US2689792A - Process for producing and developing light-sensitive photographic layers - Google Patents

Process for producing and developing light-sensitive photographic layers Download PDF

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Publication number
US2689792A
US2689792A US218893A US21889351A US2689792A US 2689792 A US2689792 A US 2689792A US 218893 A US218893 A US 218893A US 21889351 A US21889351 A US 21889351A US 2689792 A US2689792 A US 2689792A
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United States
Prior art keywords
solution
parts
layers
acid
film
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US218893A
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English (en)
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Rossi Carlo
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BASF Schweiz AG
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Ciba AG
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    • 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
    • G03C1/64—Compositions containing iron compounds as photosensitive substances

Definitions

  • sensitising solutions made with light-sensitive diazo compounds are known to have the disadvantage of a relatively high instability, so that it is necessary for copying purposes to expose and develop the sensitised material immediately after it has been dried.
  • the decomposition of the diazo solutions used leads to the formation of phenol derivatives having a reducing action, and these derivatives cause undesired fogging especially in colloid layers, when an intensifying development by means of unstable noble metal baths is used.
  • Sensitising solutions such as are described, for example, in German Patent No. 707,461, deposit considerable amounts of solid decomposition products in the course of 24 hours at room temperature and are therefore diflicult to use in a copying establishment.
  • the present invention is based on the observation that substantially grainless water-absorbent layers or films for recording images can be sensitised by treating them with a solution of acid reaction which contains a complex iron salt and a silver salt.
  • the waterabsorbent-layers or films used asstarting materials in the present process should be sufficiently inert towards the Sensitising solution and especially should contain no substances which themselves reduce silver salts or prevent such a reduction taking place owing to their oxidising action. Moreover these layers or films must be substantially grainless.
  • substantially grainlesshydro- 2 philic colloid materials such as cellulose hydrate films or layers, for example, films which consist wholly of regenerated cellulose or films which consist of cellulose esters, such as cellulose acetate or mixed esters, such as cellulose acetate butyrate, which have been partially hydrolyzed, but preferably gelatine layers, and which films or layers may as stated above have a special form, for example, a lenticular grating, for producing special effects.
  • the solutions used for sensitising in the present process may contain as a complex iron salt, especially a complex ferric salt, for example, a complex salt of an inorganic acid such as ferric ammonium sulphate, but especially complex salts of organic carboxylic acids, which may be mono-, di-, or polycarboxylic acids, which advantageously contain one or more hydroxyl groups.
  • a complex iron salt especially a complex ferric salt, for example, a complex salt of an inorganic acid such as ferric ammonium sulphate, but especially complex salts of organic carboxylic acids, which may be mono-, di-, or polycarboxylic acids, which advantageously contain one or more hydroxyl groups.
  • the iron bound in complex union may be present in an anion or a cation.
  • hexaaceto-hydroxo-triferric acetate nitrate ferric ammonium oxalate, potassium diglycollato-ferrate, sodium dilactato ferrate, potassium disalicylato-ferrate and especially ferric complex compounds which contain as the organic carboxylic acid citric acid for example, the brown and especially the green ferric ammonium citrate.
  • dyestuffs to the sensitising solutions described above.
  • suitable dyestuffs it is possible, for example, to increase the absorption of light in a desired region of the spectrum.
  • suitable dyestuffs which then act as damping dyestuffs.
  • damping dyestuffs in addition to possessingthe desired optical properties, must sufliciently fulfil the condition of not leading to reactions with the other components of the sensitising solution, which reactions would adversely ,affect the present photo-chemical system, and depending on the purpose in view they must be 3 easily removable.
  • damping dyestuffs there are suitable for example tartrazine or a pyrazclone dyestuif of the constitutional formula
  • the aforesaid acid-reacting solutions which contain a complex iron salt of an organic carboxylic acid and a silver salt, usually produce precipitates shortly after they have been prepared or mixed, and these precipitates are harmful in the production of light-sensitive layers or films.
  • the treatment of the water-absorbent layers or films with the aforesaid solutions may be carried out in a manner in itself known, for example, by immersion or impregnation by means of a roller or in any other'manner, so that the waterabsorbent layer or film is uniformly impregnated with the solution.
  • the resulting layers or films are considerably more stable than the hitherto known layers or films produced with diazo compounds and can be stored, for example, for pcriods ranging from several days to weeks before they need be used.
  • the new photographic layers of films possess a resolving power (about 1000 lines per mm.) similar to that of layers or films prepared with metal diazo compounds. When used for copying they yield pale yellow to pale brown images.
  • the invention is also based on the observation that these images.
  • unstable noble metal solutions for example, solutions which contain in addition to a silver salt, especially silver nitrate, a photographic developing substance, such as Metol, and also a weak acid for example tartaric acid.
  • Unexpectedly development takes place with remarkable freedom from fog, especially in the case of light-sensitive layers or films which have not been stored for long periods, for example, for not more than 1-2 weeks.
  • the aforesaid intensifying development by means of unstable noble metal solutions is advantageously carried out by means of silver nitrate and a reducing component, such as ferrous sulphate, hydroquinone or parahydroxymethyl aniline, in an acid medium.
  • a reducing component such as ferrous sulphate, hydroquinone or parahydroxymethyl aniline
  • the silver nitrate may be used either in admixture with the reduction component or before or after the action of the component precipitating the silver.
  • Images developed in the manner described above generally have a valuable neutral grey to black tint.
  • the image may possess more or less pronounced half-tones.
  • slight brownish borders may be present between the covered and uncovered parts in the record.
  • Example-1 A layer consisting of light-tanned gelatine, for example, a double lenticular film made by the process of Dr. Gretener A. G., Zurich, is impregnated with a sensitising solution, which has been clarified by filtration after about 4 hours, of the following composition:
  • the wet film is driedin a dust-free-current of air heated at 33-35 C.,. and is then used for copying.
  • the exposed film is developed by .immersi'ng it in a freshly preparedmixture of iO sparts by volume of an aqueous solution consisting of.
  • Example 2 instead of the :sol'u tionv used. in Example 1,
  • Example 2 In parts of distilled water containing 0.2 per cent. of a wetting agent described in Example 1 are dissolved 0.2 part of potassium diglycollatoferrate and 0.1 part of glycollic acid. The clear solution is mixed with 5 parts of a silver nitrate solution of per cent. strength, and then freed from small quantities of insoluble matter by filtration.
  • the resulting solution is used for impregnating the hardened gelatine side of a double grating film and the resulting film is dried at 33-36 C. in dust-free air.
  • the layers obtained in accordance with the foregoing examples can be stored in the dark for a long time, for example for a month at a room temperature of 18-20" C. without any crystalline deposits or chemical decomposition reactions being observed. It is important to maintain protective drying conditions and to store the products in a dry state.
  • Example 4 By this treatment the coloured borders are con- 75 e? I verted into neutral grey to black parts of the image.
  • Example5 26 parts of brown ferric ammonium citrate, 9.2 parts of citric acid, 8.0 parts of the salt-free azo dyestuff obtained by coupling 1-(2::5-disulphophenyl)-3-methyl-5-pyrazolone with diazotized sulphanilic acid with the addition of pyridine; and 1.0 part of a non-ionic wetting agent of the type of a fatty alcohol-polyethylene oxide condensation product are dissolved in 100 parts of distilled water.
  • the sensitising solution so obtained can be used instead of that described in Eample 1, 2 or 3.
  • Example 6 A cellulose acetate butyrate film, which is provided with a cylinder grating, is hydrolysed on its smooth surface about 4 deep with an alcoholic solution of caustic soda by placing it for 4 minutes on the surface of the hydrolysing solution.
  • the film is freed from excess of caustic soda by washing in distilled water for 10 minutes and dried in the air. It is sensitised with the solution described in Example 3 by immersion for about 1 minute and washing the side of the film carrying the grating with distilled water.
  • the sensitised film is dried at 33-34 C. for 10-20 minutes by passing dust-free air over it.
  • the exposed film is conditioned, before development, in a room having a temperature of 20-22 C. and a relative humidity of 90-95 per cent. for A hour.
  • the same conditioning treatment may be applied to the layers used in Examples 1, 2, 3 and 5.
  • an atmosphere of high water content such as above per cent. relative humidity and preferably about to per cent. relative humidity should be used.
  • a process for producing photographic records which comprises impregnating a substantially grainless hydrophilic colloid layer supported by a substantially grainless transparent film material, with a clarified acidulated solution which contains a complex ferric salt of an aliphatic hydroxy-carboxylic acid and a water soluble silver salt, exposing the sensitized layer and developing it with a solution of Metol, a weak acid, silver nitrate and a non-ionic wetting agent.
  • a process for producing photographic records which comprises sensitizing a substantially grainless hydrophilic colloid layer on a transparent grainless film support with a clarified solution containing hexa acto-hydroxo-triferric ace- '1 tate nitrate, silver nitrate and; a non-ionic. wet.- ting agent, exposing the sensitized layer and (13- veloping it with a solution of Metol, tartaric acid, silver nitrate and a non-ionic. wetting agent.
  • sensitized layer is conditioned after exposure and before development in an atmosphere of at. least 60% relative humidity.
  • the sensitizing solution contains. a silver latent image sensitizing. dye which restricts the depth of. penetration of said latent image into said hydrophilic layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US218893A 1950-04-06 1951-04-02 Process for producing and developing light-sensitive photographic layers Expired - Lifetime US2689792A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH701529X 1950-04-06

Publications (1)

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US2689792A true US2689792A (en) 1954-09-21

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US218893A Expired - Lifetime US2689792A (en) 1950-04-06 1951-04-02 Process for producing and developing light-sensitive photographic layers

Country Status (5)

Country Link
US (1) US2689792A (de)
CH (2) CH288751A (de)
DE (1) DE896294C (de)
FR (1) FR1035112A (de)
GB (1) GB701529A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464234A (en) * 1994-03-08 1995-11-07 Ferguson; Alan C. Rearward approach curb jumper for a hand truck

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE531295A (de) * 1953-08-21

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1120580A (en) * 1913-09-22 1914-12-08 William Willis Sensitive photographic paper and process of making the same.
US1225146A (en) * 1909-05-10 1917-05-08 George W Leighton Coating material for paper for photographic uses.
US1396592A (en) * 1920-10-11 1921-11-08 Rheinberg Julius Light-sensitive collodion coating mixture and film
GB375849A (en) * 1931-03-30 1932-06-30 William Mate Improvements in and relating to photographic sensitising solutions
US1984471A (en) * 1931-07-18 1934-12-18 Siemens Ag Lenticulated film
GB439241A (en) * 1934-05-26 1935-11-26 James Morton Improvements relating to the production of photographic-sensitive sheet materials
GB538245A (en) * 1939-04-12 1941-07-25 Philips Nv Improved method of producing light-sensitive layers sensitised by means of an iron salt and layers made thereby

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1225146A (en) * 1909-05-10 1917-05-08 George W Leighton Coating material for paper for photographic uses.
US1120580A (en) * 1913-09-22 1914-12-08 William Willis Sensitive photographic paper and process of making the same.
US1396592A (en) * 1920-10-11 1921-11-08 Rheinberg Julius Light-sensitive collodion coating mixture and film
GB375849A (en) * 1931-03-30 1932-06-30 William Mate Improvements in and relating to photographic sensitising solutions
US1984471A (en) * 1931-07-18 1934-12-18 Siemens Ag Lenticulated film
GB439241A (en) * 1934-05-26 1935-11-26 James Morton Improvements relating to the production of photographic-sensitive sheet materials
GB538245A (en) * 1939-04-12 1941-07-25 Philips Nv Improved method of producing light-sensitive layers sensitised by means of an iron salt and layers made thereby

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464234A (en) * 1994-03-08 1995-11-07 Ferguson; Alan C. Rearward approach curb jumper for a hand truck

Also Published As

Publication number Publication date
CH296916A (de) 1954-02-28
CH288751A (de) 1953-02-15
DE896294C (de) 1953-11-12
FR1035112A (fr) 1953-08-17
GB701529A (en) 1953-12-30

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