US1574944A - Photographic light-sensitive material and process of making the same - Google Patents

Photographic light-sensitive material and process of making the same Download PDF

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Publication number
US1574944A
US1574944A US718411A US71841124A US1574944A US 1574944 A US1574944 A US 1574944A US 718411 A US718411 A US 718411A US 71841124 A US71841124 A US 71841124A US 1574944 A US1574944 A US 1574944A
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Prior art keywords
emulsion
gelatin
silver
compound
sensitiveness
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US718411A
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English (en)
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Samuel E Sheppard
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US718410A priority Critical patent/US1574943A/en
Priority to US718411A priority patent/US1574944A/en
Priority to US718409A priority patent/US1600736A/en
Priority to FR599932D priority patent/FR599932A/fr
Priority to FR599934D priority patent/FR599934A/fr
Priority to FR599933D priority patent/FR599933A/fr
Priority to DEE32601D priority patent/DE439372C/de
Priority to DEE32600D priority patent/DE441934C/de
Priority to DEE32599D priority patent/DE433043C/de
Priority to GB14629/25A priority patent/GB235209A/en
Priority to GB14630/25A priority patent/GB235210A/en
Priority to NL30418A priority patent/NL21355C/xx
Priority to US82847A priority patent/US1602592A/en
Priority to US82845A priority patent/US1602590A/en
Priority to US82846A priority patent/US1602591A/en
Application granted granted Critical
Publication of US1574944A publication Critical patent/US1574944A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/005—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
    • G03C1/10—Organic substances
    • 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
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • 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

Definitions

  • This invention relates to the art of photographic materials.
  • One object of the invention is toprovide photographic emulsions, especially developing-out ones, having new or lmproved properties because of the use or presence thereinof materials, the sensitizing properties-of which I have discovered.
  • Still another-object of my invention is to provide processes in which such materials are used to improve photographic emulsions, especially developing-out ones, as regards lightsensitiveness, by which term I include their ability to give the earliest visible impression or image with'the minimum exposure or their ability to give density after a given exposure or both, the usual photographic fluid treatments being used in preparing such impression or image or density.
  • a further object of the invention is to provide colloid products, such for instance as gelatins, the usefulness of which for forming light sensitive photographic emulsions, especially developing-out emulsions, is greatly increased and controlled by my said sensitizing materials incorporated therewith.
  • Another object of the invention is to provide processes for preparing said colloid products or intermediates.
  • each compound of these series contains a divalent atom of the sulfur group (a sulfur atom in one series, a selenium atom in another series, a tellurium atom in still another series) which is joined by adouble bond to a singlemetalloid atom (not one bond to one atom, and the other bond to a different atom) to which at least another groupof atoms is attached.
  • a divalent atom of the sulfur group a sulfur atom in one series, a selenium atom in another series, a tellurium atom in still another series
  • a singlemetalloid atom not one bond to one atom, and the other bond to a different atom
  • the last mentioned group of atoms be such that it induces in the compound a chemical affinity for silver halids,-for instance the compound may combine to an. appreciable extent with silver halid to form a soluble complex salt, when said atomic group is present.
  • my selenium or telfrom the above series the ourea (thiosinamine) containing an allyl radical in place of one of the hydrogen atoms of thiourea, is especially useful in practicing my invention.
  • ourea thiosinamine
  • said double bonded atom of the sulphur group is chemically held in the molecule with intermediate firmness.
  • Such atom does not react on silver halids as readily as the sulphur atom in sodium sulphide for instance, but it separates out more readily than the sulphur atom in ethyl mercaptan for example. Consequently said double bonded sulphur-group atoms in my compounds correspond roughly in the firmness with which they are held to the firmness with which the sulphur atoms are held in the so-called potential mercaptans, although there is, of course, some range of difference in the firmness with Which said doublebonded atoms are held in the different compounds of my series.
  • the sensitiveness of the grains of silver halid in emulsions has 'been shown to correspond to the presence in said grains of nuclei of unstatedvchemical composition. I, therefore, attribute the sensitizing action of my compounds to their forming in the emulsion grains small, mostly ultramicroscopic, nuclei. which includes silver combined with either sulfur, or selenium, or tellarium, such as silver sulfid,
  • sensitizing compound such as thiosinamine for instance
  • 100 pounds of gelatin (computed as dry) or 130 pounds of emulsion (computed as dry) is within the useful limits and generally excellent,say for instance with alkaline developing-out gelatino-silver-halid emulsions.
  • seusitizers are employed when less sensitizing effects are desired; but it is important not to exceed the upper limits as stated above.
  • Gelatins for instance, can be selected for their physical properties, such as setting ability, melting point and viscosity, without regard to whether they can be made into suflis-iently light-sensitive emulsions, and any deficiency insensitizing power can be made up by in corporating a little quantity of one or more of my independent compounds. .Nor are the grain-size characteristics affected by such id in the emulsions which is independent of the ratio of gelatin to silver halid. Still differently stated. the sensitizer compounds can be added without adding any colloid, such as gelatln, and are, therefore, independent thereof. i
  • the sen sitiveness is increased throughout the normal spectral range of the emulsion instead of at only those spectral points corresponding to the spectral absorption of the sensi-' tizing compound.
  • My compounds are effective in increasing the general light-sensitiveness of orthochromatic, panchromatic, X-ray, and all special emulsions, as well as the ordinary or non-color-sensitized ones. They can be added without 'or with sensitizing dyes or before or after them. They do not specifically affect the dye action; but simply increase the general sensitivenessand thus increase the ordinary sensitiveness to blue light to at least as great an extent as to light of a color corresponding to the dye.
  • My sensitizing compounds may he used in many ways. Broadly they may be incorporated in emulsions or incolloids for emulsions or both. They can also enter the emulsion mixed with other ingredients thereof whether organic or inorganic. They may be added at different stages of emulsion manufacture, even when the latter is otherwise complete ready for coating. Since their action is rapid when incorporated, the coating in such case need be delayed only long enough to mix in the sensitizing compounds. With the grain characteristics, such as size distribution, etc., already determined, and the other physical and photographic properties of the emulsion already taken care of at this stage, I can practically independently increase its light sensitiveness without impairing said other properties by adding one or more of my compounds. The latter are especially effective in emulsions which are, at least slightly, alkaline.
  • sensltlveness can be effected in one step by thoro'ughly'stirringall of the sensitizingcompound into the emulsion at one time; or it may be incorporated part at a time in successive steps.
  • correctional quantities of my s'ensi-,- tizing compounds can be premixed withan mgredient, such as gelatm.
  • thiosinamine by weight is to be incorporated into 300,000 parts by weight of the above described emulsion (computed as the weight of its non-aqueous ingredients) the emulsion is melted, the thiosinamine dissolved in ethyl alcohol or water or a mixture of them, the volume of said solvent being under approximately 1.5% 'of the volume of r the melted emulsion, and then the solution mid, thiobarbituric acid, telluro-mustard-oil (allyl isotellurocyanate) potassium tellurocyanide, allyl tellurourea. It is preferable to use these compounds in substantially pure or C. P. form; but impurities which are harmless to the emulsion and are not bulky, can be tolerated.
  • the selenocyanide and tellurocyanide are used in-higher proportions than the other listed compounds.
  • the emulsion, being melted to the desired flowability is coated on its support, such as glass, film, paper, etc., in the well known way. It is convenient to control and checkthe process by coating samples of the emulsion before and after the addition of mypse'nsitizing compounds, the coated specimens beingtried out photographically by any well known sensitometric test, or even by comparative camera exposures on the same subject under like conditions. Of course, the usual precautions are observed during the emulsion making and coating processes, such as the use of non-actinic or safe light, cleanness of vessels and air, etc. I
  • the different gelatines sold for photographic emulsion-making may be ,used in the example given above, hard ones being very useful.
  • the temperatures given are, of course, adjusted if the particular gelatin employed has physical properties, such as melting and setting points, which deviate considerably from the usual ones, such adjustment being a matter of routine control.
  • an almost inert gelatin may be employed,one which-forms an emulsion which produces a developable image, if at all, only after impractically long exposures, and then does not yield an image of desirable density.
  • a gelatin which forms such a practically inert emulsion may be prepared in the way described under the heading Preparation of ash-free gelatin in pages 1850 and 1859 of the Journal of the American Chemical Society, September, 1922, Vol. XLIV, N0. 9, being part of an article by Sheppard, Sweet, and Benedict on Elasticity of purified gelatin jellies as a function of hydrogen-ion concentration.
  • Emulsions of impractically low light-sensitiveness made by the above described process from such prepared gelatin are transformed by my sensitizing compounds into emulsions which give developable images of excellent density after usefully brief exposures.
  • I have, for example, been able to increase the light-sensitiveness of some such low sensitiveemulsions ten or even over twenty times, the exposures for a given subject in the latter case being cut to less than one twentieth of the original one and the image density being ma e excellent by I a corresponding gain.
  • I can prepare inert gelatins by treating active photographic gelatins with oxidizing agents.
  • oxidizing agents oxidize the sulfur in the sensitizing substituted (allyl) thiocarbamide or corresponding carbimide, which occurs naturally in photographic gelatins, thus converting it toa nonsensitizing compound and leaving the gelatins practically inert.
  • Dilute aqueous solutions of a peroxide, such as sodium peroxide (say from 5 to 10% by weight) is intimately mixed into the gelatin and then washed out when the oxidation has occurred.
  • the inert gelatin referred to in the preceding para-- graph can be thus oxidized to make its inertness doubly sure.
  • the oxidizing step during the regular manufacturing. operations, say the liming and/or deliming treatments.
  • the oxidizing agents should be effective as desensitizers and yet not be present in quantities capable of materially reducing the yield of gelatin or harming its quality, especially its physi- Nor should they leave ob jectionable products from the oxidation re-- action.
  • the regular liming solution of the usual gelatin manufacturing process can b e saturated with as much calcium hypochlorite as will dissolve therein;
  • My sensitizing compounds may be incorporated into gelatin from which photographic emulsions are to be. made. v This strengthen'edgelatin then constitutes a facture.
  • any good gelatin may be inert by the above described'oxidation treatment during liming or deliming is particularly ada ted to this strengthening.
  • Emulsions ma e fromth'e mixture have markedly increased light-sensitiveness as compared with those. made from corresponding unstrengthened 'gelatins.
  • the proportion of sensitizing material is, of course, adjusted to give the desired controlof the sensitiveness of emulsions made fromthe gelatin, the totalsensitizing material in the strengthened gelatin being thus brought to, or even above, normal.
  • this activating of gelatin is one of the most desirable ways of employing.
  • my sensitizing compounds In fact, premixingof one or more of my sensitizers with gelatm is my preferred system.
  • the comfpound say thiosinainine, is takenup, pre erably in as little aqueous-alcohol mixture as is practicable, and then this concentratedsolution added to the gelatin solution. In this way'imdesirable dilution of the latter is avoided.
  • the s'ensitizing'solution may be accurately and continually dosed into a regulated@ stream ofgelatin solution with continuous mixing.
  • dried or set gelatin may be allowed to swell in an aqueous solution of the sensitizing compound.
  • the nearly uniform distribution or diffusion of the compound in the gelatin thus efi'ected can be made even more nearly uniform by melting and agitating the swollen gelatin.
  • the steps of treating With ammonia and warming of the emulsion just before its final setting improve the photographic properties of the emulsion, especially when the latter is made from hard gelatins. But one or both of them maybe omitted.
  • my sensitizing compounds act by themselves to. increase the light-sensitiveness, whether ripening steps be employed or not, and so can wholly or partially replace them. But I prefer to use them because the effect of either or both of them is to help increase the light-sensitiveness of the emulsions and thus give a stronger initial sensitized condition which is multiplied or increased by using my sensitizing compounds.
  • these steps can sometimes be shortened and made more certain in effect by reason of the use of my powerful and dependable sensitizing compounds. 1
  • gelatin emulsions and emphasized the developingout and alkaline types because at the present time they are l the ones, which have the widest practical use. Moreover they form the best medium for testing new sensitizing-compounds. But other organic colloids and mixtures of them with each other or with gelatin, where their nature admits such mixtures, may be used in making light-sensitive emulsions which of the others. Y
  • a photographic emulsion comprising a colloid, particles of photographic silver salt suspended therein, and an added compound therein upon which at least part of the lightsensitiveness of the emulsion depends,
  • said compound containing a divalent atom of the sulfur group directly joined by a double bond to a single metalloid atom, -to which at least another group of atoms is attached, the pro ortion of said compound being substantiall'y independent of the proportion of said colloid.
  • a photographic developing-out emulsion comprising a colloid, particles of silver halid suspended therein, and an added compound therein upon which at leastpart of the light-sensitiveness of the emulsion depends, said compound having a chemical affinity for silver halid. and containing an atom of the sulfur group joined to a single metalloid atom,.to which at least another group of atoms is attached, the presence of said last named group inducing saidchemical afiinity, the proportion of said compound being substantially independent of the proportion of said colloid.
  • a photographic developing-out emulsion comprising gelatin, particles of silver halid suspended therein, and an added compound therein upon which at least art of the light-sensitiveness of the emulsion de pends, said com ound containing a divalent atom of the sulfur group directly joined by a double bond to a single carbon atom to which at least another group of atoms is attached, the proportion ofsaid compound being substantially independent of-the proportion of said gelatin.
  • a photographic developingout emulsion comprising a colloid, particles of photographic silver salts suspended therein, an added-compound which orms small ultra-' microscopic nuclei of a silver compound containing an atom of the sulfur group, said nuclei being located on said particles of silver halid, the proportion of said compound being substantially independent ofthe proportion of said colloid.
  • a photographic developing-out emulsion comprising gelatin, particles of silver halid suspended therein, and an added senat least part of the light sensitiveness of the emulsion depends, the propprtion of said thiocarbamid being substantially independent: of the proportion of gelatin,
  • a photographic developing-out emulsion comprising gelatin, particles of photographic silver salt suspended therein and thiosinamine added therein upon which at least art of the li ht-sensitiveness 'of the emulslon depends, file proportion of said thiosinamine being substantially independent-of the proportion of said gelatin.
  • a photographic developing-out gela tino-silver-halid emulsion of the alkaline type of relatively high light-sensitiveness comprising a mixture of the constituents of a gelatino-silver-halid emulsion of lower light-sensitiveness, and an added sensitizing compound upon which depends the difference between said lower and said high light-sensitiveness, said compound containing a divalent atom of the sulfur group directly joined by a double bond to a single metalloid atom to-which at least another group of atoms is attached, the proportion of said compound being substantially independent ofthe proportion of gelatin.
  • a photographic developing-out gelatino-silver-hahd emulsion of the alkaline type of relatively high light-sensitiveness comprisin a mixture of the constituents of a gelatin-silver-halid emulsion of lower lightsensitiveness and an added sensitizing compound upon Which depends the difference between said lower and said high light-sensitiveness, said compound having a chemical afiinit-y of silver halid and containing an atom of the sulfur group joined to a single metalloid atom to which at least another group of atoms is attached, the presence of said last named group inducing said chemical afiinity, and the proportion of said compound being substantially independent of j the proportion of said colloid.
  • a photographic developing-out gelatino-silver-halid emulsion of the alkaline type of relatively high light-sensitiveness comprising a mixture of the constituents of a gclatino-silver-halid emulsion ,of lower light-sensitiveness and an added sensitizing compound upon which depends the dillerence between said lower and said high light sensitiveness, said compound containing a divalent atom of the sulfur group directly joined by a double bond to a single carbon atom to which at least another group of atoms is attached, the proportion of said compound being substantially independentof the proportion of the gelatin.
  • a photographic developing-out gelatino-silver-halid emulsion of the alkaline type of relatively high light-sensitiveness comprising a mixture of the constituents of a gelatino-silver-halid emulsion of lower light-sensitiveness and a sensitizer comprising thiocarbamid upon which depends the difierence between said lower and said high light-sensitiveness, the proportion of sensitizer being substantially independent of the proportion of gelatin.
  • a photographic emulsion comprising a colloid, particles of photographic silver upon which at least part of the light-sen-' sitiveness of the emulsion depends, said compound having a chemical affinity for silver halid and containing an atom of the sulfur group joined to a single metalloid atom to which at least another group of atoms is attached, the presence of said last named group inducing said chemical aflinity, said emulsion being substantially free from sensitizing dye, and the proportion of said compound being substantially independent ofthe proportion of said gelatin.
  • a photographic emulsion comprising gelatin, particles of silver halid suspended therein and an added compound therein upon which at least part of the light-sensitivcness of the emulsion depends, said compound containing a' divalent atom of the sulfur group directly joined by a double bond to a single carbon atomto which at least another group of atoms is attached, the proportion of said compound being substantially independent of the proportion of gelatin, said emulsion being substantially free from sensitizing dye.
  • a photographic developing-out emulsion comprising gelatin, particles of silver halid suspended'therein and an added sensitizer containing thiocarbamid upon which at least part ofthe light-sensitiveness of the emulsion depends, said emulsion being substantially free from sensitizing dye, and the proportion of said compound being sub; stantially independent of the proportionjoi'v said gelatin.
  • a photographic emulsion comprising gelatin, particles of silver halid suspended therein and an added thiosinamine upon which at least part of the light-sensitiveness of the emulsion depends, said emulsion being substantially free from sensitizing dye, and the proportion of thiosinamine being substantially independent of the proportion of gelatin.
  • a photographic emulsion comprising a colloid, particles'of photographic silver salt suspended therein and an added compound therein upon which at least part. of the light-sensitiveness of the emulsion depends, said compound containing a divalent atom ot'the sulfur group directly joined by a double bond to a single metalloid atom, to which at least another group of atoms is attached, theamount of added compound being less than the order of '10 grains per 130 pounds of emulsion and insulticient to cause immediate fogging tendency.
  • a photographic developing-out emulsion comprising a colloid, particles ot silver halid suspended therein, and an added compound therein upon which at least part of the light-sensitiveness of the emulsion depends, said compound having a chemical affinity for silver halid and containing an atom of the sulfur group joined to'a single metalloid atom to which at least another group of atoms is attached, the presence of said last named group inducing said chemical afiinity, the amount of added compound being less than the order of 10 grains per-130 pounds of. emulsion and insufiicient to cause immediate fogging tendency.
  • a photographic developing-out emulsion comprising gelatin, particles of silver halid suspended therein, and an added compound therein upon' which atleast part of the light-sensitiveness of the emulsion depends, said compound containing a divalent atom of the sulfur group directly joined by a double bond to a single carbon atom to which at least another group of atoms is attached, the amount of added compound being less than the order. of 10 grains per 1 0 pounds of emulsion and insufficient to cause immediate fogging tendency.
  • a photographic developingout emulsion comprising gelatin, particles of silver halid suspended therein, and an added sensitizer containing thiocarbamid upon which at least part of the light-sensitiveness of the emulsion depends, the amount of added compound being less than the order of 10 grains per 130 pounds of emulsion and insuflicicnt to cause immediate fogging tendency.
  • a photographic developing-out emulsion comprising gelatin, particles of photographic silver salt suspended therein and thiosinamine added therein upon which at least part of .the light-sensitiveness of the emulsion depends, the amount of added compound being less than the order of 10 grains per 130 pounds of emulsion and insuflicient to cause immediate fogging tendency.
  • Aphotographic developing-out emulsion comprising a colloid, particles of photographic silver salt suspended therein and an added, compound therein upon which at of greater density than the set tolerance.
  • a photographic developing-out emulsion comprising gelatin, particles of silver halid suspended therein and an added thiocarbamid upon which at least part of the light-sensitiveness of the emulsion depends, the amount of said thiocarbamid being insufficient to cause fog of greater density than the set tolerance.
  • A- photographic developing-out emulsion comprising gelatin, particles of silver halid suspended therein and an added thiosinamine upon which at least part of the light-sensitiveness of the emulsion depends, the amount of said thiosinamine being insufiicie-nt to cause fog of greater density than the set tolerance.
  • creasing the light-sensitiveness thereof by incorporating with the otherconstituents thereof an independent sensitizing compound containing a divalent atonof the sulfur group directly joined by a double bond to a single carbon atom to which at least another group of atoms is attached, the amount of said added compound being less than the order of 10 grains per. 130
  • emulsion-forming colloid having incorporated therein an independent sensitizing compound containing a divalent atom of the sulfur group directly joined by a double bond, to a single metalloid atom to which at least .another group of atoms is attached.
  • An intermediate for use in making photographic emulsions comprising an emulsion-forming colloid having incorporated therein an independent sensitizing compound, said compound having a chemical aflinity for silver halid and containing an atom of the sulfur group joined to a single metalloid atom to which at least another groupof atoms is attached, the pressaidlast named group inducing said chemical affinity.
  • An inte'rmediate for use in making photographic emulsions, comprising gelatin having incorporated therein an independent sensitizing compound, containing a divalent atom of the sulfur group directly joined to O -a single carbon atom to which at least another group of atoms is attached.
  • An intermediate for use in making photographic emulsions comprising gelatin having incor orated therein an independent thiocarbami i.
  • photographic emulsions comprising gelatin having incorporated therein independent thiosinamine.
  • An intermediate for use in making photographic emulsions comprising .an emulsion-forming colloid having incorporatedtherein an independent sensitizing compound containing a divalent atom of the sulfur group directly joined by a double bond to a single metalloid atom to which at least another group of atoms -is; attached, the amount of said added compound being less than the order of 10 grains in 100 ppunds of gelatin.
  • An intermediate for use in making photographic emulsions comprising an emulsion-forming colloid having incorporated therein an independent sensitizing compound, said compound having a chemical affinity for silver halid and containing an atom of the sulfur ,group joined to a single metalloid atom to which at least another group of atoms is attached, the presence of said last named group inducing said chem.- ical aflinity, the amount of said added compound being less than the order of 10 grains in 100 pounds of gelatin.
  • An intermediate for use in making photographic emulsions comprising gelatin having incorporated therein an independent sensitizing compound "containing a divalent atom of the sulfur group directly joined to a single carbon atom to which at least another group of atoms is attached, the amount of said added compound being less than the order of 10 grains in pounds 58.
  • An intermediate for. use in making photographic emulsions comprising gelatin having incorporated therein thiosinamine, the amount of said added compound being less than the order of 10 grains in 100 pounds of gelatin.
  • An intermediate for use in making photographic developing out emulsions comprising a mixture of gelatin and an independent sensitizing com ound containing a divalent atom of the su fur group directly joined by a double bond to'a single metalloid atom,'to which at least another group of atoms is attached, the proportion. of said compound being insufficient to cause fog density exceeding the set tolerance when said intermediate is made into said developing- 1 (32.
  • Theprocess of making an intermediate for use in. the preparation of photoa double bond to a single graphic emulsions which comprises incorporating man emulsion-forming colloid an -lI1 dependent sensit zing compound, said compound having a chemical aflinity for silver amount of said added compound being less than the order of 10 grains per 100 pounds of said colloid (calculated as dry colloid) and being insufiicient to cause immediate fogging tendency.
  • The'process of making an intermediate for use in the preparation of photographic emulsions which comprises adding to an emulsion-forming colloid a thiocar- 9 bamid, the amountof said added compound being less than the order of 10 grains per 100 pounds of saidcolloid (calculated as dry colloid) and being insuflicient to cause immediate fogging tendency.

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  • 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)
  • Colloid Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
US718411A 1924-06-06 1924-06-06 Photographic light-sensitive material and process of making the same Expired - Lifetime US1574944A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
US718410A US1574943A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
US718411A US1574944A (en) 1924-06-06 1924-06-06 Photographic light-sensitive material and process of making the same
US718409A US1600736A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
FR599934D FR599934A (fr) 1924-06-06 1925-06-03 Perfectionnements dans les matières photographiques et dans leurs procédés de fabrication
FR599933D FR599933A (fr) 1924-06-06 1925-06-03 Perfectionnement dans l'industrie des matières photographiques
FR599932D FR599932A (fr) 1924-06-06 1925-06-03 Perfectionnement dans l'industrie des matières photographiques
DEE32600D DE441934C (de) 1924-06-06 1925-06-04 Verfahren zur Herstellung von organischen Stoffen zur Erhoehung der Lichtempfindlichkeit von Emulsionen, beispielsweise Gelatinesilberhaloid-Emulsionen
DEE32599D DE433043C (de) 1924-06-06 1925-06-04 Verfahren zur Herstellung eines organischen oder biochemischen lichtempfindlich machenden Stoffes
DEE32601D DE439372C (de) 1924-06-06 1925-06-04 Verfahren zur Herstellung einer lichtempfindlichen Emulsion
GB14629/25A GB235209A (en) 1924-06-06 1925-06-05 Improvements in or relating to the manufacture of photographic emulsions
GB14630/25A GB235210A (en) 1924-06-06 1925-06-05 Improvements in or relating to the manufacture of photographic emulsions
NL30418A NL21355C (enrdf_load_html_response) 1924-06-06 1925-06-06
US82847A US1602592A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing selenium and process of making the same
US82845A US1602590A (en) 1924-06-06 1926-01-21 Utilization of biochemical light-sensitizing extracts in the art of photographic materials
US82846A US1602591A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing tellurium and process of making the same

Applications Claiming Priority (6)

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US718410A US1574943A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
US718409A US1600736A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
US718411A US1574944A (en) 1924-06-06 1924-06-06 Photographic light-sensitive material and process of making the same
US82847A US1602592A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing selenium and process of making the same
US82845A US1602590A (en) 1924-06-06 1926-01-21 Utilization of biochemical light-sensitizing extracts in the art of photographic materials
US82846A US1602591A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing tellurium and process of making the same

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US718411A Expired - Lifetime US1574944A (en) 1924-06-06 1924-06-06 Photographic light-sensitive material and process of making the same
US718410A Expired - Lifetime US1574943A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
US718409A Expired - Lifetime US1600736A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
US82847A Expired - Lifetime US1602592A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing selenium and process of making the same
US82846A Expired - Lifetime US1602591A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing tellurium and process of making the same
US82845A Expired - Lifetime US1602590A (en) 1924-06-06 1926-01-21 Utilization of biochemical light-sensitizing extracts in the art of photographic materials

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US718410A Expired - Lifetime US1574943A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
US718409A Expired - Lifetime US1600736A (en) 1924-06-06 1924-06-06 Art of light-sensitive photographic materials
US82847A Expired - Lifetime US1602592A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing selenium and process of making the same
US82846A Expired - Lifetime US1602591A (en) 1924-06-06 1926-01-21 Photographic light-sensitive material containing tellurium and process of making the same
US82845A Expired - Lifetime US1602590A (en) 1924-06-06 1926-01-21 Utilization of biochemical light-sensitizing extracts in the art of photographic materials

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US2449153A (en) * 1944-04-03 1948-09-14 Urbach Franz Photographic silver bromide emulsion sensitized with cysteine
US2571688A (en) * 1946-11-29 1951-10-16 Ilford Ltd Production of colloidal silver
US2624674A (en) * 1946-06-29 1953-01-06 Eastman Kodak Co Photographic emulsion sensitized with gold compounds and sulfur sensitizers
US2644756A (en) * 1947-02-08 1953-07-07 Polaroid Corp Photographic process for forming a positive transfer image
US2743180A (en) * 1953-07-01 1956-04-24 Eastman Kodak Co Pentazaindene stabilizers for photo-graphic emulsions sensitized with alkylene oxide polymers
US2751299A (en) * 1952-11-08 1956-06-19 Eastman Kodak Co Mercury stabilizers for photographic emulsions sensitized with polyalkylene esters, amides, and ethers
US2756148A (en) * 1954-06-29 1956-07-24 Eastman Kodak Co Photographic emulsion having clayden effect susceptibility
US2999751A (en) * 1957-07-30 1961-09-12 Gen Aniline & Film Corp Chemical sensitizing of photographic silver halide emulsions
US3144336A (en) * 1961-10-26 1964-08-11 Eastman Kodak Co Synergistic sensitization of photographic silver halide emulsions
US3297446A (en) * 1964-02-10 1967-01-10 Eastman Kodak Co Synergistic sensitization of photographic systems with labile selenium and a noble metal
US3320069A (en) * 1966-03-18 1967-05-16 Eastman Kodak Co Sulfur group sensitized emulsions
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US3977880A (en) * 1973-10-18 1976-08-31 Fuji Photo Film Co., Ltd. Direct-positive emulsion containing silver halide grains internally doped with metal ions, surface ripened with gold and sulfur compound and fogged by light exposure
US4197124A (en) * 1975-07-29 1980-04-08 Fuji Photo Film Co., Ltd. Non-treatment type planographic printing plate materials
US4349623A (en) * 1979-06-15 1982-09-14 Fuji Photo Film Co., Ltd. Silver halide photographic materials
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EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
US4665017A (en) * 1983-12-08 1987-05-12 Fuji Photo Film Co., Ltd. Process for preparing silver halide emulsion and silver halide photographic light-sensitive material
US4678745A (en) * 1984-06-15 1987-07-07 Fuji Photo Film Co., Ltd. Process for producing silver halide emulsion and silver halide photographic light-sensitive material containing the same
EP0228084A2 (en) 1985-12-25 1987-07-08 Fuji Photo Film Co., Ltd. Image forming process
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
US4764457A (en) * 1981-08-17 1988-08-16 Konishiroku Photo Industry Co., Ltd. Silver halide photographic emulsion
US4863845A (en) * 1984-06-15 1989-09-05 Fuji Photo Film Co., Ltd. Internal latent image type direct positive silver halide emulsions and process for producing the same
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0567151A1 (en) * 1992-04-24 1993-10-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5273872A (en) * 1991-11-06 1993-12-28 Fuji Photo Film Co. Ltd. Silver halide photographic material and image forming method using the same
EP0580041A2 (en) 1992-07-10 1994-01-26 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing
EP0589460A1 (en) 1992-09-24 1994-03-30 Fuji Photo Film Co., Ltd. Method for processing a black & white silver halide light-sensitive material
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
US5389511A (en) * 1991-11-06 1995-02-14 Konica Corporation Silver halide photographic emulsion and light-sensitive silver halide photographic material making use of the same
US5395745A (en) * 1991-06-28 1995-03-07 Fuji Photo Film Co., Ltd. Silver halide emulsion, and light-sensitive material prepared by using the emulsion
US5459027A (en) * 1991-06-28 1995-10-17 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0708370A2 (en) 1994-10-18 1996-04-24 Minnesota Mining And Manufacturing Company Process for manufacturing diffusion transfer printing plates
EP0708371A2 (en) 1994-10-18 1996-04-24 Minnesota Mining And Manufacturing Company Additive for improving the performance of diffusion transfer printing plates
US5514534A (en) * 1991-06-28 1996-05-07 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5556738A (en) * 1994-07-18 1996-09-17 Konica Corporation Silver halide photographic element and processing method thereof
US5561033A (en) * 1991-07-24 1996-10-01 Fuji Photo Film, Co., Ltd. Silver halide photographic light-sensitive material
US5573899A (en) * 1991-11-15 1996-11-12 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
EP0777150A1 (en) 1995-11-29 1997-06-04 Konica Corporation Developing composition for silver halide photographic light sensitive material
US5800975A (en) * 1994-12-14 1998-09-01 Konica Corporation Silver halide photographic light sensitive material
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same
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US2757088A (en) * 1953-12-30 1956-07-31 Du Pont Photographic silver halide emulsions containing phytic acid
US2757089A (en) * 1954-01-05 1956-07-31 Du Pont Phytic acid sensitizer for silver halide emulsions
US3184312A (en) * 1958-11-14 1965-05-18 Eastman Kodak Co Photographic emulsions containing carboxymethylated pigskin gelatin
DE1151174B (de) * 1962-01-31 1963-07-04 Dr Karl Petz Verfahren zur Herstellung hochempfindlicher photographischer Emulsionen mit Hilfe der Sensibilisierung durch Goldsalze
GB1143673A (enrdf_load_html_response) * 1965-04-29
GB1282303A (en) * 1969-03-07 1972-07-19 Agfa Gevaert Improved light-sensitive material
US5166045A (en) * 1989-06-19 1992-11-24 Eastman Kodak Company Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains
JP2921979B2 (ja) * 1989-06-19 1999-07-19 イーストマン コダック カンパニー 改良光活性粒子生成のための第▲ｖｉ▼ｂ族化合物によるハロゲン化銀乳剤のドーピング
JPH04204640A (ja) * 1990-11-30 1992-07-27 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5240827A (en) * 1991-02-08 1993-08-31 Eastman Kodak Company Photographic element containing large, selenium-sensitized silver chloride grains
EP0514675B1 (en) 1991-04-22 1999-12-08 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
JP2699029B2 (ja) * 1991-05-08 1998-01-19 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
DE69131024T2 (de) * 1991-12-18 1999-08-05 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Photographisches silberhalogenidmaterial
EP0573649B1 (en) * 1991-12-18 1999-04-07 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0619515B1 (en) * 1993-04-07 2000-12-20 Fuji Photo Film Co., Ltd. Surface latent image type silver halide photographic emulsion

Cited By (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2449153A (en) * 1944-04-03 1948-09-14 Urbach Franz Photographic silver bromide emulsion sensitized with cysteine
US2624674A (en) * 1946-06-29 1953-01-06 Eastman Kodak Co Photographic emulsion sensitized with gold compounds and sulfur sensitizers
US2571688A (en) * 1946-11-29 1951-10-16 Ilford Ltd Production of colloidal silver
US2644756A (en) * 1947-02-08 1953-07-07 Polaroid Corp Photographic process for forming a positive transfer image
US2751299A (en) * 1952-11-08 1956-06-19 Eastman Kodak Co Mercury stabilizers for photographic emulsions sensitized with polyalkylene esters, amides, and ethers
US2743180A (en) * 1953-07-01 1956-04-24 Eastman Kodak Co Pentazaindene stabilizers for photo-graphic emulsions sensitized with alkylene oxide polymers
US2756148A (en) * 1954-06-29 1956-07-24 Eastman Kodak Co Photographic emulsion having clayden effect susceptibility
US2999751A (en) * 1957-07-30 1961-09-12 Gen Aniline & Film Corp Chemical sensitizing of photographic silver halide emulsions
US3144336A (en) * 1961-10-26 1964-08-11 Eastman Kodak Co Synergistic sensitization of photographic silver halide emulsions
US3297446A (en) * 1964-02-10 1967-01-10 Eastman Kodak Co Synergistic sensitization of photographic systems with labile selenium and a noble metal
US3320069A (en) * 1966-03-18 1967-05-16 Eastman Kodak Co Sulfur group sensitized emulsions
JPS4937850B1 (enrdf_load_html_response) * 1969-11-21 1974-10-12
DE2112729A1 (de) * 1970-03-20 1971-09-30 Eastman Kodak Co Farbphotographisches Aufzeichnungsmaterial
US3977880A (en) * 1973-10-18 1976-08-31 Fuji Photo Film Co., Ltd. Direct-positive emulsion containing silver halide grains internally doped with metal ions, surface ripened with gold and sulfur compound and fogged by light exposure
JPS511116A (ja) * 1974-06-21 1976-01-07 Mitsubishi Paper Mills Ltd Harogenkaginshashinnyuzaino seizoho
US4197124A (en) * 1975-07-29 1980-04-08 Fuji Photo Film Co., Ltd. Non-treatment type planographic printing plate materials
US4349623A (en) * 1979-06-15 1982-09-14 Fuji Photo Film Co., Ltd. Silver halide photographic materials
US4764457A (en) * 1981-08-17 1988-08-16 Konishiroku Photo Industry Co., Ltd. Silver halide photographic emulsion
EP0106306A2 (en) 1982-10-14 1984-04-25 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0115351A2 (en) 1983-01-28 1984-08-08 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4665017A (en) * 1983-12-08 1987-05-12 Fuji Photo Film Co., Ltd. Process for preparing silver halide emulsion and silver halide photographic light-sensitive material
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4678745A (en) * 1984-06-15 1987-07-07 Fuji Photo Film Co., Ltd. Process for producing silver halide emulsion and silver halide photographic light-sensitive material containing the same
US4863845A (en) * 1984-06-15 1989-09-05 Fuji Photo Film Co., Ltd. Internal latent image type direct positive silver halide emulsions and process for producing the same
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0228084A2 (en) 1985-12-25 1987-07-08 Fuji Photo Film Co., Ltd. Image forming process
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
US5514534A (en) * 1991-06-28 1996-05-07 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5459027A (en) * 1991-06-28 1995-10-17 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5395745A (en) * 1991-06-28 1995-03-07 Fuji Photo Film Co., Ltd. Silver halide emulsion, and light-sensitive material prepared by using the emulsion
US5561033A (en) * 1991-07-24 1996-10-01 Fuji Photo Film, Co., Ltd. Silver halide photographic light-sensitive material
US5273872A (en) * 1991-11-06 1993-12-28 Fuji Photo Film Co. Ltd. Silver halide photographic material and image forming method using the same
US5389511A (en) * 1991-11-06 1995-02-14 Konica Corporation Silver halide photographic emulsion and light-sensitive silver halide photographic material making use of the same
US5573899A (en) * 1991-11-15 1996-11-12 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0567151A1 (en) * 1992-04-24 1993-10-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0580041A2 (en) 1992-07-10 1994-01-26 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing
EP0589460A1 (en) 1992-09-24 1994-03-30 Fuji Photo Film Co., Ltd. Method for processing a black & white silver halide light-sensitive material
US5556738A (en) * 1994-07-18 1996-09-17 Konica Corporation Silver halide photographic element and processing method thereof
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
EP0708371A2 (en) 1994-10-18 1996-04-24 Minnesota Mining And Manufacturing Company Additive for improving the performance of diffusion transfer printing plates
EP0708370A2 (en) 1994-10-18 1996-04-24 Minnesota Mining And Manufacturing Company Process for manufacturing diffusion transfer printing plates
US5800975A (en) * 1994-12-14 1998-09-01 Konica Corporation Silver halide photographic light sensitive material
EP0777150A1 (en) 1995-11-29 1997-06-04 Konica Corporation Developing composition for silver halide photographic light sensitive material
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
US7220537B2 (en) 2003-01-31 2007-05-22 Konica Minolta Photo Imaging, Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

Also Published As

Publication number Publication date
GB235210A (en) 1926-12-06
FR599932A (fr) 1926-01-25
DE439372C (de) 1927-01-12
DE441934C (de) 1927-03-18
US1602592A (en) 1926-10-12
US1602590A (en) 1926-10-12
FR599934A (fr) 1926-01-25
US1602591A (en) 1926-10-12
GB235209A (en) 1926-12-06
US1600736A (en) 1926-09-21
FR599933A (fr) 1926-01-25
DE433043C (de) 1926-08-24
US1574943A (en) 1926-03-02
NL21355C (enrdf_load_html_response) 1930-03-15

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