US3915713A - Silver halide photographic emulsion - Google Patents

Silver halide photographic emulsion Download PDF

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US3915713A
US3915713A US412518A US41251873A US3915713A US 3915713 A US3915713 A US 3915713A US 412518 A US412518 A US 412518A US 41251873 A US41251873 A US 41251873A US 3915713 A US3915713 A US 3915713A
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silver halide
emulsion
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photographic emulsion
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Keisuke Shiba
Seiiti Kubodera
Haruo Takei
Atsuaki Arai
Mitsugu Tanaka
Takeo Sakai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

  • ABSTRACT A silver halide photographic emulsion having an improved initial speed of development, especially in an infectious development process, and capable of producing a picture image with high edge gradient, which contains as the silver halide at least 40 mol of silver chloride, with the silver halide having an average particle size of not more than 0.8 micron, and containing as a combination of the following compounds:
  • the present invention relates to an improved silver halide photographic emulsion. More particularly, the invention relates to a silver halide photographic emulsion suitably used in a lith type photosensitive material having an increased sensitivity in the initial stages of an infectious development process and having increased edge gradient of the picture image resulting therefrom.
  • edge gradient refers to the degree or rate of the change in the optical density in relation to the vertical direction to the edge formed as a contact line between the darkened and undarkened parts of the developed photographic picture image. In general, it can be said that the higher the edge gradient, the clearer or sharper the picture image is.
  • a photosensitive material having an increased edge gradient is advantageously used, for example, as a lith type photosensitive material used in photoprinting or phototypesetting where cross-line images are formed with the use of a glass screen or a contact screen.
  • this type of photosensitive material it is known to ensure simple and easy handling, that matters such as increasing the edge gradient, enhancing the sensitivity, minimizing the granularity, and accelerating the rate of developing speed are required.
  • a lith type photosensitive material for use in phototypesetting is usually developed using an infectious development process.
  • the infectious development process generally comprises developing with a developer containing hydroquinone as the major developing agent together with a very minor amount of a sulfite,;'an inorganic alkali salt or an organic amine, and using a pH as high as 9.5 or higher.
  • Development using an infectious developer inevita bly is accompanied by the disadvantages of poor sensitivity, slow initial developing speed, non-uniformity in the picture image quality obtained after every developing procedure and poor granularity of the picture image etc., as compared with another type of developer in which a developing agent capable of imparting superadditivity has been combined with the major developing agent such as is seen in the conventionally employed metolhydroquinone type developer, metolpyrazolidone type developing agent, etc.
  • a silver halide emulsion containing a polyoxyalkylene oxide derivative is used as a lith type photo-sensitive material to strengthen the infectious development and to suppress non-infectious developability.
  • spectral sensitization is often applied to lith type photosensitive materials in order to increase the sensitivity in a specific wave length region.
  • most of the sensitizing dyes tend to slow down the initial speed of the infectious development with an appreciable degradation of foot cutting".
  • Additives which have been conventionally used effectively in a black-and-white non-infectious type developer e.g., D-l6, D-l9, and D-72 (these developers and their compositions are well-known in the art) are not also always similarly effective for the infectious developer. They rather invite a decrease in the edge gradient due to the disappearance of infectious developability, generate fog and promote fatigue of the developer and like disadvantageous influences.
  • an object of the present invention is to provide a photographic emulsion in which all of the defects described hereinabove have been eliminated or reduced remarkably. More particularly, an object of the present invention is to provide a photographic emulsion which satisfies the following criteria of: (l)
  • Another object of this invention is to provide a method for the preparation of silver halide emulsions which satisfies to a large extent the above requirements simultaneously.
  • a silver halide photographic emulsion containinga silver halide comprising at least 40 .mol of silver chloride and in which the average particle diameter of the silver halide particles is not greater than 0.8 micron and further containing therein a combination of; (1) a polyalkylene oxide compound and (2) .and an organic compound having at least one hydroxyl group and at least one amino group consisting of atertiary nitrogen atom (especially one capable of promoting infectious development).
  • FIGS; 1 and 2 are each diagrams indicating the relationship between the development period and the rela- -tive sensitivity. These figures designate the speed of the development relatively.
  • FIG. 3 indicates voltage-current curve (polarograph) from which the oxidation potential (E is determined.
  • Points a and b represent the points at which the three line segments intersect, each of the lines extending through the connected middle point of the curves in the ordinate direction indicating current value.
  • the organic compound having at least one hydroxyl group and at least one amino group with a tertiary nitrogen atom should have a specific reducing activity against the oxidation product (i.e., semiquinone) formed during the development the main developing compound (e.g., hydroquinones).
  • oxidation product i.e., semiquinone
  • main developing compound e.g., hydroquinones
  • This specific compound is an aromatic compound or a heterocyclic compound (of these two, an aromatic compound is preferred) having an oxidation potential (to be defined hereinafter) (E,,,) of from about millivolt to about 200 millivolt, preferably up to l60 millivolt, or precursors (regardless of their oxidation potential) of these compounds.
  • Especially preferred compounds are those represented by the following general formula (1 GENERAL FORMULA l wherein A represents a bivalent aromatic or heterocyclic group (e.g., a benzene group, a naphthalene group, a pyrimidine group, a triazine group), and A can be substituted with substituent groups so as to satisfy the value of E required (e.g., alkyl (e.g., methyl, ethyl, propyl, butyl, etc.), alkoxy (e.g., methoxy, ethoxy, etc.), hydroxy, halogen (e.g., chlorine, bromine, etc.), alkoxycarbonyl (e.g., methoxy carbonyl, ethoxycarbonyl, etc.), quaternary aminoalkyl, aralkyl (e.g., benzyl, phenethyl, etc.), aryl (e.g., phenyl, etc.), etc
  • the compound represented by the general formula (1) usually exists in a stable state as the form of a Lewis acid-base salt with an inorganic or organic acid (e.g., hydrochloride acid, sulfuric acid, nitric acid, sulfurous acid, oxalic acid, p-methylbenzene sulfonate and sulfuric acid etc.), so that it can be employed in such a stabilized form.
  • a Lewis acid-base salt with an inorganic or organic acid (e.g., hydrochloride acid, sulfuric acid, nitric acid, sulfurous acid, oxalic acid, p-methylbenzene sulfonate and sulfuric acid etc.), so that it can be employed in such a stabilized form.
  • an inorganic or organic acid e.g., hydrochloride acid, sulfuric acid, nitric acid, sulfurous acid, oxalic acid, p-methylbenzene sulfonate and sulfuric acid etc.
  • Typical compounds represented by the general formula (1) and which can be employed in this invention are exemplified by the following compounds. However, the invention is not limited to these compounds only, and other compounds which have been described in German Pat. Laid-open Specification Nos. 2,153,632; 2,153,633, 2,153,571; 2,153,572, 2,161,431 etc. can be employed.
  • the process of development is understood as an oxidation-reduction reaction process between the silver halide and the developing compound.
  • the value of the oxidation, potential (E) can be readily determined by voltametry as described hereinafter.
  • a Britton-Robinsons buffer solution adjusted to a pH of 11.0 is prepared by mixing 825cc of a solution of sodium hydroxide (0.20N) with 1 liter of the solution containing dissolved therein 39.2g of orthophosphoric acid, 24.0g of glacial acetic acid and 24.7g of boric acid (the solution showed a pH value of ll.O at 25C).
  • the buffer solution thus prepared is then bubbled with nitrogen gas to completely replace the air, after which the samples to be measured are dissolved therein to prepare a l l'0 mol solution of each sample.
  • a voltage-current curve is plotted at 25C using a saturated calomel electrode (SCE) as a reference electrode.
  • SCE saturated calomel electrode
  • a series of the measured values sometimes gives rise to a deviation of approximately 100 millivolts depending upon the effect of the salt of the compound, although the compensations in the liquid-liquid contact potential, electric resistance, etc. specific to the appa ratus are occasionally carried out by suitable adjustments in the electric circuits of the tripolar type polarography apparatus.
  • the reproducibility of the value of the oxidation potential can be obtained by comparing and adjusting the measured value while taking -l 50:2 millivolt as the standard.
  • oxidation potential means the electric potential at which the sample is oxidized at the anode.
  • the methods for the measurement of the oxidation potential are described in a variety of publications such as P. Delahay, New Instrumenlal Methods in Electrochemistry, lnterscience Publishers, 1954; l. M. Kolthoft and J. J. Lingane, Polarography, Second Edition, lnterscience Publishers, 1952; L. Meites, Polarographic Techniques, Second Edition, lnterscience Publishers, 1965,
  • the oxidation potential as used throughout the specification refers to the one regarding the form in which a proton has been dissociated from the organic compound, and therefore it is preferred that the measurement be carried out in a solution with a sufficiently high pH value.
  • the measurement of the oxidation potential of the organic compound represented by the general formula (1 is desirably carried out within about one hour after the preparatiorj' of the alkaline solution, since the organic compound tends to undergo decomposition, for instance'fde'a'inination, in an aqueous solution having a pH in excess of about 10.
  • the polyalkylene oxide compound which can be used in this invention is a compound having therein at least a partial structure of or units of a polyalkylene oxide which serves for increasing the infectious developing effect with the use of a silver halide photographic emulsion, such as those described, for example, in U.S. Pat. Nos. 2,400,532; 3,294,537; 3,294,540; 3,516,830; 3,567,458 and 3,345,l ;(.the latter three corresponding to French Pat. Nos. 1,491,805; 1,596,673; Japanese Pat. Publication No. 23466/ 1965 respectively),
  • suitable polyalkylene oxide compounds include an addition polymer of ethylene oxide, of propylene oxide and like alkylene oxides with a compound such as water, aliphatic alcohols, aromatic alcohols, glycols, aliphatic acids, organic amines and a dehydration compound of hexitol, a condensate of a polyalkylene oxide with one of the above group of the compounds, or an inter-block copolymer of various different alkylene oxides 6 ethylene oxideand propylene oxide).
  • a compound such as water, aliphatic alcohols, aromatic alcohols, glycols, aliphatic acids, organic amines and a dehydration compound of hexitol, a condensate of a polyalkylene oxide with one of the above group of the compounds, or an inter-block copolymer of various different alkylene oxides 6 ethylene oxideand propylene oxide).
  • the polyalkylene oxide compounds used in this invention has a molecular weight ranging from about 500 to 25,000, preferably'from 1,000 to 20,000, and includes, for example, the following compounds:
  • the silver halide emulsion used in this invention contains particles of silver chloride, silver bromide, silver iodide or mixtures, thereof and preferably consists of at least 40 mol of silver chloride and less than 5 mol of silver iodide or silver bromide.
  • the silver halide particles used in this invention can have a uniformly distributed halogen composition inside the particles or the particle surface can have a different composition from that of the interior.
  • the technique of the present invention can be applied not only to conventionally employed surface sensitive type negative emulsions but also to internal latent image type emulsions, direct positive type emulsions having a chemically fogged surface, and to other emulsions such as those prepared in accordance with the processes describedffor instance, in U.S. Pat. Nos. 2,592,250; 2,996,382; 3,607,278 and 3,367,778; etc.
  • the average diameter of the silver halide particle is higher than 0.8 microns, the granularity of the image obtained after infectious development will become much coarser than that obtained after ordinary noninfectious type developing.
  • the average diameter of the silver halide particle is determined according to conventional methods.
  • the photographic emulsion used in this invention can be sensitized using conventional techniques now wellknown in the art, such as those described in C. E. K.
  • ions e.g., gold compounds, platinum compo'undsfet c 1 as disclosed in U.S. Pat. Nos. 2,540,085; 2,597,856;-'
  • Typical examples of chemical sensitizers include thiourea, sodium thiosulfate, cystine and the like sulfur'containing sensitizers; potassium chloroaurate, aurous thiosulfate, potassium chloropalladate, and the like noble metal sensitizers; tin chloride, phenyl hydrazine, reductone and the like reducing sensitizers, etc.
  • sensitizers such as polyoxyethylene compounds (as disclosed in U.S. Pat. No. 2,716,062), polyoxypropylene compounds having an oxonium or ammonium group (as disclosed in U.S. Pat. Nos. 2,271,623; 2,288,226; and 2,334,864) can also be included.
  • high contrast high gradation
  • stabilization fog inhibition or supersensitization, etc.
  • fog inhibition can be applied if desired.
  • antifoggants such as nitrobenzazoles, e.g., nitrobenzimidazole as disclosed in British Pat. No. 403,789
  • platinate salts e.g., ammonium chloroplatinate, as disclosed in U.S. Pat. Nos. 2,566,263; and 2,566,245, etc.
  • stabilizers such as 4-hydroxy-6-methyl-l 3,3a,7-tetrazaindene, thiazolium salts as disclosed in U.S. Pat. Nos. 2,131,038 and 2,694,716, azaindenes, e.g., 4-hydroxy- 6-methyl-l,3,3a,7-tetrazaindene as disclosed in U.S. Pat.
  • the photographic emulsion which can be used in this invention can contain as its protective colloid gelatin and acylated gelatin derivatives such as phthalated or malonated gelatin, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose; hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polystyrene sulfonic acid, etc.; dimension stabilizing plasticizers, polymer latices such polymethyl methacrylate, polybutyl methacrylate, and matting agents such as silicon dioxide, etc.
  • acylated gelatin derivatives such as phthalated or malonated gelatin, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose
  • hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polystyrene sulfonic acid, etc.
  • dimension stabilizing plasticizers polymer latices such polymethyl me
  • the photographic emulsion which can be used in this invention can further contain developing accelerators such as onium compound, hydroquinone derivatives, 3-pyrazolidone derivatives and cationic surface active agents; stabilizers which are used in conventional photosensitive materials such as 4-hydroxy-l ,3,3a,7- tetrazaindene derivatives; fog inhibitors such as mercaptotetrazol and lipoic acid; hardeners including inorganic compounds and organic compounds such as formaldehyde, other aldehydes, chromalum, mucochloric acid, sodium-l-hydroxy-3,5-dichlorotriazine, glyoxal, dichloroacrolein, aziridine etc., surface active agents such as saponin, sodium alkyl benzenesulfonates, anionic surface active agents such as those described in U.S.
  • developing accelerators such as onium compound, hydroquinone derivatives, 3-pyrazolidone derivatives and cationic surface active agents
  • stabilizers which
  • the layer of the photographic emulsion used in this invention can be provided with either on its upper or lower side at least one layer of a colloid which has been dyed to prevent halation or to exert a filtering activity.
  • the silver halide photographic emulsion can be spectrally sensitized using various methine dyes as disclosed in C. E. K. Mees The Theory ofthe Photographic Process Revised Ed. MacMillan; Frances M. Hamer The Cyanine Dyes And Related Compounds, lnterscience Publishers, e.g, cyanine dyes, merocyanine dyes, hemicyanine dyes, complex merocyanine dyes, styryl dyes, neutrocyanine dyes, etc.
  • sensitizing dyes represented by the following general formulae ([1) or (III) are especially desirable;
  • Z represents a group of atoms necessary for forming a heterocyclic ring such as a tetrazole ring, a pyrrolidine ring, a pyridine ring, a thiazole ring, a thiazoline ring, a selenazole ring, a selenazoline ring, an oxazole ring, an oxazoline ring, an imidazole ring, an imidazoline ring and an indolenine ring;
  • L, and L each represents a methine chain, for example, a methine chain, a methyl methine chain, an ethyl methine chain, a phenyl methine chain and 2-hydroxyethyl methine chain etc.;
  • R, and R, are each an alkyl group such as methyl or ethyl.
  • the above aromatic ring formed by Z, and Z can be further substituted with an aryl group (e.g., phenyl, etc.), a halogen atom (e.g., chlorine, bromine, etc.), an alkyl group (e.g., methyl, ethyl, etc.), an alkoxycarbonyl group (e.g., methoxy carbonyl, ethoxy carbonyl), an alkoxy group (e.g., methoxy, ethoxy, propoxy, etc.), a trifluoromethyl group, an alkylsulfonyl group (e.g., methyl sulfonyl ethylsulfonyl, etc.).
  • an alkylsulfonyl group e.g., methyl sulfonyl ethylsulfonyl, etc.
  • the heterocyclic nuclei formed may include, for example, heterocyclic nuclei such as S-phenyl-benzoxazole, S-chlorobenzoxazole, 5- methylbenzoxazole, 5-methoxycarbonylbenzoxazole, 5-chlorobenzothiazole, S-methoxybenzothiazole, 5- chloro-6-methylbenzothiazole, B-naphthothiazole, B,B'-naphthothiazole, S-methylbenzoselenazole, benzoselenazole, 5,6-dichlorobenzimidazole, S-trifluoromethylbenzimidazole, 5'chloro-6-methylsulfonylbenzimidazole, S-methoxycarbonylbenzimidazole, naphthoimidazol-1,l -dimethylindolenine, etc.
  • heterocyclic nuclei such as S-phenyl-benzoxazole, S
  • R and R each represents an alkyl group (e.g., an ethyl group, a propyl group etc.), a substituted alkyl group (e.g., a propenyl group, a hydroxyalkyl group such as a hydroxyethyl group, an amidoalkyl group such as an amidoethyl group, an aralkyl group such as a p-carboxyphenylmethyl group, a carboxyalkyl group such as a carboxymethyl, carboxy ethyl and carboxybutyl group, a sulfo group-containing alkyl group such as sulfopropyl group, a 3-sulfobutyl group, a 2-[2-(3- sulfopropoxy)-ethoxyethyl group, etc.
  • a substituted alkyl group e.g., a propenyl group, a hydroxyalkyl group such as a hydroxyethy
  • X represents an organic or inorganic anion generally used in a cya nine type dye such as a bromide ion, an iodide ion, a p-toluenesulfonic acid ion, a perchloric acid ion, etc.
  • the polyalkylene oxide compound which can be used in this invention is added in an amount sufficient to promote infectious development desirably in an amount of from 0.01 to 1 gram per mol of silver halide.
  • the organic compound used as one indispensable element of this invention is preferably added in an amount of from mole to 10 mole per mol of silver halide.
  • the sensitizing dye which can be used in this invention is incorporated in a ssnsitizing amount, preferably in an amount of from 10' to 10' mol per mol of silver halide, which is sufficient to improve the sensitivity by usual sensitometry.
  • additive compounds are added as solutions using solvents such as water or a suitable watermiscible solvent not adversely affecting the photographic properties of the silver halide emulsion such as alcohol (e.g., methanol, ethanol, methylcellusolve etc.), ketones (e.g., acetone, etc.).
  • solvents such as water or a suitable watermiscible solvent not adversely affecting the photographic properties of the silver halide emulsion such as alcohol (e.g., methanol, ethanol, methylcellusolve etc.), ketones (e.g., acetone, etc.).
  • the compound represented by the general formual (l) is preferably added as a neutral or acidic aqueous solution thereof.
  • the finished emulsion is preferably kept at the pH below 6.8, especially below 6.5.
  • additive compounds can be added directly to the emulsion itself, or added to at least one of the layers adjacent to the silver halide emulsion layer (such as a protective layer or an intermediate layer, an antihalation layer or other silver halide emulsion layers) through which the compounds eventually migrate and penetrate into the main silver halide emulsion layer.
  • the layers adjacent to the silver halide emulsion layer such as a protective layer or an intermediate layer, an antihalation layer or other silver halide emulsion layers
  • the finished emulsion of the present invention can be applied to a suitable support material such as a polyethylene terephthalate film, a polystyrene film, a cellulose acetate film, a cellulose acetate butylate film, other plastic films, glass plates, etc.
  • a suitable support material such as a polyethylene terephthalate film, a polystyrene film, a cellulose acetate film, a cellulose acetate butylate film, other plastic films, glass plates, etc.
  • the silver halide photosensitive material obtained in accordance with the present invention can be processed or treated in any conventional manner known in the art, for instance, in vat developing, automatic developing systems using rollers, belts and like mechanical transferring devices, or any other processes generally known in the art.
  • the development is carried out, for instance, using an infectious developer which is fundamentally consists of dihydroxybenzene (main developing agent), inorganic or organic bases, a minor amount of sulfite salts, and buffers containing sulfuric acid and a minor amount of sulfite salts.
  • infectious developer which is fundamentally consists of dihydroxybenzene (main developing agent), inorganic or organic bases, a minor amount of sulfite salts, and buffers containing sulfuric acid and a minor amount of sulfite salts.
  • the dihydroxybenzenes used as the main developing agent can suitably be selected from compounds wellknown per se in photographic chemistry, and include, for example, hydroquinone, chlorohydroquinone,
  • the bromide ion and the iodide ion contents were 17 mol and 0.2 mol respectively, and the amount of silver per kg of the emulsion was about 1.3 mol
  • the silver halide particles had an average diameter of bromohydroquinone, isopropylhydroquinone, methylabout 05,, hydroquihohei 2,3'diehlol'ohydroquihohe,
  • the emulsion (2.5Kg) was weighed into a pot and the thylhydroquihohei vessel was heated to about 45C to melt the contents.
  • These compounds can be e e'ther Smgly or as The contents were then spectrally sensitized by adding tures thereof as g gap g P ai of 1O 100cc of 2 x 10- mol solution of the sensitizing dye amount used can e a e to t e s1ver a1 e emu (we) in methanoL s1on.
  • the sulfite ion buffer is used in an effective amount 353332;:2 2:: Z; so as keep e concentration of the sulfifie ions as low a stabilizer to the resulting solution. Thereafter the nec- 21? 23 5313 111 5;: 332 131213? i'i iiil ilidlliii u l'fii; i additives were added acwdmg o acetone-alkali bisulfite adduct, and carbonyl bisulfuric as Show]?
  • the developer liquid can be further contain at least After cutting into P i the photosensitive material one of the following various additives well-known to so obtained was Wedge-exposed using a sehsitometel' those skilled in the art, such as, for example, benzothihaving a color temperature of 54000K-
  • a sehsitometel' those skilled in the art, such as, for example, benzothihaving a color temperature of 54000K-
  • the thus azole, 1-phenyl-5-mercaptotetrazole and like organic Posed Strip was developed using a conventional fog inhibitors, polyalkylene oxides, amine compounds, type developer having the following composition at onium compounds and organic solvent such as triefor 3 and 4 minutes respectivelythyleneglycol monoalkylether, etc.
  • the developer liquid can be prepared in the form of Composition of Dcvelopcrl a powder of the developer components which has been water 500 cc widely used up to now, or in the form of a liquid con- Hydmquinone 15 g taining the component which has been recently used gs g z Fmmaldehyde with 50mm 50 g with increasing interest to improve working efficiency 40 potassium Carbonate 35 g and along with the increasingly widespread use of auto- Triefhanolamine Ce matic developing apparatus. :15??? g
  • the techniques in accordance with this invention can Potassium Bromide be applied in combination with other already known water) make 1 techniques such as those described in U.S. Pat. Nos.
  • Example 2 Using the procedure of Example 1, a polyalkyleneoxide compound, a compound represented by the general formula (1) and 6cc of 2% solution of mucochloric acid to give finished solution were added and the emulsion was thereafter applied to a polyethylene terephthalate film and dried to form a layer having a dried film thickness of about 6p"
  • Composition of Developer Liquid 1! 500 cc 15g Water Hydroquinone Adduct of Formaldehyde with Sodium Bisulfite Sodium Carbonate Sodium Sulfite Boric Acid Potassium Bromide Water to make g g 25 g 5.0 g 2.0 g
  • Runs No. 1, 2 and 6 were carried out for the purposes of comparison.
  • the results of Run No.5 clearly demon- 65 strate the advantageous feature of the present invention in comparison with Run No. 6.
  • EXAMPLE 3 10 The values of the E of the compounds represented A chemically ripened silver iodochlorobromide by the general formula are g n as follows: emulsion was prepared according to conventional method. The emulsion had a bromide ion content of 17 (La) minim" (mv) mol and an iodine ion content of 1 mol%. The emul- (Ld) sion contained 80cc of a 4 X 10 mol solution of dye 5 3-2 1(5)? II-a in methanol and 50 cc of a 1 X mol solution (H) of dye 11-1 in methanol in each kg. to effect spectral sen- 1) 1 sitization.
  • a collo'idal composition to be used for The points at which the line segments cross are indimaking a protective layer was prepared, and thereafter cated as points a and b, respectively.
  • the middle point the compound represented by the general formula (I) p of the line segment formed between crosspoint a and was admixed thereto. 4 crosspoint b is determined.
  • the oxidation potential value (E of the present invention is then obtained as a voltage value corresponding to point p. While the invention has been described in detail and Composition of COllOICl for Protective Layer: I
  • a lithographic silver halide photographic emul- "-sion comprising at least 40 mol of silver chloride and A lij f li k l l g fizi z film g flfisfly containing silver halide particles with the average partig j g 3 l r r f m 3 40 cle diameter of not more than 0.8'micron
  • Protective ayer m a He emulsion containing the combination'of the following fllm thickness of about In. 7 compounds: 1
  • said organic compound has the general formula (I) XOAN R2 wherein A represents a bivalent aromatic or heterocylic group, R, and R each represents a group which is necessary to form a tertiary amino group with the nitrogen atom, and R, and R can combine together to form a ring;
  • X represents either hydrogen, or a group capable of being dissociated therefrom with an inorganic or organic base, or a precursor of said organic compound having the general formula (I), said compound of the general formula (I) having an oxidation potential ranging from 0 millivolt to 2OO millivolt.
  • A is a unsubstituted or substituted benzene group, naphthalene group, pyrimidine group, or triazine group, said substituents being alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary aminoalkyl, aralkyl or aryl groups;
  • R, and R each is an alkyl group, an alkenyl group, an aralkyl group or an aryl group or R, and R can combine together to form a saturated or unsaturated ring;
  • X represents a hydrogen atom, an acyl group, or an acyloxy group.
  • a sensitizing dye of the general formula ([1) wherein Z represents a group of atoms necessary for forming a heterocyclic ring; L and L each represents a methine chain; Y represents an oxygen atom, a sulfur atom or a N-R group in which R is an aliphatic group or an aryl group; n is an integer ofO or l; R, and R are each an aliphatic group or an aryl group; and a compound of the general formula (Ill) (Ill) wherein A is a hydrogen atom or a lower alkyl group containing not more than 3 carbon atoms; Z and Z each represents a group of atoms necessary for forming a benzene or a naphthalene ring; Y and Y are each an oxygen atom, a sulfur atom, a selenium atom, a
  • R and R are each an alkyl group; R and R each represents an aliphatic group; X is an anion; and p is 1 or 2, p being 1 when the compound forms an intramolecular salt.
  • Z is a tetrazole ring, a pyrrolidine ring, a pyridine ring, a thiazole ring, a thiazoline ring, a selenazole ring, a selenazoline ring, an oxazole ring, an oxazoline ring, an imidazole ring, an imidazoline ring or an indolenine ring and wherein said heterocyclic ring formed Z and Z each is S-phenyl-benzoxazole, 5 -chlorobenzoxazole, S-methylbenzoxazole, 5-methoxycarbonylbenzoxazole, S-chlorobenzothiazole, S-methoxybenzothiazole, 5- chloro-6-methylbenzothiazole, B-naphthothiazole, B,B-naphthothiazole, S-methylbenzoselenazole
  • R and R each is an alkyl group, a carboxyalkyl group, a sulfoalkyl group, an allyl group, an aminoalkyl group,
  • R-, and R each is an alkyl group, an alkenyl group, a hydroxyalkyl group, an amidoalkyl group, an aralkyl group, a carboxyalkyl group or a sulfo alkyl group.
  • L and L each is a methine chain, a methyl methine chain, an ethyl methine chain, a phenyl methine chain and a 2-hydroxyethyl methin chain
  • R is' an alkyl group, a cyanoalkyl group, an allyl group, carboxyalkyl group, an aminoalkyl group, an aralkyl group a hydroxyalkyl group or an aryl group
  • R is an alkyl group, an ally] group, an acetoxyalkyl group, a cyanoalkyl group or group and R and R are each an alkyl group.
  • A is a unsubstituted or substituted benzene group, naphthalene group, pyrimidine group, or triazine group, said substituents being alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary aminoalkyl, aralkyl or aryl groups;
  • R, and R each is an alkyl group, an alkenyl group, an aralkyl group or an aryl group or R and R, can combine together to form a saturated or unsaturated ring;
  • X represents a hydrogen atom, an acyl group, or an acyloxy group.
  • a, b and c are integers with b being an integer of 14 to 55 and with a+c being an integer of 4 to 2l0; d.
  • HOCH CH O(-CH,CH,O-) ;CH CH,Ol-l;

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  • Spectroscopy & Molecular Physics (AREA)
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US412518A 1972-11-02 1973-11-02 Silver halide photographic emulsion Expired - Lifetime US3915713A (en)

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JP11007472A JPS5313124B2 (xx) 1972-11-02 1972-11-02

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DE (1) DE2354790A1 (xx)
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GB (1) GB1399331A (xx)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011082A (en) * 1974-06-06 1977-03-08 Fuji Photo Film Co., Ltd. Silver halide photographic material
US4078937A (en) * 1974-11-26 1978-03-14 Fuji Photo Film Co., Ltd. Process for sensitizing a fine grain silver halide photographic emulsion
US4121935A (en) * 1974-09-17 1978-10-24 Konishiroku Photo Industry Co., Ltd. Lith-type silver halide photographic light-sensitive material
US4126463A (en) * 1976-09-14 1978-11-21 Agfa-Gevaert Aktiengesellschaft Method of stabilizing photographic silver halide emulsion layers
DE2830418A1 (de) * 1977-07-12 1979-02-01 Fuji Photo Film Co Ltd Lithographisch-photographisches silberhalogenidmaterial und dessen verwendung
US4175966A (en) * 1975-08-02 1979-11-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof
US4209329A (en) * 1977-05-02 1980-06-24 E. I. Du Pont De Nemours And Company Low silver coating weight, high speed films having two similar emulsion layers
US4221864A (en) * 1977-02-01 1980-09-09 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
DE3243907A1 (de) * 1981-11-26 1983-06-01 Konishiroku Photo Industry Co., Ltd., Tokyo Lichtempfindliches photographisches silberhalogenid-aufzeichnungsmaterial
US4894323A (en) * 1986-05-27 1990-01-16 Fuji Photo Film Co., Ltd. Silver halide photographic material comprising a polyoxyethylenic compound and a sensitizing dye
US5550013A (en) * 1994-12-22 1996-08-27 Eastman Kodak Company High chloride emulsions having high sensitivity and low fog and improved photographic responses of HIRF, higher gamma, and shoulder density

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5133622A (ja) * 1974-09-17 1976-03-22 Konishiroku Photo Ind Risugataharogenkaginshashinkankozairyo
JPS5952821B2 (ja) * 1980-02-08 1984-12-21 富士写真フイルム株式会社 リス型ハロゲン化銀写真感光材料
JPS58144680U (ja) * 1982-03-24 1983-09-29 コニカ株式会社 テ−プカセツト用滑性シ−ト

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3320068A (en) * 1963-04-24 1967-05-16 Agfa Ag Silver halide emulsions with increased sensitivity
US3321312A (en) * 1963-01-05 1967-05-23 Agfa Ag Stabilized polyalkylene oxide sensitized emulsions
US3615528A (en) * 1968-12-23 1971-10-26 Agfa Gevaert Ag Photographic silver halide emulsion having an increased sensitivity and reduced fogging
US3632340A (en) * 1968-09-09 1972-01-04 Eastman Kodak Co Cored direct positive silver halide emulsion developed with polyhydroxybenzene
US3707376A (en) * 1969-11-21 1972-12-26 Charlotte Weber Process of sensitizing silver halide emulsion with poly(alkylene oxide) and sulfur compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3321312A (en) * 1963-01-05 1967-05-23 Agfa Ag Stabilized polyalkylene oxide sensitized emulsions
US3320068A (en) * 1963-04-24 1967-05-16 Agfa Ag Silver halide emulsions with increased sensitivity
US3632340A (en) * 1968-09-09 1972-01-04 Eastman Kodak Co Cored direct positive silver halide emulsion developed with polyhydroxybenzene
US3615528A (en) * 1968-12-23 1971-10-26 Agfa Gevaert Ag Photographic silver halide emulsion having an increased sensitivity and reduced fogging
US3707376A (en) * 1969-11-21 1972-12-26 Charlotte Weber Process of sensitizing silver halide emulsion with poly(alkylene oxide) and sulfur compounds

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011082A (en) * 1974-06-06 1977-03-08 Fuji Photo Film Co., Ltd. Silver halide photographic material
US4121935A (en) * 1974-09-17 1978-10-24 Konishiroku Photo Industry Co., Ltd. Lith-type silver halide photographic light-sensitive material
US4078937A (en) * 1974-11-26 1978-03-14 Fuji Photo Film Co., Ltd. Process for sensitizing a fine grain silver halide photographic emulsion
US4175966A (en) * 1975-08-02 1979-11-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof
US4126463A (en) * 1976-09-14 1978-11-21 Agfa-Gevaert Aktiengesellschaft Method of stabilizing photographic silver halide emulsion layers
US4221864A (en) * 1977-02-01 1980-09-09 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4209329A (en) * 1977-05-02 1980-06-24 E. I. Du Pont De Nemours And Company Low silver coating weight, high speed films having two similar emulsion layers
DE2830418A1 (de) * 1977-07-12 1979-02-01 Fuji Photo Film Co Ltd Lithographisch-photographisches silberhalogenidmaterial und dessen verwendung
DE3243907A1 (de) * 1981-11-26 1983-06-01 Konishiroku Photo Industry Co., Ltd., Tokyo Lichtempfindliches photographisches silberhalogenid-aufzeichnungsmaterial
US4517284A (en) * 1981-11-26 1985-05-14 Konishiroku Photo Ind. Co., Ltd. Light-sensitive silver halide photographic material
US4894323A (en) * 1986-05-27 1990-01-16 Fuji Photo Film Co., Ltd. Silver halide photographic material comprising a polyoxyethylenic compound and a sensitizing dye
US5550013A (en) * 1994-12-22 1996-08-27 Eastman Kodak Company High chloride emulsions having high sensitivity and low fog and improved photographic responses of HIRF, higher gamma, and shoulder density

Also Published As

Publication number Publication date
JPS4969124A (xx) 1974-07-04
FR2205679A1 (xx) 1974-05-31
GB1399331A (en) 1975-07-02
FR2205679B1 (xx) 1982-03-19
JPS5313124B2 (xx) 1978-05-08
DE2354790A1 (de) 1974-05-09

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