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
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
  • C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone

Definitions

• This invention relates to an improved photographic material and more especially to silver halide emulsion layers having a better developability and an increased general light-sensitivity.
• these polyglycols and alkylene oxide polymers must have a molecular weight of at least 400 and that it is practically necessary to use compounds having a molecular weight from 1500 to 2000 and more to obtain a substantial effect.
• the developa'bility of the light-sensitive emulsions can be favorably influenced by adding to at least one emulsion layer or other layer comprised by the photographic element, a phosphoric acid ice ester of a polycxyalkylene compound as hereinafter described, said polyoxy-alkylene compound showing substantially less action on itself.
• the new developing activators are phosphoric acid esters of a polyoxyalkylene compound corresponding to one of the following general formulae:
• R is an alkylene group of from about 2 to about 3 carbon atoms, preferably an ethylene group,
• n is a positive integer from 5 to 35
• R is a member selected from the group consisting of an alkyl radical containing from about 1 to about 20 carbon atoms, preferably of at least 15 carbon atoms, and an aralkyl radical,
• R is a member selected from the group consisting of an aryl radical such as a phenyl radical, an alkylaryl radical, such as a nonylphenyl radical and a hydrogen atom,
• R is an alkyl radical containing from about 1 to about 20 carbon atoms
• X is an acid radical
• the phosphoric acid esters used according to the invention increase the relative sensitivity and particularly the gamma of the photographic material.
• the polyoxyalkylene compounds used for preparing said phosphoric acid esters may be prepared by polymerization of ethylene oxide or by reaction of ethylene oxide with an alcohol, a phenol, a glycol, an amine, an amide or an acid.
• the amount of said phosphoric acid ester yielding a very good developing activation without any substantial fog increase is between 30 mg. and 6 g. per mole of silver halide of the emulsion layer to be developed.
• the phosphoric acid esters the monoesters and the diesters as well as the triesters of phosphoric acid are included.
• the triesters of phosphoric acid or mixtures of diesters and triesters of phosphoric acid are preferably used.
• polyethylene oxide derivatives are used; but there may be also used polyalkylene oxide derivatives of the same type,
• R is a member selected from the group consisting of an alkyl radical, containing from about 1 to about 20 carbon atoms and an aralkyl radical,
• R is a member selected from the group consisting of an aryl radical such as a phenyl radical, and an alkylaryl radical, such as nonylphenyl radical and a hydrogen atom,
• R is an alkyl radical containing from about 1 to about 20 carbon atoms
• X- is an acid radical
• n is a positive integer from 5 to 35.
• the phosphoric acid esters can also be prepared by reesterification of a lower phosphoric acid alkyl ester with one of the polyoxyalkylene compounds mentioned above.
• PREPARATION 1 A mixture of 50 g. (0.056 mole) of p-nonylphenoxytetradecaethylenoxy-ethanol of the following structure:
• the viscous residue consists of 23.6% of mono(p-nonylphenoxy-tetradecaethylenoxy-ethyl) phosphate, 10.4% of di(p-nonylphenoxytetradecaethylenoxy-ethyl)phosphate and 66% of tri(pnonylphenoxy-tetradecaethylenoxy-ethyl)phosphate.
• PREPARATION 2 A mixture of g. (0.4 mole) of octadecanoyl-tetraethylenoxy-ethanol of the structure:
• the viscous residue consists of 10.1% of di(octadecanoyl tetraethylenoxy ethyl)ph0 sphate and 89.9% of trioctadecanoyl tetraethylenoxy ethyl) phosphate.
• PREPARATION 4 A mixture of g. (0.03 mole) of polyoxyethylene glycol having an average molecular weight of 4000, 0.76 g. (0.005 mole) of phosphorus pentoxide and 250 cm. of benzene is refluxed for 2 hours. The solution is filtered and the filtrate is evaporated under vacuum. The residue consists practically entirely of the phosphoric acid triester of the above polyoxyethylene glycol.
• PREPARATION 5 A mixture of 122 g. of Mulgofen O (trade name for a condensation product of a polyoxyalkylene glycol with a higher alphatic alcohol, sold by Antara Chemicals, a Division of General Aniline & Film Corporation, New York, N.Y., U.S.A.), 4 g. (0.028 mole) of phosphorus pentoxide and 25 0 cm. of benzene is refluxed for 2 hours. The solution is filtered and the filtrate is evaporated under vacuum. The residue consists practically entirely of the phosphoric acid triester of the above polyoxyalkylenc glycol.
• Mulgofen O trade name for a condensation product of a polyoxyalkylene glycol with a higher alphatic alcohol, sold by Antara Chemicals, a Division of General Aniline & Film Corporation, New York, N.Y., U.S.A.
• PREPARATION 7 A mixture of 27 g. of a polyoxyethylene derivative having the following structure:
• R represents the alkyl radicals present in the coconut fat in the following ratios: C H -about 8% C H about C H about 49% C H about 18% C H about 9% C 7H353.bOut C H about 2.4 g. (0.017 mole) of phosphorus pentoxide and 250 cm. of benzene is refluxed for 2 hours on a water-bath. The formed residue is filtered off and the filtrate is evaporated under vacuum. Titration shows that the residue did not consist entirely of the phosphoric acid triester of the above polyethylene oxide derivative, but that it contained still 0.3 milliequivalent of the phosphoric acid diester of this derivative per gram of residue.
• the developing activators used in the present invention are added directly to the silver halide emulsion.
• they may also be added to one or several layers forming a water-permeable element with the emulsion layer, e.g., a hydrophilic colloid layer adjacent to said emulsion layer.
• the addition of these compounds may eventually be effected in the form of an aqueous solution or of a mixture of water and an organic solvent which does not impair the photographic properties of the light-sensitive material.
• a solution of the developing activators may eventually be coated on the emulsion layer.
• the developing activators used in the present invention may be incorporated at different steps of the emulsion preparation. For instance, they may be added as a separate addition or in admixture with one or several other ingredients used for the initial precipitation of the silver halide grains, during the physical or chemical ripening process or in any other step before coating the emulsion. However, they are preferably added to the emulsion after its chemical ripening and just before coatmg.
• the optimum amount added to the emulsion depends upon the selected compound, the nature of the colloidal binding agent for the silver halide grains and the amount and the nature of the silver halide present in the emulsion.
• the developing activators used in the present invention are added in an amount of from 30 mg. to 6 g. per mole of silver halide. If necessary, these compounds, however, may still be added in amounts beyond these values.
• the developing activators used in the present invention can be incorporated into the silver halide emulsion layer in combination with small amounts of a sulfur containing compound, such as allyl isothiocyanate, allyl thiourea and sodium thiosulfate, small amounts of reduction sensitizers, such as the tin compounds described in the Belgian patent specifications 493,464 and 568,687 and the iminoaminomethane sulfinic acid compounds described in the British patent specification 789,823, or small amounts of precious metal compounds, such as of gold, platinum, palladium, iridium, ruthenium and rhodium.
• the sensitizing effect of the compounds initially present in the gelatin may be very advantageously completed by the new developing activators.
• stabilizers may also be used, e.g., mercury compounds, and the compounds mentioned in the prior art and claimed in the Belgian patent specifications 571,916 and 571,917. It is also usual to sensitize and/or to stabilize silver halide emulsions by incorporating cadmium salts or by processing these emulsions in the presence of cadmium salts.
• other ingredients such as fog inhibiting agents, color couplers, developing substances, hardeners and wetting agents, may also be added in a known manner to the emulsion, without impairing it in any way.
• the new compounds may be very efficiently used to increase the X-ray sensitivity and the general lightsensitivity of orthochromatic, panchromatic and all special emulsions as Well as the conventional non spectrally sensitized emulsions. They may be added separately or in combination with optically sensitizing dyestuffs. In the latter case, the addition must be effected before or after the addition of the optically sensitizing dyestuffs. In addition, they may be very advantageously used in the most various emulsions, since they lead to an outstanding sensitivity increase in the negative as well as in the positive emulsion types.
• Example 7 shows that the use of phosphoric acid esters induces a higher light-sensitivity and less fog than when using the known polyoxyalkylenes or the polyoxyalkylene derivatives which are used to prepare the phosphoric acid esters according to the invention.
• Example 1 A washed negative coarse-grained gelatin silver bromoiodide emulsion (average grain size: 0.8 in which the silver halide consists of 94.5 mole percent of silver bromide and 5.5 mole percent of silver iodide, is ripened until the optimum light-sensitivity is obtained. After the addition of a panchromatic sensitizing dyestulf and other usual ingredients, the emulsion is coated on a support (sample 1).
• samples are prepared'by adding every time to determined amounts of the same emulsion before coating, the hereafter indicated amounts of developing accelerators per mole of silver halide present. Then, they are processed in the same manner as sample 1. After drying and exposure, the samples are developed for 7 minutes at 20 C. in a solution having the following composition:
• Example 4 The emulsion has the same composition as that desa-mple Added wmpolmdin $011016 Relative Gamma Fog scribed in Example 1 but the average grain size of the of silver halide sensitivity silver halide grams amounts to 1,41. and the silver halide 1 100 33 0 07 consists of 96 mole percent of silver bromide and 4 mole 2 0.034 g.
• the emulsion samples contain cording to preparation 1. 3 0.34 g. of the compound w 162 Q38 0 08 the hereafter indicated amounts of developmg acceler cording to preparation 1. ators: 4 3.40 gd of the compound ac- 178 0.42 0. 08 5 0.511.1 5 11522 552231 O. 3., 0. o sample Adda i a ese Gamma Fog cording to preparation of silver hahde sensitivity 6 0.34 g(.1 01 the compound 210- 282 0.48 0.10
• Example 1 the following sensitometric results 7 340 g the compound w 230 (L54 MO are obtained: cording to preparation 5.
• Example 6 the following sensitometric results are ob- Example 6 tained:
• the emulsion is coated on a support (Sample 1).
• R is an alkylene group of from about 2 to about 3 carbon atoms
• n lsaposltlvemteger fmmsto R is a member selected from the group consisting of an obtained:
• alkyl radical containing from about 1 to about 20 carbon atoms, and an aralkyl radical
• R 13 is a member selected from the group consisting of a hydrogen atom, an aryl radical and an alkylaryl radical, R is an alkyl radical containing from about 1 to about 20 carbon atoms, and X is an acid radical.
• a light-sensitive photographic material comprising a support and at least one gelatino silver halide emulsion layer containing a phosphoric acid ester of a polyoxyalkylene compound in an amount between 30 mg. to 6 g. per mole of silver halide said phosphoric acid ester being a condensation product of a phosphorus compound selected from the group consisting of phosphorus pentoxide and phosphorus oxychloride with a polyoxyethylene compound corresponding to one of the following general formulae:
• R is a member selected from the group consisting of an alkyl radical, containing from about 1 to about 20 carbon atoms and an aralkyl radical,
• R is a member selected from the group consisting of an aryl radical, an alkylaryl radical, and an hydrogen atom,
• R is an alkyl radical containing from about 1 to about 20 carbon atoms
• X- is an acid radical
• n is a positive integer from 5 to 35.
• n has a value of about 50.

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Cited By (4)

Citations (6)

• 0
  • BE BE611864D patent/BE611864A/xx unknown
• 1962
  • 1962-12-21 US US246357A patent/US3210192A/en not_active Expired - Lifetime
  • 1962-12-24 GB GB48584/62A patent/GB1015023A/en not_active Expired

Patent Citations (6)

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