DE2211769A1 - Process for making positive photographic images - Google Patents

Description

Process for producing positive photographic images

The invention relates to a method for producing positive photographic images by imagewise exposure and development of a photographic material having at least one light-sensitive silver halide emulsion layer.

It is known, for example, from U.S. Patents 2,497,875, 2,588,982 and 2,456,953, British Patent Specification 1,151,363 and Japanese Patent Specification 29 405/68, positive photographic images in recording materials with non-fogged Silver halide emulsion views by imagewise exposure and subsequent development in fogging developers to manufacture. The recording materials used in these known processes are characterized in that to their production so-called internal image or internal grain overhalide emulsions can be used, for example those emulsions which are known from US Pat. No. 2,592,250 Conversion method can be prepared, or such emulsions, for example according to the from the British patent 1 011 062 known processes can be obtained.

In the conversion method known from US Pat. No. 2,592,250 an emulsion of a silver salt is first prepared in the presence of inert gelatin, the grains of which at least partly consist of a silver salt that is more soluble in water than silver bromide. The z. B. consisting of silver chloride Silver halide grains are then made into silver bromide by adding alkali bromides and / or alkali iodides to the emulsion. or silver iodobromide grains.

In the process known from British Patent 1,011,062, a very fine-grain silver halide emulsion is produced mixed with a chemically sensitized, considerably coarser-grained emulsion, whereupon the mixture undergoes a ripening process is subjected, in which the fine grains partially

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dissolve and deposit on the surface of the coarser grains. In this way, the grains of the coarser-grained emulsion get a kind of shell.

Disadvantages of the known processes for producing positive Images using unfogged silver halide emulsions have the same sensitivities as these emulsions are quite satisfactory and that too high D values and too low D values are obtained when they are used.

The object of the invention was therefore to provide a method for producing positive photographic images that would allow production positive images of improved quality.

The invention was based on the knowledge that photographic Allowing images of improved properties to be obtained in the production of reversal images or positive images if to carry out the process, photographic recording materials are used which have at least one internal image or internal grain emulsion layer have which silver halide grains

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hold, remove the polyvalent Freadmet all ions included.

It has been found that from such recording materials, improved positive images can be obtained in various ways. Thus, it was found that 5 to Aufzeictinungsinaterialien with at least one Silberhalogenidemulsionsschicut whose Silberhalogenidkorner polyvaleiite lietallionen included contain, after the imagewise exposure in the presence of a veil center Is in a Silbernalogenidoberfläcnenentwickler develop or flash expose during development in Einein Silberhalogenidoberflächenentwickler or to a temperature of at least 1UO ⁰ C and then develop in a silver halide surface developer.

The invention thus provides a process for the production of positive photographic images by image-appropriate exposure and developing a photographic material at least one light-sensitive silver halide emulsion layer, which is characterized in that one

1) a recording material with at least one silver halide emulsion layer, their silver halide grains are polyvalent j-iet al! Ions included, properly exposed and daii man

2) the exposed silver halide emulsion layer of the recording material either

a) In the presence of a fogging agent in a silver halide surface developer developed,

b) during development in a silver halide surface developer flash exposed or

c) heated for at least 1 second to a temperature of at least 100 ⁰ C and then in e.
surface redeveloper developed.

100 ⁰ C heated and then in a silver halide surface

riUk a Lesortders advantageous embodiment of the

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v / ground recording materials to carry out the procedure used with at least one silver halide emulsion layer, while silver halide grains include polyvalent metal ions and which contain the sensitizing concentrations of sensitizing dyes adsorbed.

The silver halide emulsions used to produce the recording materials can be prepared by precipitation of silver halide in the presence of ionized metal salts.

Advantageously, to carry out the method of the Invention recording materials with at least one light-sensitive Silver halide emulsions are not used, their silver halide grains Have ion inclusions. The use of such recording materials is also particularly advantageous whose silver halide grains contain trivalent or tetravalent metal ions included. Preferably the silver halide grains of the emulsion layers contain antimony, bismuth, arsenic, gold, Iridium or rouium ions or osmium, iridium or platinum ions.

«Tetravalents

The invention is also of particular advantage for the known Image transfer processes according to which direct positive transfer images can be produced. Thus, the known film elements can also be used to carry out the method of the invention or film units for the production of transfer images are used, which apart from at least one image-recording Layer nocii have an image receiving layer and a cleavable one Container with the developing liquid or for the development of the required working fluid, which by the action of pressure split up, so he can divide his content between photosensitive over halide emulsion layer and Image receiving layer capable of pouring. The splitting can be done by passing the film element or the film unit through a pair of pressure-exerting clippers arranged one above the other are carried out,

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which can be arranged, for example, in a photographic camera can. Advantageously, a selective veil can be arranged in the film unit or the film element, which comes into contact with the silver halide when the developing solution is released from the working solution from the splittable container got. The fogging agent can be in one layer of the unit or the element or be contained in the splittable container.

The polyvalent metal ions in the silver halide grains are so-called foreign metal ions; h * metal ions, which differ from the silver ions from which the silver halide grains are built up. »Emulsions of this type can be, as previously stated, by producing the silver halide grains in the presence of a MeIaIion ens al ζ it generate. In the case of manufacture of the silver halide grains in aqueous media, it has proven to be expedient to use such a metal salt for producing the metal inclusions to be used, which is at the fermentation temperature the silver halide grains have at least some water solubility.

The manufacture of the silver halide emulsions required for manufacture of a recording material suitable for carrying out the method of the invention can, for example, according to Methods are as disclosed in U.S. Patents 3,272,257, 3,447,927, and 3,531,291.

Advantageous divalent metal ions are, for example, lead ions, while particularly advantageous trivalent metal ions, for example Are antimony, bismuth, arsenic, gold, iridium and rhodium ions. Particularly advantageous tetravalent metal ions are, for example Platinum, osmium and iridium ions. If necessary, the silver halide grains can also contain mixtures of various polyvalent ones Have metal ions.

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The metal ions or metal ion mixtures can advantageously be used in the production of emulsions with the water-soluble silver salt, for example silver nitrate, or the water-soluble one Halide, for example sodium or potassium iodide, or sodium or potassium bromide or sodium or potassium chloride, can be added in the preparation of the silver halide emulsions. On the other hand, however, the polyvalent ions can also be used together with a hydrophilic colloid, for example gelatin, into the reaction vessel used for silver halide precipitation. The polyvalent metal ions can be in In the form of water-soluble inorganic salts, in the form of organometallic compounds or in the form of complexes or in the form of other substances, when used during the Formation of the silver aloyenide grains to produce polyvalent metal ions To be available.

The concentration of polyvalent metal ions can vary widely. It has proven to be useful if at least

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1 χ 10, preferably about 1 χ IO to about 2 MoI-I metal ions, based on the silver halide used. The presence of polyvalent metal ions in the silver halide grains can be determined analytically, through successively washing the precipitated silver halide grains with a silver halide solvent such as an organic one Thioether or an alkali metal thiocyanate. Are the polyvalent metal ions only on the surface of the Silver halide grains, practically all of these ions are found in the first V / ash solutions, whereas in the case of inclusions Ions in silver halide grains, substantial amounts of polyvalent ions are found in V / ash solutions, which are short occur before complete dissolution of the silver halide grains.

Advantageously, the silver halide grains of the silver halide emulsions be sensitized on their surface with the help of spectral sensitizing dyes. the

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Dyes can be used in concentrations such as are known in the art for spectral sensitization photographic Emulsions are used or in concentrations at which conventional known, chemically surface-sensitized Prior art emulsions, which can be negative or direct positive emulsions, a Desensitization is caused. Typical dyes that can be used to sensitize the emulsions, are for example methine dyes, e.g. B. cyanine and merocyanine dyes, as for example from the USA patents 1 846 301, 1 S46 302, 1 942 854, 1 990 507, 2 112 140, 2 165 338, 2 493 747, 2 739 964, 2 493 748, 2-503 776, 2 519 001, 2 666 761, 2 734 900 and 2 739 149, also the British U.S. Patent 450,958 and U.S. Patent Application 56,700 are known.

According to a particularly advantageous embodiment of the invention, the sensitizing dyes are used in concentrations at which the blue sensitivity of a sulfur-gold-surface-sensitized silver- gold iodide emulsion with 6 Uol-% iodide of the same grain size and the same grain size distribution by at least 0.3 log Ε units would be reduced if this silver bromide iodide emulsion were developed in a surface developer, for example a developer of the following composition, at 25 ° C.

Water, about 50 ^° C. 500 ml

N-methyl-p-aminophenol sulfate 2.0 g

Sodium sulfite, dehydrated 90.0 g

Hydroquinone 8.0 g

Sodium carbonate, monohydrate 5 2.5 g

Potassium bromide 5.0 g

filled up to 1.0 liter with cold water

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As very particularly advantageous for carrying out the method of Invention have recording materials with at least one A silver halide emulsion layer comprising silver halide grains which have lead ion bonds and which has one or more Contain sensitizing dyes in a concentration that has a desensitizing effect. Contained in a particularly advantageous manner such recording materials as fogging agents N-substituted quaternary cyclammonium salt, which in at least such a layer of the photographic recording material is placed in the presence of an aqueous solution such as developing solution in the silver halide emulsion layer diffuse or migrate.

As used herein, "sensitizing dye" means dyes known to be silver halide emulsions able to sensitize spectrally. As particularly advantageous dyes for sensitizing the process photographic recording materials used in the invention Such organic dyes have been shown to have a cathodic half-wave potential that is less positive as -1.0, i.e. H. for example -1.5 or -2.0. The cathodic Ilalstufenpotential can for example can be determined by the method known from US Pat. No. 3,501,307.

The silver halide grains of the silver halide emulsion layers of the recording material used for carrying out the process of the invention are not fogged. The emulsions contain only minimally developable latent surface images, a density of less than 0.4, preferably less than 0.25, being achieved with a development time of 5 minutes with a developer of the composition given below at 27 ^{° C.}

Water, about 5 2 ⁰ C 500 ml

N-methyl-p-aminophenol sulfate 2.5 g

Sodium sulfate, dehydrated 30.0 g

Iiydroquinone 2.5 g sodium nitrate

Potassium bromide 0.5 g

made up to 1.0 liter with water

However, the surface of the silver halide grains of the emulsion layers of the recording materials used for practicing the method of the invention may be chemically sensitized to a level below that which would achieve a fair density (ie a density of less than 0.25) using a surface developer of the type indicated The composition after imagewise exposure would provide if the emulsion layer had a thickness of about 300 to 400 mg Ag per 0.0929 square meters of support area (300 to 400 mg Ag / Ft ² ).

Under a chemical sensitization there is a sensitization to adjust, as described, for example, by A. Hautot and H. Saubenier in "Science et Industries Photographiques", volume XXVIII, January 1957, pages 1-23 and January 1957, pages 57-65. Such chemical sensitization leaves can be divided into three main classes, namely a gold or precious metal sensitization, a sulfur sensitization, for example by using a compound having a labile sulfur atom, and reduction sensitization, i.e., a Treatment of the silver halide with a strong reducing agent which does not noticeably obscure the silver halide, however, introduces tiny dots of metallic silver into the silver halide grains or silver halide crystals.

The method of the invention enables positives to be made Images through a simple exposure and development process. For example, positive images can be produced once by using a recording material with at least one silicon / halide emulsion layer of the type described imagewise exposed and then in the presence of a fogging agent in one Silver halide surface developer is developed. On the other hand, positive images can also be produced by

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that the recording material is flash-exposed during the surface development or that the imagewise exposed recording material is thermally fogged by increasing the temperature of the emulsion layer or layers to at least 100 ^° C. for at least 1 second, followed by development in a surface developer.

Under "surface developer" are meant here those developers which expose latent surface images on silver halide grains, however, do not lead to any substantial exposure of latent internal grain images in the case of internal grain or internal image emulsions, and which, under the conditions under which they are generally used, are surface-sensitive silver halide emulsions to develop. Such surface developers can be the conventionally known silver halide developing agents or reducing agents active compounds contain, but they contain no or practically no silver halide solvent, for example water-soluble thiocyanates, water-soluble thioethers, thiosulfates or ammonia, which lead to a solution or splitting of the Grains exposing the inner grain pattern. It can optionally be advantageous in the developer or the or the emulsion layers a slight excess of water-soluble halide salts, e.g. B. potassium or sodium bromide or Potassium or sodium iodide, but higher concentrations of such salts should be avoided to prevent that a cleavage of the silver halide grains takes place, in particular with respect to iodide, liberating compounds.

Typical silver halide developer compounds used in the developers HydroquinoneQ can be used, for example Pyrocatechols, aminophenols, 3-pyrazolidones, ascorbic acid and ascorbic acid derivatives, reductones, phenylenediamines, or combinations thereof. The developer compounds can thereby be accommodated in the photographic recording materials themselves, in which case they follow with the silver halide the imagewise exposure thereof. In general, ^^ p ^ e ^ Qch in advantageous kei-se in

Form of a developer bath or a developer solution in the presence of the silver halide fogging agent or nucleating agent Applied means.

To carry out the embodiment of the method of the invention, in which a flash exposure takes place during surface development, the conventionally known flash lamps can be used and flash devices are used, in a known manner the flash exposure can be the shorter / the higher the intensity the flash lamp used. For example, a contact printing lamp emitting cold light can be used for exposure can be used with a tungsten light source such as in the form of Model 919 from Colwell Litho Products, Inc., Minneapolis, Minnesota, U.S.A., on the market used xvird.

The developers used in carrying out the method of the invention can optionally use conventional known antifoggants and / or contain development retarders. If appropriate, such compounds can also be used in the layer or layers of a for Carrying out the method of the invention used recording material be accommodated. Typical antifoggants are, for example, benzotriazoles, benzothiazoles, for example 5-methylbenzothiazole, 5-methylbenzotriazole and also heterocyclic Thiones, for example l-methyl-2-tetrazoline-5-tliion, and also aromatic and aliphatic mercapto compounds.

When using eixies fogging agent this can in at least a layer of the recording material are accommodated, this layer being in a water-permeable bandage with the silver halide emulsion layer. On the other hand, can the Schlierinittel, however, also by means of a special bath or a special solution can be brought into contact with the silver halide emulsion layer or simultaneously with the silver halide surface developer in which the fogging agent the developer solution is added.

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In carrying out the method of the invention, all are fogging agents suitable, which lead to nucleation or create veil centers or veil points, which the development of the Initiate silver halides in the unexposed areas before developing the exposed areas of the inner grain emulsion layer in which surface developer is initiated. Such Fogging agents are generally not themselves useful developer compounds for silver halides. In the literature they are used as selective fogging agents or as silver halide fogging agents or nucleating agents.

Selective veils have proven to be particularly advantageous ILydrazine compounds and iOXSC & idtööXXMXiipC N-substituted cycloammonium salts proven.

Hydrazine compounds which can advantageously be used as fogging agents are known, for example, from U.S. Patents 2,588,982 and 3,227,552.

Furthermore, the Χ & Χ & ΚΧ «& χ £ ΧΟ & 3Β0Χ N-substituted quaternaries, for example, have proven particularly advantageous as fogging agents Cyclammonium salts proved, for example from the USA patent 3,615,615 and are further described in U.S. Patent Applications 85,706 and 85,709 (dated October 30, 1970) will.

Such Χ £ ΧΚΚ £ «ΑΧ £ Χ <Χ} ίρί N-substituted quaternary cy el ammonium salts can be represented, for example, by the following structural formula:

Φ i \ £ - CH ■ - CII '

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Herein mean:

Z to complete a heterocyclic

Ring with 5 or 6 ring atoms, including the quaternary nitrogen atom Atoms, with the rule that the atoms apart from the nitrogen atom can consist of carbon, nitrogen, Oxygen, sulfur and / or selenium atoms;

j = 1 or 2;

a = 2, 3, 4, S or 6;

X is an acid anion;

R either a formyl radical or a radical of

Formula:

- σι

^T 2

where mean:

T ₁ and T ₂ individually alkoxy or alkylthio radicals

or together to complete a cyclic oxyacetal or cyclic Thioacetal ring with 5 to 6 atoms in the heterocyclic acetal ring required Atoms, or a 1-hydrazonoalkyl radical and

Rj Hin hydrogen atom or an alkyl, aralkyl,

Alkylthio or an optionally substituted aryl radical, preferably of the phenyl or naphthyl series.

The use of such N-substituted compounds can be of particular advantage be quaternary cyclammonium salts, the N-subsfcLtuiert Have alkyl radicals whose terminal carbon atom is replaced by a

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liydrazonorest, an acyl radical, for example a formyl radical, an acetyl radical or a benzoyl radical is substituted and those, which have a dihydroaromatic core, for example a dihydropyridinium nucleus.

Although the fogging agent is in any layer of the recording material Bond with the silver halide emulsion layer permeable in water or by means of a pretreatment bath prior to development with the emulsion layer can be brought into contact or can be brought to use with the developer solution, it has yet to be considered They have proven particularly advantageous in the silver halide emulsion layer accommodate yourself.

Preferably the lubricants are used in concentrations of about 75 to about 1500 mg per mole of silver of the silver halide emulsion layer used, especially in concentrations of about 90 to 1200 mg per mole of silver. These concentrations correspond the concentrations usually used. In the case of special However, reverse emulsions or the use of special fogging agents of different chemical activity and, under special process conditions, concentrations can also be used outside of the specified ranges may be beneficial.

Advantageous selective fogging agents for carrying out the process of the invention are for example;

2-methyl-3 - ^ "3- (p-sulfophenylhydrazone) propyl7benzothiazoliuBibromidi hydrazine dihydrochloride; phenylhydrazine hydrochloride; p-methylsulfonamidoethylphenylhydrazine; formyl-4-iaethyl-phenylhydrazide; 3- (2-formylethyl) -2-methylbenzidethyl; 3- ( ) -2-benzylbenzothiazolium bromide; 3- (2-acetylethyl) -2-benzylbenzoselenazoliumbroraid; 1, Z-dihydro-S-methyl-i-phenylpyrido ^,! - ^ - benzothiazolium bromide; 4,4'-ethylene-bis (I _f 2-dihydro-3-methylpyrido ^ ~ 2,1-b7benzothiazolium bromide and 2-methyl-3- ^ ~ (3-p-nitrophenylhydraono) propyl7naphtho ^ "2, ld ^ thiazoliuajodid.

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The silver halide emulsions used for the production of the photographic recording materials can be produced by the customary known precipitation and ripening processes which are used for the production of silver halide emulsions with silver halide grains with metal inclusions or metal dopants. To prepare the emulsions, thus, so-called E infacheinlaufverfahren or double-jet method can be applied as well to use Verfaiiren with automatic control or control devices for maintaining specific pAg and pK values as well as further procedures, the ripening agents, for example Tniocyanate, thioether and / or ammonia, and also Processes in which increased flow velocities are used, as are known, for example, from Belgian patent specification 763 Ü40 and processes which can be referred to as so-called nucleation processes, are described, for example, in US patent application 31 351 of April 23, 1970.

So-called monodisperse silver halide emulsions are preferably used to produce the recording materials, it may be particularly advantageous to use emulsions with large silver halide grains, which can be produced, for example, by the process of Belgian patent 763 040. Monodisperse emulsions are understood as meaning those emulsions whose silver halide grains have a practically uniform diameter. As a rule, monodisperse emulsions are considered to be those in which no more than about 5% by weight of the silver halide grains have a grain size that is smaller than the average grain size and in which no more than about 5% of the silver halide grains have a grain size which is larger than the average or mean grain size and whose diameter deviates from the mean grain diameter by more than about A0%. Particularly advantageous silver halogenide emulsions have proven to be those for which at least 95 Cew. -% of the silver halide grains have a diameter which deviates from the mean grain diameter by no more than 40%, in particular no more than 30%.

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The mean grain diameter, i.e. H. the average grain size can be determined by customary known methods, for example by the methods described by Trivelli and Smith in ■ of the magazine "The Photographic Journal", Volume LXXIX, 1939, Pages 330-333 under the title "Empirical Relations between Sensitometric and Size-Frequency Characteristics in Photographic Emulsion Series ".

The uniform grain size distribution of the silver halide grains is a characteristic of the grains of dispersed photographic material Silver halide emulsions. Silver halide grains with a narrow grain size distribution can be produced in that under Application of the double inlet process the conditions under which the silver halide grains generated can be precisely controlled. In such processes, the silver halide grains are through simultaneous running in of an aqueous solution of a water-soluble silver salt, for example a silver nitrate solution, and an aqueous solution of a water-soluble halide such as a solution of an alkali metal halide, for example a potassium bromide solution, into a vigorously agitated aqueous solution of a silver halide peptizing agent, preferably Gelatin, a gelatin derivative or another protein peptizer, generated. The pH value and the pAg value are closely related in this process. For example one value changes while the other value is kept constant at a certain temperature, so the grain size distribution can be adjusted of the silver halide grains are changed. Temperatures of about 30 to about 90.degree. C. are advantageously used applied, a pH of up to about 9, preferably about 4 or below, and a pAg of up to about 9.8.

Processes can be used here, as they are, for example, in the journal "The Journal of Photographic Science", Volume 12, 1964, pages 242-251 and in The Journal of Photographic Science ", Volume 13, 1965, pages 85-89 and the like Zeitschrift, Volume 13, 1965, pages 98-103 and 104-107.

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The emulsions used to make the recording materials can be prepared using the commonly known colloidal binders. Typical hydrophilic ones are mentioned colloidal binders for example the known naturally occurring substances such as proteins, for example gelatin and gelatin derivatives, also cellulose derivatives, polysaccharides, for example dextran, gum arabic and the like, as well as further the known synthetic binders, for example water-soluble Polyvinyl compounds, for example polyvinylpyrrolidone, Acrylamide polymers and the like.

In addition to the hydrophilic water-permeable colloidal binders described, synthetic polymers, for example dispersed polyvinyl compounds, e.g. B. in latex form, in particular those which improve the dimensional stability of the recording material. Such synthetic polymers are, for example, from the US Patents 3,142,568 _s 3,193,386, 3,062,674, 3,220,844, 3,287,289 and 3,411,911 is known. The water-insoluble polymers or latex copolymers of alkyl acrylates and alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates, which have cross-linked centers which facilitate curing or which have recurring sulfobetaines, such as those from, for example, are of particular importance for the structure of the layers of the recording materials Canadian patent 774 054 and US patent 3 488 708 are known "

The supports of the recording materials can be made from the usual known layer carriers consist, for example, of films made of cellulose nitrate, cellulose esters, Polyvinylacetaleiij, Polystyrene, polyesters, e.g. polyethylene terephthalate, Polycarbonates and other polymers, but also made of glass, paper and iMetall. Typically, flexible substrates can be used are used to produce the recording materials,

in particular paper backings that have been partially acetylated may or may have a barite layer and / or a layer made of a cf-olefin polymer, in particular a layer made of a polymer of an α-01efin having 2 to 10 carbon atoms, for example a polyethylene or polypropylene layer, or a layer of an ethylene-butene copolymer.

The method of the invention can advantageously be used, for example consist of a colloid transfer process such as the colloid transfer process disclosed in the United States patent 2 716 059 known type, also a silver salt diffusion * transfer process in which the development of the silver halide r which is preceded by a solution of the silver halide, as is described, for example, in U.S. Patents 2,352,014, 2,543,181, 3,020,155 and 2,861,885 and a color image transfer method such as that of the United States patents 3 087 817, 3 185 567 and 2 983 606 as well as 3 253 915 and 3 227 550 as well as 3 227 551, 3 227 552, 3 415 644, 3 415 645 and 3 415 646 i

known type, and also a suction transfer method,:

for example that known from US Pat. No. 2,882,156 Type. :

The method of the invention is also suitable for manufacture color photographic images in which case the recording materials can contain color couplers, for example those of the type known from U.S. Patents 2,376,679, 2,322,027, 2,801,171, 2,698,794, 3,227,554 and 3,046,129. the Color photographic images can also be produced, for example, by the recording materials be developed in solutions containing color couplers, for example that of US Patents 2 252 718, 2 592 243 ί and 2,950,970 known types. Finally, so-called false sensitization can also be used to carry out the method of the invention. te color recording materials are used, such as from U.S. Patent 2,763,549.

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The following examples are intended to illustrate the invention in more detail.

example 1

First, a silver bromide iodide inner grain emulsion with 2.6 hol% iodide and cubic Si.lberhalogenid grains of 0.2 microns was prepared by simultaneously an aqueous silver nitrate solution and an aqueous potassium bromide-potassium iodide solution in a vigorously agitated aqueous gelatin solution of 10.7 mg Potassium hexachloroiridate was allowed to flow in per mole of silver. The precipitation of the silver halide was carried out in an acidic medium at 70 ⁰ C and a pAg of 8.9 within 60 minutes. After the precipitation (for the silver halide, the emulsion was noodled, washed and quenched. A 10% saponin solution as a coating aid and a 40% formaldehyde solution as a hardening agent were then added to the emulsion in the usual way, whereupon it was applied to an adhesive-coated cellulose acetate base in a layer thickness, Measured wet, applied from 0.015 cm. 200 mg of silver and 800 mg of gelatin accounted for a support area of 0.0929 m. The dry recording material was then measured using a 100 watt tungsten lamp, which had been set up at a distance of 1.20 m , Exposed for 5 seconds in an imagewise manner. The material was then immersed in a surface developer of the following composition:

Sodium sulfite 10 g

Hydroquinone 10 g

2.5 η sodium hydroxide solution 10 g made up to 1 liter with water.

During the immersion of the recording material in the developer solution the emulsion layer was uniformly exposed to white light using a 100 watt lamp running in a distance of about 90 cm was exposed for 20 seconds. In this way a direct positive image was obtained.

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Example. 2

A silver chlorobromide emulsion was first prepared using the procedure described in Example 18 of U.S. Patent 3,447,927 made with bismuth ions in the core of the silver halide grains. The emulsion was then coated on a cellulose acetate base, whereupon the emulsion layer was applied for 1/2 second at a Slot width of 1.0 mm in a spectrograph (Bausch and Lomb) was exposed. The emulsion layer was then bleached in a potassium ferricyanide solution for 1 minute. After washing it was the recording material is immersed in a developer of the following composition:

Water, about 50 ^° C. 500 ml

N-methyl-p-aminophenol sulfate 2.0 g

Sodium sulfite, dehydrated 90.0 g

Hydroquinone 8.0 g

Sodium carbonate, monohydrate 5 2.5 g

Potassium bromide 5.0 g

made up to 1.0 liter with cold water

and for 10 seconds with a photoflood lamp flash exposed. The flash exposure completely obscured the unexposed areas, but not the image areas, whereby a positive image was obtained.

Example 3

First several inner grain emulsions were prepared according to the method described in Example 1, but this time different concentrations of lead nitrate, namely 5, 25, 125, 600 and 3000 mg per mole of silver nitrate, were used instead of the iridium salt used in Example 1. For comparison purposes, another emulsion was prepared without the addition of lead nitrate. ^v

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Portions of the emulsions produced were then coated on cellulose acetate film supports applied using suitable spreading and hardening agents.

Strips of the recording materials obtained were then 1/125 seconds in a spectrograph (Bausch and Lomb) at a Slit width of 1.0 mm exposed and then exposed in a developer of the composition given in Example 2 and developed uniformly for 5 seconds with a 100 watt tungsten lamp exposed. The test specimens were left in the developer solution for a further 2 hours before they were removed from the developer bath became.

The following results were obtained:

In the recording material with the emulsion layer, its SiI superhalide grains did not contain lead ions, no positive image was developed, whereas in the other cases, i.e. H. in those cases where the emulsions were formed in the presence of lead ions, positive images of excellent quality were obtained were, which showed that the suitability of the recording material for producing positive images of excellent quality with the lead nitrate concentration increased. It was found that an advantageous concentration of 125 mg of lead nitrate per mole of silver halide lay.

Example 4

First, an inner grain emulsion with 125 mg of lead nitrate per Moles of silver prepared according to the method described in Example 3. 400 mg of the sensitizing dye 5 - / "" (5,6-dichloro-1-ß-diethylaminoethyl-3-ethyl-2-benzimidazolinylidene) ethylidene-7-3-ethylrhodanine were then added to the emulsion added per mole of silver. The emulsion was then coated on a cellulose acetate film support applied and exposed in a spectrograph at a slit width of 1.0 mm 1/1000 of a second. Thereon-

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the test piece was then immersed in a developer having the composition given in Example 2 and uniformly for 5 seconds exposed for a long time with a 100 watt tungsten lamp. In this way, a highly sensitive positive image was obtained.

Example 5

First, an emulsion was prepared according to the method described in Example 4. The emulsion was then applied to a layer support, whereupon the material obtained was exposed in a spectrograph with a slit width of 1.0 mm for 1/1000 of a second. The recording material was then ^{heated to 200 °} C. for 5 seconds on an aluminum block. The recording material was then developed in a developer of the composition given in Example 2. In this way, a positive image of excellent quality was obtained.

Example 6

This example compares the effects when using an emulsion doped with lead ions (invention) and when using a halide conversion emulsion (conversion emulsion) obtained will.

First, the emulsions A and B described in more detail below were prepared:

Emulsion A

An emulsion doped with lead ions was prepared according to the method described in Example 3 using 125 mg of lead nitrate made per mole of silver.

Emulsion B

A conversion emulsion was made according to the in Example I of U.S. Patent 2,592,250.

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Various proportions of the emulsions were then used as a fogging agent 2-methyl - / "3- (p-sulfophenylhydrazone) propyl_7benzo» -thiazolium bromide added in various concentrations. To determine the optimal concentration of the dye, its use is known, for example, from Example 7 of US Pat. No. 2,917,516, different emulsion proportions were each 100, 200, 400 and 800 mg of dye added per mole of silver.

The emulsions were then measured wet at a layer thickness of 0.015 cm on cellulose acetate support with an adhesive layer applied, whereupon the emulsion layers in a spectrograph at a slit width of 1.0 mm 1/1000 second long exposure. After the exposure, the recording materials became developed in a developer of the type described in Example 2. The results were as follows obtain:

In the case of emulsion A, optimal spectral sensitization occurred at a dye concentration of 400 mg per mole of silver, whereas the optimal concentration of the dye im The case of emulsion B was 200 mg of dye per mole of silver. Furthermore, was in the spectrally sensitized areas of the emulsions (460 to 610 nm) reduced emulsion A by 0.6 log E units more sensitive.

Correspondingly advantageous results in terms of photographic Sensitivity, higher D and lower D. Values

max ^to mm

and the usability of higher concentrations of spectral sensitizers Dyes without adversely affecting other photographic properties were found to be lead-doped Emulsions of this example when compared to emulsions made according to Example 2 of U.S. Patent 3,206,313 became.

Example 7

First, three silver bromide iodide emulsions with 5 MoI- ⁰ S Jo-. did prepared by simultaneously and slowly aqueous silver nitrate solutions and aqueous alkali metal halide solutions, e.g. B. potassium bromide and potassium iodide solutions, too

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vigorously agitated gelatin solutions of 35 C and a pH of about 2.0 were allowed to run. Three different gelatin solutions were used, one 0.45 mg and the other 4.5 mg and finally contained 45 mg of osmium trichloride per mole of silver.

The emulsions were then washed and coated on film supports, exposed and following that described in Example 1 Process developed. In all cases, positive images were obtained with improved image resolution and improved photographic sensitivity obtained with increasing concentration of osmium trichloride, if they are obtained with the US Pat. No. 2,592,250 and British Patent 1,011,062 known / ~ For comparison purposes, another recording material was used with prepared and tested a silver halide emulsion layer without osmium trichloride. In this case, no one could interfere with the Develop a positive image that can be recognized by the eye.

Example 8

First, a silver bromide iodide emulsion was prepared according to the method described in Example 1, but this time instead of the iridium salt H-PtClg was used. Under use The emulsion was then prepared as described in Example 1, and a recording material was used to produce a positive Image used. The positive image obtained was of excellent quality.

Example 9

First, after the procedure described in Example 1, a Silver bromide iodide emulsion prepared, with the exception, however, that instead of the iridium salt 4.5 mg of rhodium trinitrate per mole Silver were used. Using the emulsion was then in the manner described in Example 1, a recording

/ Reverse systems were compared.

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material made. Following the procedure described in Example 1 a positive image of excellent quality was produced from this recording material.

Similar results were obtained when recording materials with silver halide emulsion layers, the silver halide grains of which contain metal inclusions from palladium ions, Had ruthenium ions or gold ions.

Example 10

An internal grain emulsion was prepared according to the process described in Example 3, 125 mg of lead nitrate per mole of silver halide to be produced being added to the vessel used for the precipitation of the silver halide before the beginning of the precipitation. The emulsion was then washed, after which it was coated on a film base. The emulsion layer was finally exposed in a conventional Eastman 1B sensitometer for 1/50 second and then in a masking developer of the type disclosed in U.S. Patent 2,588,982 for T minute developed known type of 27 ⁰ C * After washing and drying, a reverse image excellent photographic builds character was obtained teristics *.

Correspondingly favorable results were obtained when 2-methyl-3- (3-phenylhydrazonopropyl) benzothiazolium bromide was used as the fogging agent at a concentration of 0.027 mg / 0.1929 m of substrate area was present in the recording material and if this was the recording material after imagewise exposure in a surface developer was developed.

Beisel 11

This example illustrates the creation of positive transfer images.

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First, an internal grain silver bromide iodide emulsion was prepared by adding 125 mg of lead nitrate per mole of silver halide to the vessel used to precipitate the silver halide before the start of the precipitation. After the emulsion had been washed, it was applied to a paper support in a concentration of 100 mg silver per 0.0929 m 2 support area. Before the emulsion was applied to the substrate, 107 mg of the color coupler: l-hydroxy-4- {4- / ~ ot- (3-pentadecylphenoxy) -butyramid_7-phenoxy} -N-octadecyl-3 ^f , 5'- dicarboxy-2-naphthanilide (see Example 2 of US Pat. No. 3,476,563) and, as a fogging agent, 200 mg of formyl-4-methylphenylhydrazine / 0.0929 m ^{2 of support area} , as described in US Pat. No. 3,227,550, were added.

The resulting recording material was then exposed and thereby developed an image-receiving element on the recording material that in Example 1 of U.S. Patent 3,445,228 and a rupturable container with the liquid necessary to develop the material became. The one from the recording material, the splittable container and the image-receiving member was then sandwiched by exerting pressure on the splittable container, as a result of which the developing liquid contained in this is set free was developed. A positive dye image of excellent quality was obtained in the image receiving element.

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Claims (9)

Patent claims 1. Process for making positive photographic images by image-appropriate exposure and development of a photographic Recording material with at least one light-sensitive silver halide emulsion layer, thereby marked τ draws that one 1} a recording material with at least one silver "halide emulsion layer, its silver halide grains Contain polyvalent metal ions included, exposed imagewise and that one 2) the exposed silver halide emulsion layer of the recording material either a) in the presence of a fogging agent in a silver halide surface developer developed, b) during development in a silver halide surface developer flash exposed or c) heated to a temperature of at least 100 ^° C. for at least 1 second and then developed in e: surface developer. 100 ⁰ C heated and then in a silver halide surface 2. The method according to claim 1, characterized in that one is a Recording material having at least one silver halide emulsion layer used, the silver halide grains contain lead ions or tri- or tetravalent metal ions included. 209839/1110 3. Process according to Claims 1 and 2, characterized in that a recording material having at least one silver halide emulsion layer is used used their silver halide grains in the presence of tri- or tetravalent metal ions in an acidic • Medium were created. 4. Process according to Claims 1 to 3, characterized in that a recording material having at least one silver halide emulsion layer is used whose silver halide grains were generated in the presence of iridium ions were used. 5. \ ferfahren according to claims 1 to 4, characterized in that a recording material having at least one silver halide emulsion layer used, the silver halide grains of which contain polyvalent metal ions included and those of the further contains at least one spectral sensitizing dye in a desensitizing concentration. 6. The method according to claims 1 to 5, characterized in that the exposed recording material in the presence of one from a hydrazine compound or a fogging agent consisting of an N-substituted quaternary cycloammonium salt. 7. The method according to claims 1 to 6, characterized in that a recording material is used in at least one in contact with the silver halide emulsion layer standing layer contains a lubricant. 8. Process according to Claims 1 to 6, characterized in that the exposed recording material is treated with a fogging agent containing silver halide surface developer developed. 209839/11 10 9. Process according to Claims 1 to 8, characterized in that there is a recording material with an image-receiving layer and a splittable container which, when pressure is applied, its contents consisting of a silver halide surface developer distributed between the silver halide emulsion layer and the image-receiving layer. 209839/1110