GB2223859A - Silver halide photographic material containing a biocide - Google Patents
Silver halide photographic material containing a biocide Download PDFInfo
- Publication number
- GB2223859A GB2223859A GB8821434A GB8821434A GB2223859A GB 2223859 A GB2223859 A GB 2223859A GB 8821434 A GB8821434 A GB 8821434A GB 8821434 A GB8821434 A GB 8821434A GB 2223859 A GB2223859 A GB 2223859A
- Authority
- GB
- United Kingdom
- Prior art keywords
- silver halide
- biocide
- layer
- photographic material
- hydroxyethoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 47
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 46
- 239000004332 silver Substances 0.000 title claims abstract description 46
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 40
- 239000003139 biocide Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 22
- YSPADHLUBJTJLN-UHFFFAOYSA-N 2-(2-hydroxyethoxymethoxy)ethanol Chemical compound OCCOCOCCO YSPADHLUBJTJLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims description 37
- 239000004816 latex Substances 0.000 claims description 21
- 229920000126 latex Polymers 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002334 glycols Chemical class 0.000 abstract description 2
- 241000894006 Bacteria Species 0.000 description 14
- 108010010803 Gelatin Proteins 0.000 description 11
- 229920000159 gelatin Polymers 0.000 description 11
- 239000008273 gelatin Substances 0.000 description 11
- 235000019322 gelatine Nutrition 0.000 description 11
- 235000011852 gelatine desserts Nutrition 0.000 description 11
- 230000012010 growth Effects 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 241000233866 Fungi Species 0.000 description 4
- 241000589516 Pseudomonas Species 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000004133 Sodium thiosulphate Substances 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930024421 Adenine Natural products 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 239000004285 Potassium sulphite Substances 0.000 description 1
- 206010037867 Rash macular Diseases 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 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
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/37—Antiseptic agents
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A light sensitive silver halide photographic material comprises at least one hydrophilic colloid layer comprising as a biocide di(2-hydroxyethoxy)methane, eg in amount 0.01 to 1.0 wt%. Di(2-hydroxyethoxy)methane is obtainable commercially in equilibrium with the precursors used in its preparation since di(2-hydroxyethoxy)methane as the pure compound is difficult to isolate. Such precursors include dioxolane, formaldehyde and glycols such as ethylene glycol and HO-CH2-O-CH2-CH2-O-CH2-OH. It appears that the presence of these precursors does not detract from the biocidal properties of the liquid which comprises di(2-hydroxyethoxy)methane and may even increase them.
Description
BIDOlEE IN PHOTOGRAPHIC MATERIALS This invention relates to light-sensitive silver halide photographic material. To prepare a silver halide coating solution silver halide crystals are dispersed in a binder and this solution is coated on a photographic support base to form photographic material. The usual binder for such use is gelatin or gelatin together with albumin, casein a hydrolysed cellulose derivative or a synthetic binder such as polyvinyl alcohol or polyacrylamide.
Aqueous gelatin solutions are particularly susceptible to biological growths occurring therein such as bacteria, fungi and yeasts. Often warm aqueous gelatin coating solutions are prepared in advance of their being coated. During this period before the water is removed from the solution very rapid biological growth can occur. Such biological growth can lead to marked sensitometric defects in the silver halide material which are visible when the material has been exposed and processed.
Usually a biocide is added to such aqueous gelatin solutions to prevent biological growth and the most common biocide is phenol. However phenol is unpleasant to use and has a disagreeable smell. Further it has to be used in comparatively large quantities. Also it is not particularly effective against fungi such as moulds which are becoming increasingly troublesome.
It has proved difficult to find biocides which can be used to prevent biological growth in aqueous gelatin solutions which are to be used in the preparation of photographic materials which are effective in small amounts, which do not smell and which do not affect the sensitometric properties of the photographic material in which they have been included. For example the use can not be tolerated of compounds which contain a thio-group or a quaternary ammonium group.
However we have found a biocide which surprisingly fulfils all the above requirements.
Therefore according to the present invention there is provided a light sensitive silver halide photographic material which comprises at least one hydrophilic colloid layer comprising as a biocide di(2-hydroxyethoxy)methane.
Di(2-hydroxyethoxy)methane is obtainable commercially as a liquid. This liquid is in equilibrium with the precursors used in its preparation since di(2-hydroxyethoxy)methane as the pure compound is difficult to isolate. Such precursors include dioxolane, formaldehyde and glycols such as ethylene glycol and HO CH O CH CH O CH OH. It appears that
2 2 2 2 the presence of these precursors does not detract from the biocidal properties of the liquid which comprises di(2-hydroxyethoxy)methane and may even increase them.
This commercially available liquid was used in the Example which follow and is referred to hereinafter as biocide P.
The hydrophilic colloid layer is often a silver halide emulsion layer and usually a gelatino silver halide emulsion layer. However the hydrophilic colloid layer may be a subbing layer and in particular a gelatino subbing layer or an protective or non-stress layer and in particular a gelatino non-stress layer. It has been discovered that when aqueous gelatin solutions which are to be used for non-light sensitive layers such as subbing or non-stress layers are allowed to become contaminated with biological growth then the silver halide material which comprises such layers exhibits sensitometric defects on exposure and processing as if the contamination had been in the silver halide layer.
The preferred amount of the biocide to be added to a hydrophilic coating solution is from 0.01 to 1.0 % by weight and most preferably from 0.02 to 0.2% by weight.
Also it is common to add to gelatino silver halide emulsions polymer latexes and in particular acrylic latexes. Such acrylic latexes are also very susceptible to biological contamination and biocide P has also been found to be very useful protecting them against such contamination. It has been found that when such latexes which comprise biocide P are added to aqueous gelatino silver halide emulsions then the biocide P also prevents biological growth in the aqueous emulsions as a whole.
This is a useful way of adding the biocide to a silver halide emulsion as the latexes have to be made up and stored a long time before use and thus must be protected during this period against biological growth. On the other hand silver halide gelatino silver halide coating solutions are made just prior to coating but if they are not coated fairly shortly after preparation then biological contamination can then occur.
The silver halide used in the silver halide emulsion layer may comprise any of many silver halides used in a photographic emulsion such as silver chloride, silver bromide, silver iodobromide or silver chlorobromide.
The silver halide crystals may have been chemically sensitised by any of the well known means for example by use of sulphur, selenium and noble metals. Examples of suitable sensitising compounds are sodium thiosulphate and mercury, gold, palladium and platinum salts.
The photographic emulsion may contain any of the additives commonly used in photographic emulsions for example wetting agents, stabilising agents, polyethylene oxides, metal sequestering agents and growth or crystal habit modifying agents commonly used for silver halide such as adenine.
The photographic base may be any of those used for photographic film materials for example cellulose triacetate, cellulose acetate-butyrate, biaxially orientated polyethylene terephthalate, glass plates or paper or resin coated paper.
Bacteria and fungi are known to infect polymer latex dispersions, aqueous gelatin solutions and aqueous gelatino silver halide emulsion coating solutions. Further they are known to infect coated photographic products containing gelatin under conditions of high storage temperature and humidity. The effect of bacteria and fungi in coating solutions is to alter the coating properties of the solutions and either to increase or decrease their viscosity leading to uneven coatings. Further bacteria often produce chemical breakdown products such as nitrates which can produce adverse sensitometric results in the silver halide photographic material. The effect in coated photographic material leads to a number of defects. For example an uneven loss of contrast over the coated material. The nett effect of all these defects is to produce, after exposure and processing, an impaired image.
In the Example which follows coating solutions and coated products were both examined.
The following Example will serve to illustrate the invention.
EXAMPLE
The following solutions were prepared :
An aqueous latex dispersion, an aqueous gelatino silver halide emulsion and an aqueous gelatino silver halide emulsion containing a proportion of the latex dispersion.
Preparation of the latex dispersion. A carboxylated latex was prepared using butyl acrylate (65% of total monomers), methyl methacrylate (41%) and methacrylic acid (3%) with a mixed surfactant system comprising aryl polyether phosphate sodium salt (80% of surfactant) and aryl polyether (20%) such that the total level of surfactant was 4% of the total monomer by weight. A potassium persulphate initiator was used. A final solids content of 31% was obtained for the latex.
Aqueous gelatino silver halide emulsion. A gelatin silver chloro-bromide emulsion containing 55 mol percent silver chloride and 54 mole per cent silver bromide and of median crystal size 0.31 Zu was prepared using the controlled crystal techniques described in British
Patent Specification 1,335,925.
This emulsion was desalinated and chemically sensitised by the addition
o of sodium thiosulphate followed by chemical ripening at 55 C until the optimum levels of speed and contrast were obtained. The amount of gelatin in the aqueous emulsion was 10% by weight.
The bacterium psuedomonas aeruginosa and the mould aspergillus niger were innoculated into the latex and into the gelatino silver halide emulsion.
Results in latex
Biocide Tested % WT/WT of Latex % Survivors After X Days
Phenol 0.1 Asp Niger ( 14%, 28 days
0.3 ( 20%, 28 days
1.0 ( 0%, 28 days
None Asp Niger ( 83%, 1 day
(Control : latex only) ( 64%, 7 days
Pseudomonas ( 422%, 1 day
(1352%, 7 days
Biocide P 0.02% Asp. Niger 0%, 28 days
Pseudomonas 0%, 2 days
0.05% Asp. Niger 0%, 2 days
Pseudomonas 0%, 2 days
It is possible that a latex could be made-up for 28 days before use and thus it is necessary to test it for this period of time.
In the absence of a biocide bacterial growth is very rapid and mould are able to survive for at least one week. When phenol is added there is some reduction in moulds but only at a level of 1% phenol and there are no moulds after 28 days. At this level of phenol there is a flocculating effect on the latex.
However when biocide P is used there is complete freedom both from moulds and bacteria using a concentration as low as 0.02 %, and there is no destabilising effect of biocide P on the latex.
Results in gelatino silver halide emulsion.
Biocide Tested % WT/WT of Latex % Survivors After X Days
Phenol 0.3 Psuedo ( 6 hours 55
( 1 day 601
A Niger ( 6 hours 24
( 1 day 16
None Psuedo ( 6 hours 76
( 1 day 689
A Niger ( 6 hours 24
( 1 day 14
Biocide P 0.02 Psuedo ( 6 hours None
( 1 day None
A Niger ( 6 hours 0.4
( 1 day 0.02
0.05 Psuedo ( 6 hours None
( 1 day None
A Niger ( 6 hours 0.3
( 1 day 0.007
This shows that biocide P kills all the bacteria and very nearly all the mould after both six hours and 1 day. This table also shows that the bacteria in particular increase rapidly in a gelatino silver halide emulsion containing no biocide after 1 day. It is unlikely that a gelatino silver halide emulsion will remain uncoated for more than a day but other results showed that there were no moulds or bacteria in the P treated emulsions after 28 days.
As latex dispersions are often stored for up to 2 months and such latexes were found to contain neither moulds or bacteria when treated
3 with the specified amounts of biocide P, 30cm of the latex containing
3 0.05 % P were stored for two days and added to 60cm of the gelatino silver halide emulsion which had been freshly prepared. This is a normal amount of latex to be added to a silver halide emulsion.
RESULTS
Biocide Amount WT/WT emulsion 2 survivors
Biocide P 0.017 Pseudomonas ( 6 hours None
( 1 day None
Asp. Niger ( 6 hours None
( 1 day None
After 1 day samples of this silver halide emulsion containing the latex were coated on a paper base (Sample A).
Also samples of the gelatino silver halide emulsion containing 0.05 8 of biocide P were stored 1 day and coated on a paper base. (Sample B).
Samples of the gelatino silver halide emulsion containing no biocide were stored for 1 day and coated on a paper base (Sample C).
Samples of the gelatino silver halide emulsion containing no biocide were prepared and at once coated on a paper base (Sample D).
The dried coated samples A, B and C and some of D were then cut into strips and each of these strips was then imagewise exposed and processed using firstly a developing solution of the basic formula :potassium sulphite 15 g hydroquinone 3.5 g 4-methyl, 4-hydroxymethyl-l
phenyl-3-pyrazolidinone 0.03 g potassium carbonate 10 g potassium bromide 0.4 g potassium hydroxide 2.5 g benzotriazole 0.04 g ethylenediamine tetraacetic acid 1.5 g water to 1 litre pH 10.8
o temperature 20 C
All the strips were then fixed in a fixing bath, at 20 C for 30 seconds, of the formula ammonium thiosulphate 140 ml
(of 60% w/w solution) boric acid 7 g sodium hydroxide 2.5 g sodium metabisulphite 6 g glacial acetic acid 9 ml water to 1 litre
All the strips were then washed and dried and the photographic image in each was examined.
In this case the image were compared with strip D which was the freshly coated and exposed sample.
Strip A, B and D all exhibited comparable images with no blemishes.
This showed that biocide P had not interfered with the sensitometric properties of the silver halide emulsion. However the image in strip C appeared blotchy. This showed that the bacteria and/or moulds which were present in the emulsion when coated had affected the emulsion in some way.
Other strips of sample D which contained no biocide but which contained
o no bacteria or moulds when coated were stored for 1 month at 37 C and at 50% RH after coating but before exposure and processing. These strips were then exposed and processed as before. The image was then examined and showed differences in contrast over its area. This shows that moulds and bacteria can affect even coated material in the absence of a biocide.
This is to be compared with other strips of sample B which contained 0.05% biocide P in the emulsion. After coating but before exposure and 0 processing these strips were stored for 1 month at 37 C and 50% RH. The strips were then exposed and processed and the image examined.
The image was found to be exactly the same as those of strips A, B and C which had been exposed and processed after coating. This shows that the presence of the biocide prevents storage or incubation deterioration of the film material as well as the build up of moulds and bacteria in stored coating solutions.
Claims (7)
1. A light sensitive silver halide photographic material which
comprises at least one hydrophilic colloid layer comprising as a
biocide di(2-hydroxyethoxy)methane.
2. A light sensitive silver halide photographic material according to
claim 1 wherein the biocide di(2-hydroxyethoxy)methane is present in
equilibrium with its precursors.
3. A light sensitive silver halide photographic material according to
either claim 1 or claim 2 wherein the biocide is present in a silver
halide emulsion layer.
4. A method of preparing a light sensitive silver halide photographic
material as claimed in claim 1 which comprises preparing a
hydrophilic colloid coating solution which comprises from 0.01 to
1.0% by weight of the biocide and coating the solution on to a
photographic base to form a layer thereon and drying the layer.
5. A method according to claim 4 wherein the hydrophilic colloid
coating solution comprises from 0.02 to 0.2 % by weight of the
biocide.
6. A method according to either claim 4 or claim 5 wherein the
hydrophilic colloid coating solution is a gelatinous silver halide
emulsion or a gelatinous solution to be used as a nonstress or
subbing layer.
7. A method of preparing a light sensitive silver halide photographic
material according to claim 4 which comprises preparing an aqueous
polymer latex which comprises from 0.03 to 1.0% by weight of the
biocide, adding the aqueous polymer latex to an aqueous gelatinous
silver halide emulsion layer and coating the silver halide emulsion
layer containing the latex on to a photographic film base to form a
layer thereon and drying the layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8821434A GB2223859B (en) | 1988-09-13 | 1988-09-13 | Biocide in photographic materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8821434A GB2223859B (en) | 1988-09-13 | 1988-09-13 | Biocide in photographic materials |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8821434D0 GB8821434D0 (en) | 1988-10-12 |
| GB2223859A true GB2223859A (en) | 1990-04-18 |
| GB2223859B GB2223859B (en) | 1992-01-29 |
Family
ID=10643504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8821434A Expired - Lifetime GB2223859B (en) | 1988-09-13 | 1988-09-13 | Biocide in photographic materials |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2223859B (en) |
-
1988
- 1988-09-13 GB GB8821434A patent/GB2223859B/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB8821434D0 (en) | 1988-10-12 |
| GB2223859B (en) | 1992-01-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940913 |