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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G7/00—Compounds of gold
  • C01G7/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D263/48—Nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
  • C22B3/34—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing sulfur, e.g. sulfonium
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/20—Recycling

Definitions

• Photographic light-sensitive silver halide emulsions comprising as a sensitizer at least one water-soluble gold (I) salt of a mercapto compound comprising a sulphonic acid group in an acid or salt form is described.
• the sensitizers do not give rise to an increase of the sensitivity to red light when used in combination with sensitizers having a labile sulphur atom as is the case with most gold (I) sensitizers.
• the present invention relates to an improved photographic material and more particularly to silver halide emulsion layers having an increased general light-sensitivity and gradation.
• sulphur sensitizers i.e. compounds containing a labile sulphur atom e.g. allyl isothiocyanate, thiourea, allyl thiourea, sodium thiosulphate etc. and the gold compounds are particularly worth mentioning.
• Gold (I) as well as gold (III) compounds have been described for this purpose.
• gold (III) compounds act as oxidants with the result that the physical properties of the gelatin are disadvantageously altered. Therefore, gold (I) compounds are favoured.
• Gold (I) compounds comprising complex gold (I) ions with a high degree of dissociation such as ammonium dithiocyanato aurate (I), which is commonly used as gold sensitizer, can give rise to complex formation with gelatin i.e. they form little ditfusible gold (I)-gelatin complexes whereby sensitization is reduced.
• ripening should take place at elevated temperature and larger amounts of ammonium dithiocyanate aurate (I) should be used; this results, however, in a reduction of the gold salt by the gelatin and in an increase of the fog formation.
• X represents a bivalent organic radical e.g. an aliphatic aromatic or heterocyclic bivalent radical such as alkylene including substituted alkylene, arylene including substituted arylene, aralkylene including substituted aralkylene and a bivalent radical comprising a heterocyclic nucleus including a substituted heterocyclic nucleus and M represents hydrogen, an alkali metal or alkaline earth metal, ammonium, an organic amine, guanidine etc.,
• the high water-solubility obtained by the presence of a sulphonic acid group in the gold (I) mercaptide compound, guarantees a homogeneous distribution of the sensitizer in the emulsion.
• the low degree of dissociation of these gold (I) mercaptides is responsible for the very low interaction with gelatin.
• the gold (I) mercaptides of the type described above practically do not give rise to an increase of the sensitivity to red light when used in combination with sensitizers having a labile sulphur atom, particularly when longer ripening times are applied.
• water-soluble gold (I) mercaptides of use according to the present invention are:
• ALIS-CHz-CH-CHz-SOaNB (AuS-CHz-CH-CHz-S 92 I s oaH S0 11
• the compounds of use according to the present invention can be prepared according to the process described 3 and claimed in our application 'filed on even date herewith entitled: Method for the Preparation of Thiogold (I) Compounds. The following preparations illustrate more particularly how the gold (I) mercaptide compounds can be prepared.
• a solution of 121 g. (0.44 mole) of 1-(m-sulphofluorobenzoyl)-thiosemicarbazide in 2 litres of acetone is added to 1.5 litres of N sodium hydroxide.
• the acetone is removed by evaporation and the residual aqueous solution is refluxed for 4 hours.
• After cooling the solution is conducted over the cation exchange resin IR 120 and the eluate is evaporated till dry.
• the resulting product is dried over phosphorus pentaoxide. Yield: 90 g. (80% p
• the water-soluble gold (I) mercaptides of use according to the present invention can be added to the light-sensitive silver halide emulsion during different preparation steps of the light-sensitive material. They are preferably added to the silver halide emulsion composition after the physical ripening process and after the soluble salts have been removed from the emulsion by washing.
• the optimum amount of gold (I) mercaptide added to the silver halide emulsion depends on the very compound, on the nature of the colloid binding agent for the silver halide grains, and on the amount and the kind of the silver halide in the emulsion. This optimum amount can be determined for each particular emulsion in a very simple way of application of the usual tests. In general, however, the gold (I) mercaptides are added to the lightsensitive material in amounts equivalent to from 0.1 mg. to 100 mg. of metallic gold per mole of silver halide.
• the step of increasing the sensitivity according to the present invention can be combined with chemical sensitization by means of known chemical sulphur sensitizers e.g. sulphur-containing compounds such as allyl isothiocyanate, allylthiourea, or sodium thiosulphate.
• chemical sulphur sensitizers e.g. sulphur-containing compounds such as allyl isothiocyanate, allylthiourea, or sodium thiosulphate.
• the gold (I) mercaptides applied in the present invention can also be used in combination with stabilizers and fog-inhibiting compounds for the silver halide emulsion, for instance with mercury compounds or organic sulphurcontaining compounds that form an insoluble silver salt with silver ions, preferably heterocyclic nitrogen-containing thione compounds such as benzothiazoline-Z-thione and 1-phenyl-2-tetrazoline-5-thione, the compounds described in the Belgian patent specifications 571,916 and 571,917 both filed Oct. 10, 1958, by Gevaert Photo- Producten NV. and compounds of the hydroxytriazolopyrimidine type, e.g. 5-methyl-7-hydroxy-s-triazolo[1,5-a] pyrimidine.
• the combination with sensitizing and stabilizing cadmium salts in the light-sensitive material as well as in the developing bath can also be applied.
• quaternary tetraalkylammonium salts alkylpyridinium salts, bis-alkylenepyridinium salts, alkylquinoline salts, and tri-alkylsulphonium salts can also be used together with the gold (I) mercaptides according to the invention in the developing solution as well as in the light-sensitive material.
• Other ingredients such as colour couplers, developing substances, hardening agents, and wetting agents can also be added to the emulsions in the ordinary way.
• the gold (I) sensitizers according to the present invention are suitable for the sensitization of all kinds of light-sensitive silver halide emulsions including silver bromide, silver chloride, silver chlorobromide, silver bromoiodide and silver chlorobromo-iodide emulsions.
• the sensitivity and gradation of fine-grain as well as of coarse-grain silver halide emulsions is increased by the action of the above-mentioned gold (I) mercaptides.
• These products can be applied for increasing the sensitivity of X-ray emulsions as well as of the most divergent spectrally or non-speetrally sensitized emulsions. They can be incorporated into the photographic emulsion for increasing the sensitivity of negative emulsions as well as of positive emulsions.
• gelatin is preferably used as hydrophilic colloid for the light-sensitive silver halide emulsion
• water-soluble colloidal materials or mixtures of them can be used too such as polyvinyl alcohol, zein, casein, alginic acid, carboxymethylcellulose etc.
• a silver bromide dispersion is prepared by addition at 25 C., in a period of 5 seconds, of a 0.1 molar solution of silver nitrate to a 0.1 molar solution of potassium bromide. The ratio of volume of both solutions is chosen so that finally a 0.013 molar excess of potassium bromide is present.
• the precipitate is stirred with water to form a suspension containing 50 g. of silver bromide per liter.
• the pH of the suspension is comprised between 6.3 and 6.8 and the pAg between 8.4 and 8.7..
• the suspension is then divided into two aliquot portions A and B.
• To portion B inert gelatin (the labile sulphur content of the gelatin is less than 1 gamma per gram of gelatin) is added up to a concentration of gelatin of 7.5%.
• ammonium dithiocyanato aurate (I) A and B or the gold (I) salt of 3-mercapto-propane sulphonic acid sodium salt (A and B in the amounts given in Table I below.
• suspensions are then ripened at 30 C. and C. whereupon to the suspensions A an amount of inert gelatin is added up to a concentration of 7.5
• the suspensions are then separately applied to a cellulose triacetate support and dried.
• test strips A B A and B obtained are then image-wise exposed for sec. through a Wedge with constant 0.15 by means of a 500 watt lamp having a colour temperature of 2.850 K.
• the exposed film-strips are then developed at 20 C. for 5 min. in a developing bath having the following composition:
• EXAMPLE 2 Two silver bromide dispersions A and B are prepared as described in Example 1. Both dispersions are divided into three aliquot portions to which are added respectively per 50 g. of silver bromide: 9 mg. of sodium thiosulphate (Aa and Ba), an amount of sodium di(thiosulphato) aurate (I) equivalent to 6 mg. of gold (Ab and Bb), and an amount of the gold (I) salt of 3-mercaptopropane sulphonic acid guanidine salt equivalent to 6 mg. of gold together with 9 mg. of sodium thiosulphate (Ac and Be). The 6 mixtures are ripened at 55 C. To the dispersions Aa, Ab and Ac an amount of inert gelatin is then added up to a concentration of 7.5%.
• the dispersions are then coated, dried, exposed and developed as described in Example 1.
• X is a bivalent organic radical
• M represents hydrogen, an alkali metal, an alkaline earth metal, ammonium, an organic amine or guanidine.
• Photographic light-sensitive silver halide emulsion according to claim 1 wherein said gold (I) salt of a mercapto compound corresponds to the formula:
• X is an aliphatic, aromatic or heterocyclic bivalent radical
• M represents hydrogen, an alkali metal, an alkaline earth metal, ammonium, an organic amine of guanidine.
• Photographic light-sensitive silver halide emulsion according to claim 1 comprising in addition to the gold (I) mercaptide compound(s) at least one chemical sulphur sensitizer.
• Photographic light-sensitive material comprising a silver halide emulsion layer formed from a light-sensitive silver halide emulsion according to claim 1.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Manufacturing & Machinery (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Mechanical Engineering (AREA)
• Geology (AREA)
• Environmental & Geological Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Physics & Mathematics (AREA)
• Inorganic Chemistry (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=26267514

Family Applications (2)

Family Applications After (1)

Country Status (6)

Cited By (23)

Families Citing this family (7)

Citations (2)

Family Cites Families (3)

• 1965
  • 1965-12-29 GB GB55043/65A patent/GB1132474A/en not_active Expired
• 1966
  • 1966-12-14 GB GB55996/66A patent/GB1160728A/en not_active Expired
  • 1966-12-19 US US602584A patent/US3503749A/en not_active Expired - Lifetime
  • 1966-12-19 US US602492A patent/US3438748A/en not_active Expired - Lifetime
  • 1966-12-27 FR FR89252A patent/FR1506891A/fr not_active Expired
  • 1966-12-27 DE DE19661568063 patent/DE1568063A1/de active Pending
  • 1966-12-27 FR FR89253A patent/FR1506237A/fr not_active Expired
  • 1966-12-28 BE BE691857D patent/BE691857A/xx unknown
  • 1966-12-28 BE BE691856D patent/BE691856A/xx unknown
  • 1966-12-29 NL NL6618336A patent/NL6618336A/xx unknown
  • 1966-12-29 NL NL6618337A patent/NL6618337A/xx unknown

Patent Citations (2)

Also Published As

Similar Documents