US3352682A - Photographic silver halide emulsion containing finely divided uinert particles dispersed in a synthetic colloid medium and a silver halide developer - Google Patents
Photographic silver halide emulsion containing finely divided uinert particles dispersed in a synthetic colloid medium and a silver halide developer Download PDFInfo
- Publication number
- US3352682A US3352682A US395319A US39531964A US3352682A US 3352682 A US3352682 A US 3352682A US 395319 A US395319 A US 395319A US 39531964 A US39531964 A US 39531964A US 3352682 A US3352682 A US 3352682A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- photographic
- finely divided
- emulsion
- uinert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title description 26
- 229910052709 silver Inorganic materials 0.000 title description 14
- 239000004332 silver Substances 0.000 title description 14
- -1 silver halide Chemical class 0.000 title description 13
- 239000000084 colloidal system Substances 0.000 title description 9
- 239000002245 particle Substances 0.000 title description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 239000000463 material Substances 0.000 description 24
- 239000000377 silicon dioxide Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 9
- 229920000159 gelatin Polymers 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NQYDQWFTVBEGSG-UHFFFAOYSA-N 1,2,4-oxadiazolidine-3,5-dithione Chemical class S=C1NOC(=S)N1 NQYDQWFTVBEGSG-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 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
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 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
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000725 suspension 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
-
- 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
- G03C1/42—Developers or their precursors
-
- 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
- G03C5/262—Processes using silver-salt-containing photosensitive materials or agents therefor using materials covered by groups G03C1/42 and G03C1/43
Definitions
- Photographic material which comprises a film support and a layer of a gelatino silver halide photographic emulsion, the emulsion containing (1) a photographic developer, notably hydroquinone, and (2) finely divided particles of a photographically inert substance, particularly silica, dispersed in polyvinyl alcohol, i.e. a synthetic colloid medium compatible with gelatin.
- a photographic developer notably hydroquinone
- finely divided particles of a photographically inert substance, particularly silica dispersed in polyvinyl alcohol, i.e. a synthetic colloid medium compatible with gelatin.
- This invention relates to novel photographic materials and to their use.
- a known process for the production of photographic records makes use of a light-sensitive material which comprises a sheet support carrying a layer of gelatino silver halide photographic emulsion which includes a developing agent for the silver halide.
- a so-called activator solution which is a solution containing alkali which serves to activate the developer in the emulsion
- stabiliser solution which is a solution which contains a substance, usually a water-soluble thiocyanate, which forms a complex with the residual silver halide, rendering it non-light sensitive.
- the sheet material on which the photographic emulsion is coated is paper and since this is an absorbent material the salts formed in the emulsion layer during processing are partially absorbed into the paper base.
- a photographic material in which the developer-containing emulsion is coated as a layer on a film base e.g. a base of cellulose triacetate, cellulose acetate-butyrate, polystyrene, a polyethylene terephthalate, a polycarbonate or like film material
- this absorption cannot take place and, accordingly, there is a tendency for salts formed during processing to crystallise out on the surface of the material when it is dry, a circumstance which is deleterious to the quality of the product.
- a photographic material which comprises a film support and a layer of a gelatino silver halide photographic emulsion, the said emulsion containing (1) a photographic developer compound and (2) finely divided particles of a photographically inert substance dispersed in a synthetic colloid medium compatible with gelatin.
- the finely divided material is silica and the synthetic colloid medium in which such particles are dispersed is polyvinyl alcohol.
- the side of the film support opposite to that which carries the photographic emulsion is itself provided with a layer comprising particles of a photographically inert material in a medium of gelatin and synthetic colloid, preferably finely divided silica in a medium of gelatin and polyvinyl alcohol.
- the film support may be a film of any of the materials referred to above as suitable for the purpose, or any other known per se for use with photographic materials. It is preferably colourless, clear and of thickness three to five thousandths of an inch,
- the photographic emulsion may be any gelatino silver halide emulsion known per se for use in a process of the type in which the emulsion contains a developing agent and is processed by treatment with activator and stabiliser as aforesaid.
- the developer used is preferably hydroquinone.
- the particulate material used must be of very small particle size and, typically, silica of particle size 2 to 3 microns is very suitable.
- the silica is dispersed in the colloid medium such as polyvinyl alcohol and the dispersion added to the photographic emulsion, preferably in such quantity that it will give, when the emulsion is coated, a silica coating weight of 0.4 to 0.6 grams per square metre of coating.
- concentration in the dispersion may be, conveniently, from 612% by weight, e.g. an 8% by weight dispersion of silica in a 10% by weight aqueous solution of polyvinyl alcohol.
- the backing of the film support (when a backing is used, as is preferable) conveniently consists of a similar dispersion of silica in polyvinyl alcohol, added to a gelatin solution of gelatin concentration comparable to that used in the photographic emulsion, and is applied to give a similar silica coating weight and similar or slightly greater gelatin coating weight.
- the new photographic materials may be processed using activator and stabiliser solutions known per se.
- the activator solution preferably consists of an aqueous solu tion of sodium hydroxide at 5-8% concentration (preferably 6%) and containing 340% alkali metal sulphite (preferably 5% sodium sulphite).
- the stabiliser solution is preferably an aqueous solution of a water-soluble thiocyanate, preferably ammonium thiocyanate but it is found that it is generally sufiicient to provide a solution of much less thiocyanate content than is commonly optimal when treating a photographic material of the same type coated on paper base.
- a photographic emulsion is prepared by a conventional technique which contains 1000 g. of silver as silver halide, 540 g. of hydroquinoue, 5000 g. of gelatin and an 8% by weight suspension of very finely divided silica in a 10% by weight aqueous solution of polyvinyl alcohol is prepared and is added to the emulsion to provide 370 g. of silica in the emulsion.
- the resulting emulsion is coated on film base at a coating weight of 1.2 g. silver/square metre which provides a silica coating weight at 0.44 g./square metre.
- the photographic film thus obtained is imagewise exposed, and treated with an activator solution which is a 6% by weight aqueous solution of sodium hydroxide con- 3 taining 5% by. weight of sodium sulphite.
- the film is then treated in a stabiliser bath of the formula:
- These compounds can alternatively or in addition be included, as their metal salts which are insoluble in water but soluble in the stabiliser solution, in the photographic.
- the synthetic colloid medium used to disperse the inert substance in the pro ducts of the invention is preferably polyvinyl alcohol because that substance is most readily available, nevertheless the invention is not confined to the use of polyvinyl alcohol; any water-soluble or water-dispersible synthetic colloid which is compatible with gelatin can be employed and commerce provides a wide choice of such materials.
- any other inert finely divided material may be employed e.g. other oxides such as alumina, titania, insoluble starch and its water-insoluble derivatives.
- a photographic material which comprises a film support anda layer of a gelatino silver halide photographic emulsion, the said emulsion containing (1) hydroquino'ne and (2) finely divided silica dispersed in polyvinyl alcohol, the silica being present in 'a proportion suflicient to provide 0.4 to 0.6 g. of silica per square metre of the emulsion layer.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB36192/63A GB1028748A (en) | 1963-09-13 | 1963-09-13 | Photographic materials and processes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3352682A true US3352682A (en) | 1967-11-14 |
Family
ID=10385812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US395319A Expired - Lifetime US3352682A (en) | 1963-09-13 | 1964-09-09 | Photographic silver halide emulsion containing finely divided uinert particles dispersed in a synthetic colloid medium and a silver halide developer |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3352682A (de) |
| BE (1) | BE653011A (de) |
| CH (1) | CH438932A (de) |
| DE (1) | DE1447725A1 (de) |
| GB (1) | GB1028748A (de) |
| NL (1) | NL6410557A (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3884692A (en) * | 1972-03-14 | 1975-05-20 | Fuji Photo Film Co Ltd | Photographic support |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2989417A (en) * | 1958-12-24 | 1961-06-20 | Du Pont | Hardening of gelatin with titanium compounds |
| DE1174157B (de) * | 1963-02-23 | 1964-07-16 | Agfa Ag | Lichtempfindliches photographisches Waermekopiermaterial |
| US3257205A (en) * | 1960-10-12 | 1966-06-21 | Gevaert Photo Prod Nv | Method for heat development |
-
1963
- 1963-09-13 GB GB36192/63A patent/GB1028748A/en not_active Expired
-
1964
- 1964-09-09 CH CH1173464A patent/CH438932A/de unknown
- 1964-09-09 US US395319A patent/US3352682A/en not_active Expired - Lifetime
- 1964-09-10 DE DE19641447725 patent/DE1447725A1/de active Pending
- 1964-09-10 NL NL6410557A patent/NL6410557A/xx unknown
- 1964-09-11 BE BE653011A patent/BE653011A/xx unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2989417A (en) * | 1958-12-24 | 1961-06-20 | Du Pont | Hardening of gelatin with titanium compounds |
| US3257205A (en) * | 1960-10-12 | 1966-06-21 | Gevaert Photo Prod Nv | Method for heat development |
| DE1174157B (de) * | 1963-02-23 | 1964-07-16 | Agfa Ag | Lichtempfindliches photographisches Waermekopiermaterial |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3884692A (en) * | 1972-03-14 | 1975-05-20 | Fuji Photo Film Co Ltd | Photographic support |
Also Published As
| Publication number | Publication date |
|---|---|
| BE653011A (de) | 1964-12-31 |
| DE1447725A1 (de) | 1969-10-09 |
| NL6410557A (de) | 1965-03-15 |
| GB1028748A (en) | 1966-05-04 |
| CH438932A (de) | 1967-06-30 |
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