en) | 2003-11-05 | 2003-11-05 | Photographic bleach composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005054947A1 true WO2005054947A1 (en) | 2005-06-16 |
Family
ID=29725946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2004/004233 WO2005054947A1 (en) | 2003-11-05 | 2004-10-07 | Photographic bleach composition |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB0325762D0 (en) |
| WO (1) | WO2005054947A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3113026A (en) * | 1959-01-19 | 1963-12-03 | Gen Aniline & Film Corp | Polyvinyl alcohol photographic silver halide emulsions |
| US4294914A (en) * | 1978-09-14 | 1981-10-13 | Eastman Kodak Company | Photographic bleach compositions and methods of photographic processing |
| US5547817A (en) * | 1994-10-20 | 1996-08-20 | Fuji Photo Film Co., Ltd. | Photographic processing using a novel chelating complex |
| US6162947A (en) * | 1998-07-10 | 2000-12-19 | Dibra S.P.A. | Process for the preparation of 4-carboxy-5, 8,11-tris (carboxymethyl)-phenyl-2-oxa-5, 8 11-triazatridecan |
-
2003
- 2003-11-05 GB GB0325762A patent/GB0325762D0/en not_active Ceased
-
2004
- 2004-10-07 WO PCT/GB2004/004233 patent/WO2005054947A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3113026A (en) * | 1959-01-19 | 1963-12-03 | Gen Aniline & Film Corp | Polyvinyl alcohol photographic silver halide emulsions |
| US4294914A (en) * | 1978-09-14 | 1981-10-13 | Eastman Kodak Company | Photographic bleach compositions and methods of photographic processing |
| US5547817A (en) * | 1994-10-20 | 1996-08-20 | Fuji Photo Film Co., Ltd. | Photographic processing using a novel chelating complex |
| US6162947A (en) * | 1998-07-10 | 2000-12-19 | Dibra S.P.A. | Process for the preparation of 4-carboxy-5, 8,11-tris (carboxymethyl)-phenyl-2-oxa-5, 8 11-triazatridecan |
Non-Patent Citations (3)
| Title |
|---|
| B.T. GOLDING ET AL: "Chemistry of nitrogen mustard [2-chloro-N-(2-chloroethyl)-N-methylethanamine]studied by nuclear magnetic resonance spectroscopy", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 2., 1987, GBCHEMICAL SOCIETY. LETCHWORTH., pages 705 - 713, XP002308330 * |
| H. KUMITA ET AL: "Site-selective recognition of amino acids by Co(III) complexes containg a (N)(O)3-type tripodal tetradentate ligand.", BULLETIN OF THE SOCIETY OF JAPAN, vol. 74, no. 6, 2001, pages 1035 - 1042, XP002308329 * |
| WESTERBERG ET AL: "Synthesis of novel bifunctional chelators and their use in preparing monoclonal antibody conjugates for tumor targeting", JOURNAL OF MEDICINAL CHEMISTRY, AMERICAN CHEMICAL SOCIETY. WASHINGTON, US, vol. 32, no. 1, 1989, pages 236 - 243, XP002104515, ISSN: 0022-2623 * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0325762D0 (en) | 2003-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6119985B2 (en) | ||
| EP0020397B1 (en) | Photographic bleach compositions and methods of photographic processing | |
| JPS604980B2 (en) | Color photo processing method | |
| JPH09120130A (en) | Aqueous solution for photographic processing and bleaching or bleaching-fixing method using it | |
| WO2005054947A1 (en) | Photographic bleach composition | |
| US5763634A (en) | Process for the preparation of ferric chelate solutions of alkali metal polyamino succinic acids | |
| JP4742419B2 (en) | Ethylenediamine-N, N'-dimalonate tin (II) complex, process for its production and use thereof | |
| JP3150192B2 (en) | Anthranilic acid derivatives | |
| JP3720860B2 (en) | Novel aminopolycarboxylic acid derivative and process for producing the same | |
| JP2013023475A (en) | Method for producing 1,3-diiodohydantoins | |
| JP4759809B2 (en) | Dialkylethylenediamine dimalonic acids, process for producing the same and uses thereof | |
| JP2991643B2 (en) | Method for producing sulfur-containing amino acids | |
| US4719175A (en) | Novel pyrazole compounds having silver halide development groups | |
| JP3086341B2 (en) | Novel iron complex and method for producing the same | |
| JP3294303B2 (en) | Aminopolycarboxylic acid derivative and chelating agent | |
| JP3161793B2 (en) | New aminopolycarboxylic acid derivatives | |
| JP4399972B2 (en) | Process for producing β-alanine-N, N-diacetic acid trialkali metal salt | |
| JP2000086606A (en) | Production of antioxidant, color developing composition containing the compound and its production | |
| JP2000095738A (en) | Production of polyaminosuccinic acids | |
| JP3598131B2 (en) | Novel substituted alkylsulfinic acid ammonium salts | |
| JP2001322971A (en) | Method for producing ferric ethylenediamine-n,n'- dimalonate complex | |
| JP4423733B2 (en) | Aminopolycarboxylate, process for its production and use thereof | |
| JP3503993B2 (en) | Method for producing N-mono-t-butyloxycarbonylalkylenediamine | |
| JP3124980B2 (en) | Novel iron complex and method for producing the same | |
| JPH09227481A (en) | Production of multi-hydrophilic group type n-long chain acylcarboxylic acid or its salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 122 | Ep: pct application non-entry in european phase |