DE2553127A1 - PROCESS FOR INCREASING THE SENSITIVITY OF A PHOTOGRAPHIC SILVER HALOGENIDE EMULSION, THE PRODUCTS CONTAINED WITH IT AND THEIR USE FOR THE MANUFACTURE OF A PHOTOGRAPHIC MATERIAL - Google Patents

Description

PATENT LAWYERS A. '3RUNECKER

H. KINKELDEY

CR IPjG

W. STOCKMAIR

**} Γ "Γ ™ **} Λ r \ ΓΗ OFI-ING-AhE (CALTECH)

L · 0 0 J I £. I. _K SCHUMANN

DR. REa NAT ■ DtPL-PHYS

P. H. JAKOB

DIPL ING

G. BEZOLD

DR. RER. NAT - DlPL-CHfM

MUNICH E. K. WEIL

DR ΒΕΠ OEC INC.

LINDAU

8 MUNICH 22

MAXIMILIANSTRASSE 43

26th November 1975 P 9733

Photo Film Co., Ltd.
No. 210, Nakanuma, Minami Ashigara-Shi, Kanagawa, Japan

Process for increasing the sensitivity of a photographic Silver halide emulsion, the products obtained thereby and their use for the production of a photographic

Materials

The invention relates to a method for increasing the sensitivity a photographic silver halide emulsion, particularly a method for sensitizing a photographic one Silver halide emulsion, especially for further increasing the sensitivity of a fine grain fine grain sensitized with sulfur photographic silver halide emulsion, the products obtained thereby and their use for the production of a photographic material or element.

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TELEPHONE (039) 22 28 62 TELEX Ο5-29 38Ο TELEGRAMS MONAP ORIGINAL INSPECTED

Efforts have long been made to reduce the sensitivity of .photographic To further improve silver halide emulsions. In addition, efforts have long been made to produce silver halide photographic emulsions to make it finer-grained, in order to reduce the graininess or image sharpness of the photosensitive materials made from it to improve photographic materials. The sensitivity however, it decreases as the granules become finer. Efforts have therefore been made for a long time, especially sensitivity of fine-grain photographic emulsions.

On the other hand, it is extremely important to keep fogging in photographic silver halide emulsions under control. Various compounds have been used for this purpose. Hydroxytetrazainden compounds are known stabilizers for photographic emulsions, which are incorporated into them in order to reduce their formation of fog. However, it is also known that these compounds frequently reduce the photographic sensitivity (cf., for example, the article by VC Chambers in "Phot. Sci. Eng. ¹¹ , Volume 3, £, pages 268 to 271 (1959)," with entitled "A Correlation of the Chemical Structures of Some Triazolopyrimidines with Their Photographic Effects").

In Japanese patent application 46 398/73 it has already been proposed the sensitivity of a silver halide emulsion by incorporating a sulfur-containing compound in Combination with a hydroxytetrazaindene compound into a monodispersed silver halide emulsion containing cubic grains (with a silver bromide content of not less than 8 Mo 1%)

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to increase. In Japanese Patent Laid-Open No. 11 122/74 It has already been pointed out that by incorporating a substituted tetrazaindene compound into a 20 mol% or more Silver halide photosensitive material containing silver chloride a hard (high-contrast) sensitization can be achieved.

The aim of the present invention is therefore to provide a method to increase the sensitivity of a photographic silver halide emulsion, particularly a fine grain photographic silver halide emulsion. The aim of the invention is It also aims to provide a method by which it is possible to measure the sensitivity of a silver halide photographic emulsion and at the same time to keep the fogging under control.

It has now surprisingly been found that the above Objectives achieved thereby and the photographic sensitivity regardless of the shape of the silver halide grains, it can be increased by making a sulfur-sensitized one photographic silver halide emulsion comprising silver halide grains of an average grain size (with an average Particle diameter) of not more than 0.5 µm contains one or more specific hydroxytetrazaindene compounds clogs.

The invention relates to a process for increasing the sensitivity of a photographic silver halide emulsion, which is characterized by the fact that one is sensitive to sulfur

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lized silver halide photographic emulsion, the Contains silver halide grains an average size of not more than 0.5 »µm, at least one Incorporated hydroxytetrazaindene compound of the general formula

wherein R. and H "each represent a hydrogen atom, an aliphatic one or an aromatic group and η denotes the number 1 or 2.

The invention also relates to the one described above Way sensitized silver halide photographic emulsion, a process for their production and their use for the production of a photographic material (element), that of a support and at least one photographic silver halide emulsion layer of the above provided thereon specified composition.

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In the general formulas I and II given above, R ₁ and R ₉ , which may be the same or different from one another, preferably each represent a hydrogen atom, an aliphatic group having 1 to 32 carbon atoms (this term includes, for example, an alkyl group having 1 to 10 carbon atoms, preferably with 1 to 6 carbon atoms, such as a methyl, ethyl, propyl, pentyl, hexyl, octyl, isopropyl, sec-butyl, t-butyl, cyclohexyl, cyclopentylmethyl, decyl group and the like; an alkyl group having 1 to 10, preferably 1 to 4 carbon atoms which is substituted by one or two aryl groups, such as benzyl, phenethyl, benzhydryl, 1-naphthylmethyl, 3-phenylbutyl and the like; an alkoxy-substituted alkyl group having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl and alkoxy radicals, such as methoxymethyl, 2-methoxyethyl, 3-ethoxypropyl, 4-methoxybutyl and the like; an alkyl group which is replaced by a hydroxy or carbonyl group substitute is ert, the alkyl group having 1 to 12, preferably 1 to 5 carbon atoms, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxybutyl, carboxymethyl, 2-carboxyethyl and the like; an alkoxycarbony! substituted alkyl group having 1 to 10, preferably 1 to 5 carbon atoms in each alkyl and alkoxycarbonyl radical, such as 2- (methoxycarbonyl) ethyl, 3- (pentoxycarbonyl) butyl group and the like, or the like, or an aromatic group having 6 to 30 carbon atoms (e.g. an aryl group such as phenyl, 1-naphthyl group and the like, which term includes a substituted aryl group having one or more alkyl groups having 1 to 10, preferably 1 to 3 carbon atoms such as p-ToIyI, m-ethylphenyl, m-cumenyl, mesityl, 2,3-xyIyI, 1-methyl-2-naphthyl and the like; one or more halogen atoms such as chlorine, bromine or iodine, e.g. B. a p-chlorophenyl, o-bromophenyl

Group and the like; one or more hydroxyl groups, ζ. Β. ρ-hydroxyphenyl, 1-hydroxynaphthyl and the like; one or more alkoxy groups having 1 to 10, preferably 1 to 3 carbon atoms, e.g. B. a m-methoxyphenyl, p-ethoxyphenyl, p-isopropoxyphenyl group and the like; one or more carboxy groups, e.g. B. a p-carboxyphenyl, 4-carboxynaphthyl group and the like; one or more alkoxycarbonyl groups with 1 to 10, preferably 1 to 3 Carbon atoms, e.g. B. an o-methoxycarbonylphenyl, m-ethoxycarbonylphenyl group and the like., or the like) · and η preferably denotes the number 1 or 2. When η is the number 2 and R, denote an alkyl group, this alkyl group can be in In the form of a cyclic chain.

The silver halide emulsions according to the invention can according to various conventional processes (see e.g. T. H. James, "The Theory of the Photographic Process", 3rd Edition, pages 31 to 44, The Macmillan Co., New York (1966)) The silver halide emulsion can be physically if desired . "may or may not be allowed to mature. After making a By superhalide precipitation or physical ripening, the soluble salts are generally determined by one of several methods conventional methods, for example using a noodle washing method or a fluffing method using an inorganic salt with a multivalent anion (such as ammonium sulfate), an anionic surfactant, an anionic polymer (such as polystyrene sulfonic acid) or a gelatin derivative (such as an aliphatic or aromatic acylated gelatin), removed from the emulsion. In some manufacturing processes

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of emulsions (ζ. B. in the production of silver halide grains if the pAg is high), the procedure for removing the soluble salt can be omitted.

A sulfur-containing compound is added to the emulsion thus prepared in order to make it chemically mature, preferably at a temperature of about 40 to about 75 ° C., in particular at 50 to 60 ° C., for a period of about 5 to about 180 ° Minutes, preferably from 20 to 100 minutes, and at a pH of about 5 to about 8, preferably from 6 to 7, and in addition, at least one hydroxytetrazaindene compound of the general formulas I or II given above is added. The ripening of the emulsion can be continued after the addition. The above-mentioned hydroxytetrazaindene compound can at any stage, d. H. before, during or after the chemical ripening described above.

That contained in an emulsion used according to the invention Silver halide suitably has an average grain size of less than 0.5, and preferably more than 0.35 .mu.m, in particular less than 0.3 aim. The average grain size can be determined by conventional methods such as those described in the article by A.P.H. Trivelli and W. F. Smith, "Empirical Relations between Sensitometric and Size-Frequency Characteristics in Photographic Emulsion Series ", Photographic Journal, 79, pp. 330 to 338 (1949) are.

A monodispersed emulsion, the silver halide grains, can be used as the emulsion for carrying out the process according to the invention that contains at least 95% within

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of the range of + about 40% of the average grain size, or a polydispersed emulsion can be used containing silver halide grains whose grain size is widely dispersed beyond the average grain size are.

The silver halide used for ϋμ ^ ηϋϋΙνηΗ ^ of the invention • Process silver bromide, silver chloride bromide, silver chloride iodide, silver chloride bromide iodide, silver bromide iodide or one Mixture of these can be used.

For carrying out the process according to the invention, a silver halide is preferably used which contains 97 Mo1% or more silver bromide and has an average grain size of not more than 0.5 µm, or it becomes a used containing 97 Mo 1% or more silver bromide and the balance silver iodide and an average grain size of not more than 0.5 µm. Particularly preferred is such a silver halide containing 98.6 mol% or more of silver bromide and an average grain size of not more than 0.5 µm. A silver halide which contains 98.6 mol% or more of silver bromide is very particularly preferred and has an average grain size of not more than 0.35 µm, or that which is 98.6 mol% or more Contains silver bromide and the balance silver iodide and has an average grain size of not more than 0.35 µm.

The crystal form of the silver halide emulsion used in the invention The granules contained therein are not particularly limited, and the granules may have any shape

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to have. From a practical point of view, however, emulsions are preferred which are grains of an octahedral, cubic, tetradecahedral, spherical or another so-called "irregular" shape (e.g. a platelet shape, an irregular spherical shape, an irregular polyhedral shape, a "potato firm", e.g. B. the shape of a wafer and Like.) or mixtures thereof.

As sulfur-containing compounds in the invention Methods are used, generally known sulfur sensitizers can be used. For the Compounds containing sulfur which are suitable for the present invention are compounds which contain at least one free sulfur or can release thiosulfuric acid residue. Preferred examples are thiosulfates, allythiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like. In addition, those described in U.S. Patents

1 574 944, 2 278 947, 2 410 689, 2 440 206, 3 187 458,

3,415,649, 3,501,313 and in French patent specification

2,058,245 and the like. Compounds described can be used. The sulfur-containing compound is useful in added in an amount sufficient to increase the inherent sensitivity of the silver halides in an effective manner. These Amount varies within a wide range under varying conditions, but in general an amount is about 10 to about 10 moles per mole of silver are preferred. When the sulfur-containing compound is in an amount greater than corresponds to this range is added, the sensitivity of the emulsion is not increased, but even decreased and the tendency to fog increases. On the other hand, by adding the sulfur-containing

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Compound in an amount below the stated range does not effectively increase sensitivity the emulsion achieved. The sulfur-containing compound is added in a conventional manner. I. E. , water-soluble Compounds are in the form of an aqueous solution and compounds soluble in an organic solvent are in the form of a solution in a water-miscible organic solvent such as methanol, ethanol or the like., admitted.

If desired, in combination with the sulfur sensitization Sensitization processes are used in which salts of precious metals such as platinum, palladium, iridium, Rhodium, ruthenium and the like.> Can be used as in the US patents 2,448,060, 2,540,086, 2,566,245, 2,566,263, and the like. Instead of or in combination with the Sulfur sensitization can also be used as described in U.S. Patent 3,297,446.

Below are some specific examples of the present invention Usable Hydroxytetrazaindenverbindungen indicated, however, it should be noted that this list is not is complete and that the invention is by no means limited to its use of the connections mentioned below is limited. Compound I 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene "II 4-hydroxy-1,3,3a, 7-tetrazaindene

III 4-Hydroxy-6-methyl-1,2,3a, 7-tetrazaindene

IV 4-Hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene

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link

V 4-methyl-6-hydroxy- 1,3,3a, 7-tetrazaindene

VI 2, e-dimethyl-4-hydroxy-.1,3,3a, 7-tetrazaindene VII 4-Hydroxy-5-ethyl-6-methyl-1,3,3a, 7-tetrazaindene

VIII 2, e-Dimethyl ^ -hydroxy-S-ethyl-1,3,3a ₅ 7-tetrazaindene

IX 4-Hydroxy-5,6-dimethyl-1,3,3a, 7-tetrazaindene

X 2,5,6- »trimethyl-4-hydroxy-1,3,3a, 7-tetrazaindene

XI 2-methyl-4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene

XII 4-Hydroxy-6-ethyl-1,2,3a, 7-tetrazaindene

XIII 4-Hydroxy-6-phenyl-1,2,3a, 7-tetrazaindene

XIV 4-Hydroxy-1,2,3a, 7-tetrazaindene

XV 4-methyl-6-hydroxy-1,2,3a, 7-tetrazaindene

XVI 4-hydroxy-5,6-trimethylene-1,3,3a, 7-tetrazaindene

XVII 4-Hydroxy-5,6-tetramethylene-1,3,3a, 7-tetrazaindene

XVIII 4, S-trimethylene-e-hydroxy-1,2,3a, 7-tetrazaindene

XIX '4, S-tetramethylene-B-hydroxy-1,2,3a, 7-tetraza

in the

The hydroxytetrazaind compound used in the present invention is expediently added in an amount sufficient to effect the inherent viscosity of the silver halide used Way to increase. This amount varies widely depending on the emulsion conditions, but it is preferably within in the range from about 0.001 to about 0.5, particularly preferably νοηΟ, ΟΙ to 0.2 mol per mol of silver halide.

With regard to those illustrated by the examples given above Hydroxytetrazaindene compounds should be noted that it is possible to use any of these compounds within the above

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Range or two or more compounds in a total amount within the above range of the emulsion. These compounds are added to an emulsion in the conventional manner used for addition to a photographic emulsion. For example, they can be added in the form of a solution by dissolving them in a suitable solvent which has no adverse effect on the photosensitivity of the material obtained as the end product (e.g. in the form of an aqueous solution or in the form of an aqueous alkaline solution, such as e.g. B. an aqueous solution of sodium carbonate, sodium hydroxide, barium hydroxide and the like.). ■ ..'.- ■ -I

The hydrophilic colloid (carrier for the silver halide) is conventional; suitable examples are proteins (such as gelatin, colloidal albumin, casein and the like), cellulose derivatives (such as carboxymethyl cellulose, hydroxy « ethyl cellulose and the like), sugar derivatives (such as agar-agar, sodium alginate, Starch derivatives and the like), synthetic hydrophilic colloids (such as polyvinyl alcohol, poly-N-vinylpyrrolidone, Polyacrylic acid copolymers, polyacrylamide, derivatives thereof and the like.). If desired, a compatible mixture can also be used of two or more of these compounds can be used. According to the invention, gelatin is preferably used. gelatin can be partially or completely by a synthetic substance with a high molecular weight, by a so-called Gelatin derivative (prepared by treating gelatin with a reagent having a group corresponding to one in the Functional group containing gelatin molecule (i.e. an amino, imino, hydroxy or carboxy group) react can) or by a graft polymer prepared by

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Grafting a molecular chain of another substance with a high molecular weight onto gelatin.

Various conventional Compounds of the pho t ο gr aiii see emulsion added in order to avoid obfuscation during their manufacture, during storage of the photosensitive materials made from them or to prevent it from developing. That is, azoles (e.g. benzotriazole), nitroazoles (e.g. nitroindazole, nitrobenzotriazole and the like), halogen-substituted Azoles (ζ. B. 5-chlorobenzimidazole, 5-bromimidazole, 6-chlorobenzimidazole and the like) or compounds as described in U.S. patents 2,131,038, 2,324,123, in British Patent 403,789, in U.S. Patent 3,251,691, in Japanese Patent Publication No. 17,932/68, U.S. Patent 2,394,198, Japanese Patent Publication No. 4,136/68, in U.S. Patent 3,236,652, in British Patent 623,448, in U.S. Patent 2,839,405, 3,220,839, 2,566,263, 2,597,915, 2,691,588, in British Patent 623,488, in Japanese Patent Publications Nos. 4 941/68 and 13 496/68 and the like can be added.

The photographic ones used in the process of the present invention Emulsion layers or other hydrophilic colloidal Layers can be used to increase their sensitivity or their contrast or to accelerate the development contain conventional additives, such as those in the US Patents 2,441,389, 2,708,161, British Patent 1,145,186 in the Japanese patent publications

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Nos. 10 989/70, 15 188/70, 43 435/71, 8 106/72, 8 742/72, in U.S. Patents 3,046,132 to 3,046,135, in Japanese. See Patent Publication Nos. 9 019/70, 11 119/72, 28 325/72, in U.S. Patent 3,772,021, in Japanese Patent Publication Nos. 27 03.7 / 70, 23 465/65, 45 541/72, 26 471/70 and 27 670/70 and the like. Are described.

In addition, conventional inorganic or organic mercury compounds can be added to the photographic emulsion to sensitize it or to prevent fogging. For this z. B. Compounds can be used as described in US patents 2,728,664, 2,728,667, 2,728,663, 2,732,302, 2,728,665, 3,420,668, and the like.

The photosensitive layer of the photosensitive material to which the method according to the invention can be applied can contain, in addition to the above-mentioned compounds, various conventional gold compounds (e.g. potassium chloroaurate, gold (III) trichloride and the like, cf. US Pat. No. 2,399,083 , 2,540,085, 2,597,856, 2,597,915, a gold (I) dithiocyanate complex salt, a gold (I) dithiosulfate complex salt and the like, see J. Pouradier, MC Gadet and H. Chateau, "Electrochimie des SeIs D'or Ic Acides auro et aurichlorhydriques et sels correspondants "in ¹¹ J. Chim Phys.", 62, 2, pages 203 to 216 '(1965), various palladium compounds such as palladium chloride, see, for example, US Pat. No. 2,540,086 , Potassium chloropalladate, see, for example, U.S. Patent 2,598,079), reducing agents (e.g., tin chloride, phenylhydrazine, reductone, and the like, see, e.g., U.S. Patent Nos. 2,518,698, 2,419,974 , 2,983,610 and the like) or a mixture of these sensitizers can be added.

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When the average grain size of the silver halide grains contained in the photographic emulsion to which the present invention is applied is particularly small (less than about 0.2 µm), compounds such as those disclosed, for example, in British Patents 1 316 493, 1 317 138, 1 317 139, 1 317 709, 1 297 901, in German Offenlegungsschrift 2 235 031 and the like. ^;

After applying the according to the method according to the invention prepared emulsion in the form of a layer, the emulsion can be hardened in the usual way. Examples of hardeners that Aldehydes (such as formaldehyde, glutaraldehyde and the like), ketones (such as diacetyl, cyclopentanedione and Like.), bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, Compounds as disclosed in U.S. Patents 3,288,775, 2,732,303, British Patents 974,723,

1,167,207, U.S. Patents 3,635,718, 3,232,763, British Patent 994,869, U.S. Patents

2 732 316, 2 586 168, 3 103 437, 3 017 280, 2 983 611,

2 725 294, 2 725 295, 3 100 704, 3 091 537, 3 321 313,

3,543,292 and the like, or inorganic hardeners such as chrome alum, zirconium sulfate and the like in place of the above compounds described can also be precursors of the given compounds, such as. B. Alkalimet al Ibisulf it-Aldehyd- ■ '■ Adducts, a methylol derivative of hydantoin, a primary aliphatic Nitro alcohol and the like., Can be used.

The ₄ photographic emulsion on which the inventive

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Process is applicable, can customary surface-active Agents can be added either alone or as a combination. They are mainly used as coating aids, in some. However, cases also dilute to improve emulsion dispersion, sensitization and photographic quality Properties, added as an antistatic agent and to prevent adhesion. To these surface-active Agents include natural surfactants such as saponin; nonionic surfactants such as those the alkylene oxide series, the glycerine series, the glycidol series and the like; cationic surfactants, e.g. B. higher alkylamines, quaternary ammonium salts, heterocyclic compounds (ζ. B. pyridine and the like), phosphonium compounds, Sulfonium compounds and the like; anionic surfactants having an acidic group, such as. B. a carboxylic acid, Sulfonic acid, phosphoric acid, sulfuric acid ester, phospho.ric acid ester group and the like; amphoteric surface-active agents, such as amino acids, aminosulfonic acids, amino alcoholsulfuric acid or phosphoric acid esters and the like.

Examples of various anionic, nonionic and amphoteric surfactants are e.g. B. in U.S. patents 2 271 623, 2 240 472, 2 288 226, 2 739 891, 3 068 101, 3 158 484, 3 201 253, 3 210 191, 3 294 540, 3 415 649, 3 441 413, 3 442 654, 3 475 174, 3 545974, in the German Offenlegungsschrift 1,942,665, British Patents 1,077,317, 1,198,450 and the books by Ryohei Oda et al, "Synthesis and Application of Surface Active Agents (Maki Shoten, 1964) by A. W. Perry, "Surface Active Agents" (Interscience Publication Inc., 1958) by J. P. Sisley, "Encyclopedia of Surface Active Agents", Volume 2 (Chemical Publishing Co, 1964), and the like. specified. 609 823/0 9 27

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When the silver halide emulsion to which the method of the present invention is applicable for the preparation of color light-sensitive materials are used, the emulsion can contain conventional color couplers (color image-forming couplers) and suitable dispersants therefor are incorporated. Suitable couplers include diffusion-resistant couplers, as described, for example, in U.S. Patents 3,277,157, 3,415,652, 3,447,928, 3,311,476, 3,408,194, 2,875,057, 3,265,506, 3,409,439, 3,551,155, 3,551,156, in Japanese Patent Laid-Open Nos. 26133/72 ', 66836/73, in U.S. Patents 2 600 788, 2 983 608, 3 006 759, 3 062 653, 3 214 437, 3 253 924, 3 419 391, 3 419 808, 3 476 560, 3,582,322, Japanese Patent Publication No. 20 636/70, Japanese Patent Laid-Open No. 26 133/72, US Pat U.S. Patents 2,474,293, 2,698,794, 3,034,892, 3,214,437, 3,253,924, 3,311,476, 3,458,315, 3,591,383 in the Japanese Patent Publications Nos. 11 304/67, 32 461/69, in U.S. Patents 3,148,062, 3,227,554, 3,297,445, 3,253,924, 3,311,476, 3 379 529, 3 516 831, 3 617 291, 3 622 328, 3 701 783, 3 705 801, in German Offenlegungsschrift 2 163 811 and the like described. These couplers can be prepared by methods as described in U.S. Patent 2,801,171 and the like. be dispersed.

The silver halide photographic emulsion to which the method of the present invention is applicable can be used, if desired other conventional substances are also added, like ζ. Β. a plasticizer to improve dimensional stability Latex polymer and a matting agent. The finished emulsions are in the form of a layer on top of a conventional one applied to a suitable carrier. The photographic emulsion,

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to which the method according to the invention can be applied in the form of a layer on a conventional rigid support such as z. B. one made of glass, metal, porcelain and the like., Or be applied to a conventional flexible carrier, depending on the intended use, to form photosensitive materials. The emulsion is usually in an amount within the range of about 0.1 to about

2
2 mg of silver halide per cm in the form of a layer applied to the support, the invention being limited to the specified range, however, in its way.

Examples of typical flexible carriers include a cellulose nitrate, Cellulose acetate, cellulose acetate tityrate, cellulose acetate propionate, Polystyrene, polyethylene terephthalate, polycarbonate filra or a laminate thereof, a thin glass film, Paper and the like, as are commonly used for photosensitive photographic materials can be used. It can also papers with barite or an α-olefin polymer, in particular a polymer of an α-olfin with 2 to 10 carbon atoms, such as polyethylene, polypropylene, an ethylene / butene copolymer and the like, coated or laminated. Plastic films, the surface of which is used to improve adhesion on other polymeric substances and to improve their writability it (printability) has been roughened as described in Japanese Patent Publication No. 19 068/72, and like carriers can be used.

Transparent or opaque (opaque) carriers are selected as carriers, depending on the intended use of photosensitive materials. As a transparent carrier

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Not only colorless transparent supports but also those transparent supports can be used which, by adding have been colored by dyes or pigments. Examples of opaque supports are those that are aiysich opaque (opaque) are, such as paper, and also those that are made transparent by adding dyes or pigments, such as titanium oxide Film have been produced, as well as plastic films, their Surfaces has been treated by the method described in Japanese Patent Publication No. 19 068/72, papers or plastic films to which carbon black, a dye or the like is added has been to make them completely light-shielding, and the like. When the adhesion between the support and the phot ο graphic emulsion layer is insufficient, a conventional intermediate layer (subbing layer) as an adhesive layer be applied to which both the carrier and the photographic emulsion schidtit adhere. For improvement The surface of the carrier can also undergo a pretreatment for adhesion are subjected to, for example a corona discharge, irradiation with ultraviolet light, flame treatment lung and. dj ..

The fiction, contemporary method came to the sensitization of photographic silver hebogenide emulsions for photosensitive Color and black and white materials are used. To emulsions to which the fiction, contemporary method can be applied is, include z. B. emulsions for color positives, emulsions for color papers, emulsions for color negatives, color reversal emulsions (which are free of couplers or contain couplers), emulsions for photographic light-sensitive materials for the production of printing plates (e.g. lithographic photosensitive materials and the like), emulsions for light-

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sensitive materials for the generation of electron images (Cathode ray images), emulsions for light-sensitive materials for X-ray recording (for radiography, especially materials for direct and indirect photography using a fluorescent screen), Emulsions for electron beam recording, emulsions for photosensitive materials for manufacture of photomicrographs, emulsions for photosensitive materials for the manufacture of photomasks for use in the field of microelectronics, emulsions for colloidal transfer processes (such as in US Pat 2,716,059), emulsions for silver salt diffusion transfer processes (such as in U.S. patents

2 352 014, 2 543 181, 3 020 155, 2 861 885 and the like described ben), Emulsions for color diffusion transfer processes (such as z. B. in the US-Pdtentschriften 3,087,817, 3,185,567, 2,983,606,

3 253 915, 3 227 550, 3 227 551, 3 227 552, 3 415 644,

3,415,645, 3,415,646 and the like), emulsions for

Imbibition transfer methods (such as in U.S. Patent 2,882,156 and the like), emulsions for silver dye bleaching processes (such as, for example, by Friedman in "History of Color Photography "(American Photographie Publishers Co., 1944, especially Chapter 24), in" British Journal of Photography ", Volume 11, pages 308-309 (April 7, 1964), and The like. Described), emulsions for materials for the recording of print-out images (as, for example, in U.S. Patent

2,369,449, described in Belgian patent specification 704,255 and the like), emulsions for heat developable photosensitive Materials (such as in U.S. Patents 3,152,904,

3,312,550, 3,148,122, in British Patent 1,110,046.

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and the like), emulsions for physically developable photosensitive materials (such as in the British Patent specifications 920 277, 1131 238 and the like. Described) and the like.

The silver halide emulsion obtained by the process of the present invention is suitable for the production of lithographic photosensitive materials for photomechanical development winding (processing), for light-sensitive multilayer color materials with incorporated coupler, especially of light-sensitive color materials for reverse or negative color development, of light-sensitive, highly sensitive black-and-white negative materials, of photosensitive materials for micro negatives, from photosensitive materials for Micropositive, of photosensitive materials for recording of X-rays (in radiography), of light-sensitive Electron beam recording materials, photomask photosensitive materials for the use in the field of microelectronics and the like. In photosensitive lithographic materials These are light-sensitive materials that can reproduce extremely high-contrast images, usually using a hydroxybenzenes as a developer compound and using infectious development at low sulfite ion concentrations, thereby producing a photographic reproduction of line art or halftone halftone images. A detailed description is given by Mason in "Photographic Processing Chemistry ", pp. 163-165 (1966).

BÜ9823 / Ü32?

255312?

The invention is illustrated by the following examples, in which preferred embodiments of the invention are described, explained in more detail, but without being limited thereto.

603823/0 927

.. - ..- 23 - '
example 1

750 ml of an aqueous 1 η silver nitrate solution and 750 ml of an aqueous 1 η potassium bromide solution were added simultaneously to 750 ml of an aqueous solution containing 4 % gelatin and 0.083%, 0.028%, 0.009 % or 0% ammonia while stirring at 50 ° C. over a period of 40 Minutes added while the pAg of the reaction solution was kept at 9 »6. In this way, emulsions were prepared containing octahedral silver bromide grains with an average grain size of 0.35 / µm (Emulsion 1a), 0.27 / µm (Emulsion 1b), 0.24 / µm (Emulsion 1c) and 0.17 / um (emulsion 1d). These emulsions were desalted and 70 g of gelatin were added and then the pAg value was adjusted to 8.5 or the pH value to 7.3 at 35 ° C. and water was added to make up to 2000 g. Two 200 g portions of each of the emulsions thus prepared were taken and sodium thiosulfate pentahydrate was added to one of the two portions in an amount of 2 mg (emulsion 1a), 1.3 mg (emulsions 1b and 1c) or 2.6 mg (emulsion 1d) was added and the emulsions were ripened at 50.degree. C. for 1 hour to conduct sulfur sensitization.

In addition, three 50 g sub-portions were taken from each portion and each sub-portion of an aqueous solution of 5 was 10 ^-2 χ Mo 1/1 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (Compound I) added in an amount of 0 ml, 4 ml and 8 ml, respectively. Each coating dispersion thus obtained was applied to a gelatin-adhered transparent cellulose acetate film to a dry thickness of about 4 µm to prepare photographic light-sensitive materials. ■

After processing, one group of sub-portions contained -only the tetrazainden, while the other group of sub-portions

6098 23/0 92 7

- 24 - 255312?

Servings of both the ietrazainden and the thiosulfate contained.

Each sample was passed through a continuous optical step wedge (gray wedge) (maximum density 4-, 0) and a blue filter BEM-5 (from I ¹ UJi Photo Film Co., Ltd.) using a tungsten lamp (1000 lux, Color temperature ⁰ K) ". After the exposure, each sample became 10

For minutes at 20 ° G using a Metol ascorbic acid developer developed. The Metol ascorbic acid developer was prepared by mixing 2.5 g Metol, 10 g ascorbic acid, 1.0 g potassium bromide and 35 »O g Kodalk (or ITabox). and adding water to make up to 1 1 (pH .9 * 8) ·. '· ....

Using an automatically recording densitometer the Fuji Photo Film Co., Ltd. the photographic density was measured. The photographic density was determined by the reciprocal Expressed the value of the exposure amount which has a photographic density of 0.1 above fog (fog + 0.1) revealed. The results obtained are given in Table I below. . .

BO9823 / Q927

- 25 Table I.

255312?

Octahedral silver bromide emulsions with varying

Grain size

■ _ ",, grain test N o. _Gr5Be

(μ)

.0.35

(Comparison)

12th

0.35

0.27

(Comparison)

0.27

0.24

(Comparison)

0.24

0.17

(Comparison)

18th

0.17

HatriumiSiiosulfat per.tahydrate - (mg / m. Oil AgBr)

0 0 0

2 '2

0 0 0 connection

m ~

töl

■ mol AgBr '

10.7
21.3

0.

10.7
21.3

10.7
21.3

1) 3 10.7 21j3 0 0 0 10.7 O 21.3 ¹ ^ 0 1.3 10-, 7 21.3 0 0 0 10.7 0 21.3 ² > ⁶ . 0 2.6 10.7 2.6 21.3 60 9823/092 7

relative sensitivity

20 19 19

! (Default) '

174 174

54 54 54

100

(Default)

190 195

19 23 19

100 (standard)

200 .220

12th

10

- 100 (standard)

"224 129

255312?

From the sensitivity given in the table above It can be seen, that the sensitivity by incorporation the sulfur-containing compound in combination with the hydroxytetrazole compound in sensitizing amounts was increased considerably. The photosensitivity of a sulfur sensitization and a sensitization by Addition of the emulsion subjected to hydroxytetrazaindene compound was much higher than that of the sulfur sensitized emulsion and that of the present invention Method, therefore, provides a useful method of sensitizing emulsions for photosensitive photographic applications Represent materials that must have a high sensitivity.

Reference example 1

Example 1 was repeated, this time using an emulsion. ^ with octahedral silver bromide grains with an average Grain size of 0.7 / µm instead of the emulsions (emulsions 1a, Ib, 1c and 1d) was used, the octahedral Silver bromide grains with an average grain size of contained not more than 0.5 / µm, and being the sulfur-containing Compound and the 4-hydroxy-6-methyl-i, 3,3a, 7-tetrazaindene (Compound I) were added in the amounts shown in Table II below. The received Results are given in Table II below.

609823/0 92 7

255312?

Table II

Octahedral SiltoerTjromide emulsion with an average

Grain size of O ₁

Attempt ITr. Uatrium
t.hio5ulfate ~
pentahydrate; yerhinduas I . , relative
Sensitivity (mg / »ol AgBr) , m. Mol>, 21 ■ 0
0
O . ^lMol ' ¹ AgBr ^; '
0
21.1 19th
22nd
19 ■. 22nd 2.2
■ 2.2
2.2 0
5.3
21.1 41
35
34 23 4.4
4.4
4.4 0
5.3
21.1 74;
83
96 24 8.8
8.8
8.8 0
5.3
21.1 100
(Default)
105 *
123 - 25th 17.5
17.5
17.5 0
5.3 ■
21.1 ^ 81
85
-100, 26th 35.1
3.5.1
35.1 - o * ·
5.3
21.1 51
• .63
100 27 70.2
70.2.
70.2 0
5.3
21.1 * 42 y
"39 .1
76 \ 28 140.4
l4o, 4th
140.4 0
5.3
.21.1 O OO O
OO CM OO

60 9 82 3 / 0J2 7

255312?

From the sensitivity values given in Table II above it can be seen that in the octahedral silver bromide emulsions with an average grain size of 0.7 / µm » those with the sulfur-containing compound in varying Degrees had been sensitized to sulfur, the sensitivity decreased fairly much or, if increased, the degree of increase was very small, even if the procedure the addition of the hydroxytetrazaind compound was applied.

Attachment example 2

A platelet-like grain of silver bromide with an average A photographic emulsion containing a grain size of 1.1 / µm was prepared by a conventional single jet process, i.e. by adding an aqueous silver nitrate solution with stirring to an aqueous potassium broinide solution containing gelatin. This emulsion contained 0.30 mol per kg Silver bromide and about 4-5 g gelatin. The one in the reference example Procedure described in 1 was repeated using the emulsion described above. The results obtained are given in Table III below. ■

9823/0927

Table III

Platelet-shaped silver bromide emulsion with an average Grain size of 1.1 / µm

Attempt no. Sodium-
thiosulfate
Pentahydrate Connection, 1 relative
sensitivity (mg / mole AgBr) , m mol ν ¹ %> 1 AgBr ^; 31 0 0 20th 0 6.7 15th 0 26.7 15th 32 5.6 0 54 5.6 6.7 71 5.6 26.7 50 33 11.1 0 100
(Default) . 11.1 6.7 132 11.1 26.7 34 22.2 0 22.2 6.7 ' 22.2 26.7. 132 35 44.4 0 100 44 _? 4th 6.7 ' 115 44.4 26 ^ 7 "115 ■
i 36 88.9 0 "71 88.9 6.7 88.9 26.7 49 ' 49 56 26th 18th

609823/09 2 7

As shown in Table III above, the flaky silver bromide grains had an average Grain size of 1.1 / µm containing emulsions which vary with the sulfur containing compound Degrees had been sensitized to sulfur, the sensitivity mostly decreased and, when it was increased, the degree was the Increase little even if the hydroxytetrazaind compound was admitted.

Reference example 3

A ammoniakali see aqueous Si Ib ernit rat solution containing ammonia in an amount of 2 mol per mol of silver nitrate ^ using a conventional a photographic emulsion, the un regular spherical silver bromide grains having an average grain size of 1 / um was prepared using Single jet method (hereinafter this emulsion is referred to as ammoniacal silver bromide emulsion). This emulsion contained 0.30 mol of silver bromide and about 4-5 g of gelatin per kg. The same procedures as in Reference Example 1 were carried out using the emulsion described above. The results obtained are given in Table XV below.

60 98 2 3/09 2 7

Table IV

Irregular spherical silver bromide emulsion with an average grain size of 1 / µm

• relative,. Compound-I sensitivity

Versucji Ur. • 42 • 43 Sodium-
thiosulfate
pentahydrate (mg / ⁴ oil AgBr) 4l O O O 2.5 2.5 2.5 5 5 5

45

46

10 10

20 20 20

40 40 40

AgBr '
O

6.7
26.7

6.7
26.7

6.7
26.7

26.7

6.7
26 _? 7th

6.7
26.7

6 7 7

10 6 8

14th

. 14 11

100 (standard)

. 96 110

76-83

- 87

- 39 46 42

609823/0927

From the sensitivity values given in Table IY above it emerges that "with the anmioniakalischen Silver bromide emulsions with an average grain size of 1 / µm, that with the sulfur-containing compound in who had been sensitized to varying degrees of sulfur Sensitivity was decreased rather much, or, if increased, the degree of increase was slight even if the Hydroxytetrazaind compound was added.

It can be seen from Example Λ and Reference Examples 1 to 3 that by applying the method of the present invention to an emulsion containing grains having an average grain size of not more than 0.5 / ura, the sensitivity is extremely increased.

Example 2

To 2000 g of an octahedral silver bromide emulsion with a average grain size of 0.2 / µm based on the same In a manner as prepared in Example 1, 5 ml of a 0.1% strength by weight aqueous solution of sodium thiosulfate pentahydrate was added and the emulsion was ripened at 50 ° G for 60 minutes left to conduct sulfur sensitization · In addition, this emulsion was divided into 50 g portions and added 0.05 mol / l of an aqueous alkali solution of the above-mentioned hydroxytetrazaindene compounds II to V, the sodium carbonate contained in an amount equivalent to the compounds II to V, each added and the obtained dispersion was in the form of a layer in a Dry film thickness of about 4yum on a transparent one Cellulose acetate film applied, which was provided with a gelatin adhesive layer, for the production of photosensitive photographic materials. The sensitivity of the photosensitive materials thereby obtained became the same Measured as in Example 1 and the results obtained are shown in Table V below.

609823/0927

Table V

Octahedral silver broiaid emulsion with an average Grain size of 0.2 / µm

"Attempt Sodium
'thiosulfatr
· " ^{R <} pen t nhy d ra t tiydroxy-
tetrazainden. ""
link admitted
lot relative
Sensitivity (mg A- ¹ IoI AgBr) mälol. ^ o 1 AgB r ^; 51 6.7 - O 100
(Default) 52 6.7 II 5.3 270 6.7 II 10 _? 6th 282 6.7 II. 21.3 224 6 _? 7th II 42.7 200 53 6.7 III 5 _; 3 195 6.7 III 10j6 195 6.7 III 21.3 151
j 54 6.7 IV 5 _? 3 302 V IV 10 _; 6th 302 V -IV
• 21.3 437 6.7 IV 302 · 55 6.7 V * 5.3 '<
246 6.7 V 10.6 145

b 0 9 8 2 3 / Π H 1 7

255312?

From the sensitivity values given in Table V above it can be seen that the incorporation of Hydroxytetraazaindenverbindungen into the sulfur-sensitized fine-grain octahedral silver bromide emulsion in each case an extremely large increase in photosensitivity was observed.

Example 3

The silver bromide photosensitive material used in Example 1, Experiment 18 was filtered through a blue filter BPIJ "-45 (der Fuji Photo Film Go., Ltd.) and then through a continuous optical step wedge (gray wedge) as in Example 1 using a xenon flash lamp from EGG Co. Exposed for 1/100 second and developed in the same way as in Example 1 ;. The results obtained are in of the following Table VI.

Table VI

O 1/100 100 (Default) 10.7 1/100 245 21.3 1/100 240

Octahedral silver bromide emulsion with an average

Grain size of 0.17 / µm

Attempt sodium thio-

He. sulfate penta compound I exposure relative

hydrate , mmol \ time Sensitivity -

- (mg / mole AgBr) <- _{Mo1 AD> Wri} ^; (Sec.)

61 2.6

.2.6

2.6

As from the sensitivity given in Table VI above As can be seen from the results, the sensitivity was considerably increased in the case of the short exposure as well as by the method of incorporating the hydroxytetrazaindene compound into the sulfur sensitized fine grain silver halide emulsion.

609823/0927

2b53127

Example 4

A loaf silver bromide iodide emulsion containing grains of an average grain size of 0.3 µm, no more than 95 % of which in number were within the range of + 40 % of the average grain size, and containing 0.25 mol% of silver iodide prepared in the same manner as in Example 1, this time maintaining the pAg-S7ert at 50 ⁰ G at 7.9 to prepare the granules. 300 g of this emulsion was taken out, and 2 ml of a 2% aqueous liatric thiosulfate pentahydrate solution was added, then it was ripened at 50 ° C. for 1 hour to conduct sulfur sensitization.

In addition, 50 g portions of this emulsion were removed and

2 an aqueous solution of 5 × 10 Hol / l 4-hydroxy-6-methyl-1,3 ₅ 3a, 7-ketrazaindene (compound I) was added in an amount of 0 ml, 4 ml and 8 ml, respectively . Then, each coating solution was coated in the form of a layer at a dry thickness of about 4 µm on a transparent gelulose acetate film having a gelatin subbing layer thereon to prepare photographic light-sensitive materials. Using these light-sensitive materials, the same procedures as in Example 1 were carried out. The sensitivity values obtained are given in Table VII below.

Table VII

Silver bromide iodide cubic emulsion sensitized with sulfur with an average grain size of 0.3 / µm

Sodium-

Experiment thiosulfate compound I -, .. No. pentahydrate , mmol >> ΐΓΓ ^ Ι ?, .... r) ^{( }}

71 180 0 100 (standard)

180 10.7 14-1

180 21.3 152

609823/0927

From the sensitivity values given in Table VI above it can be seen that the sensitivity by employing the method of incorporation of the hydroxytetrazaindic compound in the sulfur sensitized silver bromide iodide fine grain cubic emulsion is increased considerably can be.

Example 5

In the same manner as in Example 1 an emulsion was prepared containing cubic silver bromide grains having an average grain size of 0.2 / um contained, with no more than their number were 95 ° / ° within the range of + 4-0% of the average grain size but this time the pAg value at 50 ° C was kept at 7j9. The same procedures as in Example 4 were carried out using the emulsions described above. The sensitivity values obtained are given in Table VIII below. .

Table VIII

Sulfur sensitized cubic silver bromide emulsion containing; an average grain size of 0.2 / um sodium compound I , ..

Experiment thiosulfate ₍ mmol λ? ™ ί? 7 ~ Χ? -; ^ wT ₄ - ~ Hr .. Pentahydrate ^{( }} sensitivity

(mg / mole AgBr)

81 90 0 100

(Default)

90 10.7 263

90 21.3 295

From the speed values in Table VIII above, it can be seen that the speed increased by using the Method of incorporating the hydroxytetrazaindene compound into

609823/0927

the sulfur-sensitized fine-grained cubic Silver broinide emulsion can be increased considerably.

Example 6

In the same manner as in Example 1, a silver bromido'odide emulsion containing octahedral grains having an average grain size of 0.29 µm (silver iodide content 1 mol%) was prepared, but this time the following conditions (1) to (4- ) were observed: (1) 18.3 mg of sodium thiosulfate pentahydrate was added per mole of silver halide, and the emulsion was ripened for 70 minutes at a temperature of 55 ° C to carry out sulfur sensitization; (2) after completion of ripening and before application in the form of a layer, 4-hydroxy-6-methyl-1, 3,3a, 7-fcetrazaindene (compound I) was added in an amount of 0.16 mmol, 32 mmol, 64 mmoles or 128 mmoles per mole of silver halide added to prepare the samples; (3) Each sample was then (, Färbteiiiperatur 4800 ⁰ K 100 000 lux ') exposed for 1/100 second without a blue filter with a xenon lamp or a tungsten lamp with a long (1000 lux, the color temperature 2854- ° K) for 10 seconds; (4) After exposure, each sample was developed for 3 minutes at 27 ° 0 using the following developer:

Composition of the developer

Metol 5.37 g

Sodium sulfite 54.4 g

Hydroquinone 11.5 g

Borax pentahydrate 16 g sodium hydrogen sulfite 3.8 g

Sodium hydroxide 10.54- g potassium bromide 5 S

Water ad 1 1

6 09823/0927

The results of the various measurements on the samples are given in Table IZ below.

Table IX

Octahedral silver bromide iodide emulsion with an average Grain size of 0.29 µm, sensitized with sulfur has been (sodium thiosulfate pentahydrate: 36.6 mg / mol AgBrJ)

Try him. Exposure time

(Sec.)

91

10

92

1/10

Connection -I relative τπ. J-Vi ¹ 01 Wiol AgBr 0 100
(Default) 16 195 32 251 6k 295 128 •
339 0 100
(Default) 16 166 32 209 6Ü 230 128 235

60 9823/092

From the sensitivity values given in Table IX above it can be seen that both with a long exposure to a low light intensity and in the case of a short-term exposure to a high light intensity by using the method of incorporation of the Hydroxytetrazaind compound into the sulfur-sensitized fine grain octahedral silver bromide iodide emulsion whose sensitivity can be increased considerably

Example 7

With a silver iodide emulsion (silver iodide content 1 Mo 1-%), containing octahedral grains having an average grain size of 0.29 µm, prepared in the same manner as in FIG Example 6, but this time 18.3 mg of sodium thiosulfate pentahydrate and 9 * 8 mg of chloroauric acid per mole of silver halide had been added in the initial stage of ripening (for ripening, the temperature of the system was raised to 55 ° C, then sodium thiosulphate was added (starting point of ripening)) * the sensitivity values given in Table X below obtain.

609823/0927

Table X

Octahedral silver bromide godide emulsion with an average Grain size of 0.29 µm made with a combination of a sulfur compound and a gold compound had been sensitized.

Try Mr. Exposure time

(Sec.)

relative

101

10

102

1/100:

connection I Sensitive / m M.ol \ lol AgBrJ ' 0 100
(Default) 16 · 110 32. • 126; - SK- 155 128. 178 0 · i
100
(Default) .16 126; 32 138 64 151 128 155

The sensitivity values given in Table X above show that a significant increase in sensitivity could be determined both with long-term exposure with a low light intensity and with short-time exposure with a high light intensity by using the method for incorporating the hydroxyl; etra ζ aindene compound into the fine-grained octahedral silver bromide iodide emulsion which has been sensitized with a combination of a sulfur compound and a gold compound. The exposure and development were the same as in Example 6 for the rest.

609823/0927

Example 8

With a silver bromide godide emulsion (silver iodide content 1 mol%) containing cubic grains with an average grain size of 0.29 / "UiD., Prepared in the same manner as in Example 6 except that the pAg value was added to the preparation of the silver halide grains 50 ° C kept at 7.9 and 18.3 mg of ifetrium thiosulfate pentahydrate and 9.8 mg of chloroauric acid were added in the initial stage of ripening as in Example 7, but this time a temperature of 50 G was used given in Table XI below
Get sensitivity values. The exposure and development were otherwise the same as in Example 6.

Table XI

Cubic silver bromide iodide emulsion with an average Grain size of 0.29 µm, which has been sensitized with a combination of the sulfur compound and the gold compound.

Experiment no. Exposure time

111

(Sec.)

10

112

1/100

60982 3/0927

Compound I. relative
Sensitivity -fc , m jviol ν
¹ MoI AgBr $ ' 0 16 100
( Default) 32 155 64 128 162 0 170 16 224 32 100
(Default) 64 132 128 132 135 145

From the sensitivity values given in Table XI above it can be seen that a significant increase in sensitivity could be achieved by using the Process for incorporating the hydroxytetrazaind compound into the fine grain cubic silver bromide iodide emulsion, the with a combination of a sulfur compound and a Gold compound had been sensitized.

The invention has been described above with reference to specific Embodiments explained in more detail, but it is obvious to a person skilled in the art that they are by no means on it is limited, but that these can be changed and modified in many ways without affecting the Is left within the scope of the present invention.

Claims;

BO 9823/0927

Claims (1)

Claims H.) Method of increasing the sensitivity of a photographic Silver halide emulsion, characterized in that a sulfur-sensitized photographic silver halide emulsion, which contains silver halide grains having an average size of not more than 0.5 µm, at least one hydroxytetrazaindene compound incorporated into the general formula (Ri) (D (II) where IL, and E ₂ d © ^we il ^s a hydrogen atom, an aliphatic ^ or aromatic group and η denotes the number 1 or 2. 2. The method according to claim 1, characterized in that one as silver halide, a silver bromide, a silver bromide iodide, a silver chlorobromide, a silver chlorobromide godide Silver chlorido'odide or a mixture thereof is used. 5. The method according to claim 1 and / or 2, characterized in that that a silver halide containing 97 mol% or more of silver bromide is used. 609823/0927 4. The method according to at least one of claims 1 to 3, characterized in that a silver halide is used, the 97 mol or more silver bromide and the remainder silver iodide contains. . · 5. Method according to at least one of claims 1 to 4, characterized in that a silver halide is used which contains 98.6% or more of silver bromide and, as the rest, silver iodide contains. 6. The method according to at least one of claims 1 to 5? by using a silver halide, whose diameter-cut horn size is no more than 0.35 µm. 7. The method according to at least one of claims Ί to 6, characterized in that one uses a silver halide emulsion used, dJLe granules with an octahedron, cubic, tetradekaed3? a. see, spherical, leaflet-shaped, irregular-spherical, Contains irregular polyhedral and / or "potato-shaped" crystal form. 8. The method according to at least one of claims 1 to 7 ».. characterized in that one uses a photographic silver halide emulsion used containing the sulfur-containing compound in an amount within the range of about ΊΟ "" '' contains up to about 10 moles per mole of silver halide. 9. The method according to at least one of claims 1 to 8, characterized in that at least one hydroxytetrazaindene compound is used of the general formula Ϊ or II. in an amount within the range from about 0.001 to about 0.5 Moles used per mole of silver halide. 60 9823/0 92 7 10. Procedure according to. Claim 9, characterized in that that at least one hydroxytetrazaindene compound of the general formula I or II in an amount within the From 0.01 to 0.2 moles per mole of silver halide is used. 11. The method according to at least one of claims 1 to 10, characterized in that at least one compound from the group 4-hydroxy-6-methyl ~ 1,3,3a, 7-tetrazaindene is used as the hydroxytetrazaindene compound of the general formula I or II , 4 ~ hydroxy-1,3,3a, 7-tetrazaindene, 4 ~ hydroxy-6-methyl-1,2,3a, 7-tetrazaindene, 4 ~ hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene , 4-ethyl-6-hydroxy-1, 3,3a, 7-tetrazaindene, 2,6-dimethyl-4-hydroxy-1, 3,3a, 7-tetrazaindene, 4-hydroxy-5-ethyl-6-meth3 ^ 1-1, 3,3a, 7-tetrazaindene, 2,6-dimethyl-4-hydroxy-5-ethyl-1,3,3a, 7-tetrazaindene, 2,5,6-trimethyl-4-hydroxy-1 , 3,3a, 7-tetrazaindene, 2-methyl-4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene, 4-hydroxy-6-ethyl-1,2,3a, 7-tetrazaindene, 4 --Hydroxy-6-phenyl-1,2,3a, 7-tetrazaindene, 4-hydroxy-1 ^^ a ^ -tetrazaindene, 4 ~ methyl-6-hydroxy-1 ^^ a ^ -tetrazaindene, 4 ~ hydrox3r -5,6-trimethylene-1,3 ^ a ^ -tetrazaindene, 4 ~ hydroxy-5,6-tetramethylene-1,3,3a, 7-tetrazaindene, 4,5-trimethylene-6-hydroxy-1 ^^ a ^ -tetrazainden, 4,5-tetramethylene-6-hydroxy-1 _t 2,3a, 7-'b etrazaindene and 4-hydroxy-5,6-dimethyl-1,3 »3a, 7-tetrazaindene are used. 12. The method according to claim 11, characterized in that the hydroxytetrazaindene compound of the general formula I or II is at least one compound from the group 4-hydroxy-6-methyl-1,3,3a, 7- "betrazaindene, 4 ~ hydroxy -1,3 ₄ 3a, 7-tetrazaindene, 4-hydroxy-6-methy 1-1,2,3a, 7-tetrazaindene, 4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene and 4— Methyl-6-hydroxy-1,3,3a, 7-tetrazaindene is used. 13 · Method according to claim 12, characterized in that the hydroxytetrazaindene compound of the general formula I or II used is 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. 609823/0927 14-. Photographs before silver halide emulsion, characterized that it has been sensitized by the method according to at least one of claims 1 to 13. 15. The silver halide photographic emulsion of claim characterized by being a silver halide grain contains an average size of not more than 0.35 / µm. 16. * Photographic silver halide emulsion according to claim 14- and / or 15, characterized in that they contain at least one hydroxytetrazaindene compound of the general formula I or II in an amount of from about 0.001 to about 0.5 moles per mole of silver halide. 1?. A silver halide photographic emulsion according to claim 16, characterized in that it contains at least one hydroxytetrazaindene compound of the general formula I or II in an amount of 0.01 to 0.2 mol per mol of silver halide .. 18. Silver halide photographic emulsion after at least one of claims 14 to 17, characterized in that they use the sulfur-containing compound in an amount of -5 -1 about 10 r to_about 1Q .. moles per mole of silver halide, contains » 1-9 · Method for preparing silver halide photographic emulsion according to at least one of claims 14 to 18, characterized in that a sulfur-sensitized Emulsion containing silver halide grains having an average size of not more than 0.5 µm, at least one hydroxytetrazaindene compound the general formula I or II given in claim 1 incorporated to their sensitivity to increase. 20. The method according to claim 19, characterized in that at least one hydroxytetrazaindene compound in one B09823 / 0 927 Amount from about 0.001 to about 0.5 moles per mole of silver halide used. 21. Terfahren according to claim 20, characterized in that there is at least one hydroxytetrazaindene compound in one Amount of 0.01 to 0.2 moles per mole of silver halide is used. 22. The method according to at least one of claims 19 to 21, characterized in that the emulsion is a sulfur containing compound in an amount from about 10 "" to about -1
10 moles per mole of silver halide incorporated to produce a sulfur carry out awareness-raising, 23. The method according to at least one of claims 19 to 22, characterized in that an emulsion is used which contains silver halide grains of a size of not more than 0.35 / ura contains. 24-, photographic material (element), characterized in that, that it consists of a urager and at least one on it applied layer of a sulfur sensitized photographic Silver halide emulsion, the silver halide grains with an average size of no more ... than 0 »5 / uil and at least one hydroxytetrazainden compound of the general ! Formula contains HO or R ₂ (II) where B ^ and Sp each denotes a hydrogen atom, an aliphatic or aromatic group and η denotes the number 1 or 2.