"Method for making direct positive images"

Field of the Invention

The present invention relates to a method for making direct-positive images by developing photographic light-sensitive silver halide materials in the presence of development nucleators that do not cause unevenness of development. The invention also relates to a photographic light-sensitive silver halide material for forming direct-positive images having a high maximum density.

In silver halide photography a photographic method, according to which a positive image is made without the use of a negative image or an intermediary process producing a negative image, is called a direct- positive method. A photographic light-sensitive material and a photographic emulsion for use according to such photographic method are called direct-positive material and direct-positive emulsion respectively.

A variety of direct-positive photographic methods are known. The most useful methods are the method, which comprises exposing prefogged silver halide grains to light in the presence of a desensitizing agent and developing them, and the method, which comprises subjecting a silver halide emulsion containing silver halide grains that have light-sensitive specks mainly inside the grains to an image-wise exposure and developing the exposed emulsion in the presence of a development nucleator. The present invention relates to the latter method. A silver halide emulsion comprising light-sensitive specks mainly inside the grains and which forms latent images mainly inside the grains is referred to as internal latent image-type silver halide emulsion, and thus is distinguished from silver halide grains that form latent images mainly at the surface of the grains.

It is known to develop a latent image that has been formed mainly inside the grains by means of a so-called internal developer, but the method, material, and emulsions used in accordance with the present invention are not concerned with that type of development, but rather with.the type of development using a so-called surface developer.

Description of the Prior art :

Methods for making a direct-positive image by development of an exposed internal latent image type-silver halide emulsion in the presence of a

development nucleator by means of a surface developer, and photographic emulsions and photographic light-sensitive materials used in such methods have been disclosed in i.a. GB-A 1,011,062, 1,151,363, 1,195,837, in JA Patent Publication No. 29,405/68, and in US-A 2,456,953, 2,497,875, 2,497,876, 2,588,982, 2,592,250, 2,675,318, 3,227,552, 3,761,276, 4,540,655. In the internal latent image-type method for making a direct- positive image, the development nucleator may be incorporated into a developing solution, but it is usually incorporated into the photographic emulsion layer or in another layer of the photographic light-sensitive material. Development nucleators that can be used in the above-described method for making a direct-positive image include hydrazine and derivatives thereof as described in i.a. "Zeitschrift fur Wissenschaftliche Photographie" by Arens, vol. 48, (1953) p.48, DE-A 3,021,423, and in US-A 2,563,785, 2,588,982, 3,227,552, 4,245,037, 4,374,923, 4,540,655 , in Research Disclosure 23,510, p. 346-348 and the documents referred to therein.

However, many of the known development nucleators have disadvantages. Part of them lead to a relatively low maximum density, others have to be used in high concentrations so that there may be migration to the developer and in consequence thereof may cause unevenness of development.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a method for making direct-positive images by developing photographic light-sensitive silver halide materials in the presence of development nucleators that do not cause unevenness of development.

It is another object of the present invention to provide a photographic light-sensitive silver halide material for forming direct-positive images having a high maximum density. It is a further object of the present invention to provide novel development nucleators.

Other objects of the present invention will become apparent from the description hereinafter.

It has been found now that the above objects are accomplished by a method for making direct-positive images comprising image-wise exposing a photographic light-sensitive silver halide material comprising a support and at least one internal latent image-type silver halide emulsion layer, and developing said exposed photographic material in a surface developer in the

presence of development-nucleating amounts of at least one pyrazol idin-3- one-l-yl-phenyl-substituted hydrazine compound.

Pyrazol idin-3-one-l-yl-phenyl-substituted hydrazine compounds that can be used advantageously in accordance with the present invention correspond to one of the general formulae I and II :

PYR - LINK - G - NH - NH - CO - (C0) _χ - R' (I)

PYR - CO - NH - NH - Ar (II)

wherein :

PYR stands for a monovalent pyrazol idin-3-one-l-yl-phenyl group or a monovalent substituted pyrazol idin-3-one-l-yl-phenyl group, LINK stands for a linking member, which can be a chemical bond, a polyvalent atom e.g.-O- and -S-, or a polyvalent atom group e.g. -NH, -CO-, -S0 ₂ -, -S0 ₂ -NH-, -NH-S0 ₂ -NH-, -NH-C0-NH- _. -C0-NH-, and -NH-C0-, G stands for a bivalent organic group (which can be substituted or unsubstituted) containing at least one homocyclic or heterocyclic aromatic nucleus, e.g. one phenylene group or substituted phenylene group or at least two phenylene groups or substituted phenylene groups that are linked to each other by a chemical bond, a bivalent atom e.g. -0- and -S-, or by a bridging group e.g. -S0 ₂ -, -N(R ¹ )-, -S0 ₂ -N(R ¹ )-, -N(R ¹ )-S0 ₂ -, -N(R ¹ )"S0 ₂ -N(R ² )-, -..(R^-CO-, -C0-N(R ¹ )-, -N(R ¹ )-C0-N(R ² )-, -(CH ₂ ) _y -, and

(CH ₂ ) _y -Q-(CH ₂ ) _z -, wherein each of R ¹ and R ² (same or different) represents hydrogen, a C1-C4 alkyl group e.g. methyl, or an aryl group e.g. phenyl, Q represents a bivalent atom e.g. -0- or -S-, and each of y and z may represent a positive integer from 1 to 5, x is 0 or 1,

R' stands for hydrogen or a monovalent group selected from the group consisting of an alkyl group, a substituted alkyl. group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, an aryloxy group, a substituted aryloxy group, an amino group, a substituted amino group, a heterocyclyl group, and a substituted

heterocyclyl group, and Ar stands for a homocyclic or heterocyclic aromatic nucleus e.g. a phenyl group or a substituted phenyl group, which nucleus may carry one or more substituents (same or different) e.g. chosen from the group consisting of an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, a heterocyclyl group a substituted heterocyclyl group, an alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an aryloxy group, a substituted aryloxy group-, an arylthio group, a substituted arylthio group, an amino group, a substituted amino group, cyano, a halogen atom e.g. chloro and bromo, carboxy, carbamoyl , a substituted carbamoyl group, hydroxy, nitro, sulpho, sulpha oyl, and a substituted sulphamoyl group. The present invention also provides a photographic light-sensitive silver halide material for forming direct-positive images, said material comprising a support and in at least one light-sensitive emulsion layer comprising unfogged internal latent image-type silver halide grains dispersed in a hydrophilic colloid binder and/or in a hydrophilic colloid layer in water- permeable relationship with said emulsion layer, development-nucleating amounts of at least one hydrazine, characterized in that said hydrazine corresponds to one of the above defined general formulae I and II . The present invention further provides as novel compounds pyrazol idin-3- one-l-yl-phenyl-substituted hydrazines corresponding to the above general formulae I and II.

DETAILED DESCRIPTION OF THE INVENTION

It has been established that by developing in a surface developer in the presence of development nucleators according to the present invention exposed photographic light-sensitive silver halide materials comprising an internal latent image, direct-positive images having a high maximum density can be obtained. This is especially surprising when for said development use is made of a hydroquinone surface-type developer that has a pH not higher than 12.0. A pH not higher than 12 is desirable indeed, since higher values lead i.a. to an accelerated deterioration of the developer.

In the general formulae I and II the group PYR standing for a monovalent pyrazol idin-3-one-l-yl-phenyl group preferably corresponds to the following general formul III :

wherein each of R ³ , R ⁴ , R ⁵ , and R ⁶ (same or different) represents hydrogen, an alkyl group e.g. methyl, or a substituted alkyl group e.g. hydroxymethyl . The phenyl group in general formula III may carry one or more monovalent substituents, which may be same or different and can be chosen i.a. from the group consisting of an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, an aryloxy group, and a substituted aryloxy group.

In general formula I the symbol G stands for a bivalent organic group containing at least one homocyclic or heterocyclic aromatic nucleus, e.g. one phenylene group or substituted phenylene group or at least two phenylene groups or substituted phenylene groups that are linked to each other as defined above. The at least one aromatic nucleus may carry one or more substituents (same or different) such as e.g. an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, a heterocyclyl group a substituted heterocyclyl group, an alkoxy group, a substituted alkoxy group, an alkylthio group, a substituted alkylthio group, an aryloxy group, a substituted aryloxy group, an arylthio group, a substituted arylthio group, an amino group, a substituted amino group, cyano, a halogen atom e.g. chloro and bromo, carboxy, carbamoyl, a substituted carbamoyl group, hydroxy, nitro, sulpho, sulphamoyl, and a substituted sulphamoyl group.

The hydrazines corresponding to the general formulae I and II are believed to be novel compounds and the present invention therefore also includes such

compounds per se.

Representatives of development nucleators according to the present invention are the following compounds corresponding to the general formulae I or II :

- CONH - " NH - NHCOCH3 (D03)

" CONH - { O ) - NH - NHCO-H (D04)

- CONH - " NH - NHCO-H (D05)

- CONH NH - NHCO-H (D07)

The pyrazol idin-3-one-l-yl-phenyl-substituted hydrazine compounds corresponding to the general formulae I and II can be synthesized very easily. The following reaction scheme and preparation example describe the synthesis of compound D01 and are representative of the preparation of other development nucleators corresponding to the general formula II :

-CH.

starting compound (a) intermediate compound (a)

intermediate compound (a) + -NH-NH_ ^■ & D01

Preparation of D01

Intermediate compound (a) :

A solution of 25 ml (0.24 mol) of acetylacetone in 24 ml of ethanol is added dropwise with stirring to a cooled (5°C) suspension of 49.6 g (0.2 mol of starting compound (a) in 240 ml of ethanol and 27 ml of 5N hydrochloric acid. After 2 h of stirring of the mixture on an icebath a solution has formed. The solution is kept overnight at room temperature so that a precipitate forms. The precipitate is filtered with suction, rinsed first with water and

next with ethanol, and dried over phosphorus pentoxide under reduced pressure.

Yield : 58 g of intermediate compound (a) melting at 168°C.

D01 :

A solution of 11.9 g (0.11 mol) of phenylhydrazine in 22 ml of acetic acid is added dropwise at room temperature to a solution of 31.2 g (0.1 mol) of intermediate compound (a) in 160 ml of acetic acid. After 10 min the reaction mixture is heated to 50 ^β C for 6 h. The precipitate is filtered with suction at room temperature, stirred with 125 ml of methanol, filtered with suction again, and dried. Yield : 29.2 g of D01 melting at 275°C.

The following reaction scheme and preparation example describe the synthesis of compound D04 and are representative of the preparation of other development nucleators corresponding to the general formula I :

starting compound (b) starting compound (c)

Starting compound (b) can be prepared as described in EP-A 0,196,705, whereas starting compound (c) can be prepared as described in DE-A 3,209,110.

Preparation of D04

An amount of 121.5 g (0.75 mol) of l,l'-carbonyldiimidazole (CDI) is added to a solution of 175.5 g (0.75 mol) of starting compound (b) in 990 ml of dimethylforma ide. The resulting reaction mixture is stirred for 24 h at ambient temperature under nitrogen atmosphere. Next, 113.2 g (0.75 mol) of starting compound (c) is added. The reaction mixture is stirred for 4 h and then poured out into water. The precipitate is separated by filtration, rinsed with 21 of methanol, and dried. Yield : 156 g of compound D04 melting at 263"C.

The at least one hydrazine development nucleator used in accordance with the present invention may be incorporated into the developer or in a prebath applied to the exposed photographic material before development thereof. Preferably, however, the at least one development nucleator is incorporated into the silver halide emulsion layer or into a hydrophilic colloid layer in water-permeable relationship therewith.

Mixtures of at least 2 of the above-mentioned development nucleators can be used advantageously.

As mentioned before, nucleating amounts of the development nucleators are present during development of the image-wise exposed photographic material and can be incorporated for that purpose e.g. into the light-sensitive silver halide emulsion layer or into a hydrophilic colloid layer in water-permeable relationship therewith. Alternatively, they can also be added to the developer or to a separate bath. When used in the silver halide emulsion layer the development nucleators are present in a concentration of 10 ^' ^ to 10 ^"1 mol per mol of silver halide.

Prior to the coating of the composition that will form the photographic layer comprising at least one development nucleator, the development nucleator(s) can be dissolved in an organic solvent and added to said composition. For instance, 1.3 x 10~ ³ mol of the development nucleator is added in the form of a 3.5 % solution in N-methyl-pyrrol idone per mol of silver.

According to a preferred embodiment the development nucleator(s) are added in dispersed form to the hydrophilic colloid composition that will form said emulsion layer or said hydrophilic colloid layer. When these hydrazines are present in dispersed form in a hydrophilic colloid layer, preferably in the internal latent image-type silver halide emulsion layer, the direct-positive images obtained upon development have a very fine grain.

The development nucleator(s) can be incorporated into the hydrophilic colloid composition that will form said emulsion layer or said hydrophilic colloid layer by dissolving them first in at least one water-immiscible, oil-type solvent or oil-former, adding the resulting solution to an aqueous phase containing a hydrophilic colloid preferably gelatin and a dispersing agent, passing the mixture through a homogenizing apparatus so that a dispersion of the oily solution in an aqueous medium is formed, mixing the dispersion with a hydrophilic colloid composition e.g. a gelatin silver ha ide emulsion, and coating the resulting composition in the usual manner to produce a system in which particles of development nucleator(s), surrounded

by an oily membrane, are distributed throughout the gel matrix. The dissolution of the development nucleator(s) in the oil-former may be facilitated by the use of an auxiliary low-boiling water-immiscible solvent, which is removed afterwards by evaporation. The development nucleator(s) can be dispersed in hydrophilic colloid compositions with the aid of at least one known oil-former e.g. an alkyl ester of phthalic acid. The oil-formers can be used in widely varying concentrations e.g. in amounts ranging from about 0.1 to about 10 parts by weight and preferably from 0.5 to 2 parts by weight relative to the amount of the development nucleator(s) dispersed therewith.

It may be useful to combine the oil-former with at least one auxiliary solvent that is insoluble or almost insoluble in water and has a boiling point of at most 15θ"C, such as a lower alkyl acetate e.g. ethyl acetate. According to another embodiment of the present invention the development nucleator(s) are incorporated into the hydrophilic colloid composition that will form said silver halide emulsion layer or said hydrophilic colloid layer by mixing the development nucleator(s) in the absence of an oil-former and a solvent with an aqueous hydrophilic colloid solution, preferably an aqueous gelatin solution, passing the resulting mixture through a homogenizing apparatus, adding the dispersion obtained to said hydrophilic colloid composition that will form said emulsion layer or said hydrophilic colloid layer, and coating said hydrophilic colloid composition on a support.

The homogenizing apparatus can be any of the devices currently used for making dispersions e.g. an ultrasonic power generator, a mill such as a ball mill, a sand mill, and a colloid mill.

In the photographic light-sensitive direct-positive material according to the present invention the development nucleator(s) is(are) preferably present in the internal latent image-type silver halide emulsion layer. However, the development nucleator(s) can also be incorporated into a hydrophilic colloid layer that stands in water-permeable relationship with the internal latent image-type silver halide emulsion layer e.g. in a protective hydrophilic colloid layer having a thickness in dry state of 1 to 3 pm. The hydrophilic colloid layer can be any layer that makes part of the photographic light-sensitive direct-positive material according to the present invention. It can thus be i.a. a light-sensitive layer, an intermediate layer, a filter layer, a protective layer, an antihalation layer, an antistress layer, a subbing layer, or any other layer. In other words, any layer will do provided the development nucleator(s) is(are) not prevented from diffusing to

the internal latent image-type silver halide emulsion layer.

The development nucleator(s) used according to the present invention preferably is (are) incorporated into the layer(s) in an amount that yields satisfactory maximum density values of e.g. at least 1.50 when the internal latent image-type emulsion is developed with a surface- developing solution. The amount may vary within wide limits and depends upon the nature of the silver halide emulsion, the chemical structure of the development nucleator(s), and on the developing conditions. Nevertheless, an amount of from about 0.01 to about 15 mmol per mol of silver halide in the internal latent image-type silver halide emulsion is generally effective, more preferably an amount of from about 0.1 to about 9 mmol per mol of silver halide. When the development nucleator(s) is(are) incorporated into a hydrophilic colloid layer that stands in water-permeable relationship with the internal latent image-type silver halide emulsion layer, it is adequate to incorporate the development nucleator(s) in the above amounts while taking into account the amount of silver contained in the associated internal latent image-type emulsion layer.

An internal latent image-type silver halide emulsion is an emulsion, the maximum density of which obtained when developing it with an "internal type" developing solution exceeds the maximum density that is achievable when developing it with a "surface-type" developing solution.

Internal latent image-type silver halide emulsions that can be used in accordance with the present invention have been described in e.g. US-A 2,592,250, 3,206,313, 3,271,157, 3,447,927, 3,511,662, 3,737,313, 3,761,276, GB-A 1,027,146, and JA Patent Publication No. 34,213/77. However, the silver halide emulsions used in the present invention are not limited to the silver halide emulsions described in these documents.

The internal latent image-type silver halide emulsions that are suited for use according to the present invention are emulsions that have not been prefogged externally and that have either been ripened chemically or not.

The photographic emulsions can be prepared according to different methods as described e.g. by P. Glafkides in "Chimie et Physique. hotographique", Paul Monte! , Paris (1967), by G.F. Duffin in "Photographic Emulsion Chemistry", The Focal Press, London (1966), and by V.L. Zelik an et al in "Making and Coating Photographic Emulsion", The Focal Press, London (1966). The photographic silver halide emulsions used according to the present invention can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations,

sequence of addition, and rates of addition. The silver halide can be precipitated according to the single-jet method, the double-jet method, or the conversion method. The conversion method has proved to be particularly suitable. According to this method a more soluble silver halide is converted into a less soluble silver halide. For instance a silver chloride emulsion is converted in the presence of water-soluble bromide and possibly iodide, the amounts of which are selected with regard to the finally required composition, into a silver chlorobromoiodide or a silver bromoiodide emulsion. This conversion is preferably carried out very slowly in several consecutive steps i.e. by converting a part of the more soluble silver halide at a time. Another technique by which emulsions with an increased internal latent image sensitivity can be prepared has been described in GB-A 1,011,062.

The silver halide particles of he photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms. The silver halide grains may have a multilayered grain structure.

According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes. Besides having a • differently composed core and shell the silver halide grains may also comprise different phases inbetween.

Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in the method of the present invention.

The average size of the silver halide grains may range from 0.1 to 2.0 urn, preferably from 0.15 to 0.8 μm.

The size distribution of the silver halide particles of the photographic emulsions used according to the present invention can be.homodisperse or heterodisperse. A homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.

In addition to silver halide the emulsions may also comprise organic silver salts such as e.g. silver benzotriazolate and silver behenate.

The silver halide crystals can be doped with Rh ³⁺ , Ir ⁺ , Cd ²⁺ , Zn ²⁺ , Pb ²⁺ .

The emulsion can be left unwashed or it can be desalted in the usual ways e.g. by dialysis, by flocculation and re-dispersing, or by ultrafiltration.

Chemical sensitization can be performed as described i.a. in the above- mentioned "Chimie et Physique Photographique" by P. Glafkides, in the above-mentioned "Photographic Emulsion Chemistry" by G.F. Duffin, in the above-mentioned "Making and Coating Photographic Emulsion" by V.L. Zelik an et al, and in "Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden" edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968). As described in said literature chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines. The emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds. Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au. One of these chemical sensitization methods or a combination thereof can be used.

The spectral photosensitivity of the silver halide can be adjusted by proper sensitization to any desired spectral range comprised between 300 and 900 nm e.g. to blue light of relatively long wavelengths, to green light, to red light, to infrared light, by means of the usual mono- or polymethine dyes such as acidic or basic cyanines, hemicyanines, oxonols, hemioxonols, styryl dyes or others, also tri- or polynuclear ethine dyes e.g. rhodacyanines or neocyanines. Such spectral sensitizers have been described by e.g. F.M. Hamer in "The Cyanine Dyes and Related Compounds" (1964) Interscience Publishers, John Wiley & Sons, New York. The spectral photosensitivity of the silver halide can also be adjusted for exposure by laser light e.g. helium-neon laser light, argon laser light, and solid state laser light. Dyes that can be used for adjusting the photosensitivity to laser light have been described in i.a. JA-A 62284344, 62284345, 62141561, 62103649, 62139555, 62105147, 62105148, 62075638, 62062353, 62062354, 62062355, 62157027, 62157028, 62113148,- 61203446, 62003250, 60061752, 55070834, 51115821, 51115822, 51106422, 51106423, 51106425; DE-A 3,826,700; US-A 4,501,811, 4,725,532, 4,784,933; GB-A 1,467,638; and EP-A 100,654 and in documents cited therein. The silver halide can also be sensitized with dyes providing a spectral sensitivity mainly in the range of 400 to 540 nm and not extending the sensitivity substantially beyond 540 nm so that the resulting

photosensitive material can be handled in safe-light conditions prior to the image-wise exposure. Suitable dyes that can be used for that purpose have been described in e.g. US-A 4,686,170.

Other useful sensitizing dyes that can be employed in accordance with the present invention have been described in e.g. US-A 2,503,776, 2,526,632,

3,522,052, 3,556,800, 3,567,458, 3,615,613, 3,615,632, 3,615,635, 3,615,638, 3,615,643, 3,617,293, 3,619,197, 3,625,698, 3,628,964, 3,632,349, 3,666,480, 3,667,960, 3,672,897, 3,677,765, 3,679,428, 3,703,377, 3,705,809, 3,713,828, 3,713,828, 3,745,014, 3,769,025, 3,769,026, 3,770,440, 3,770,449, GB-A 1,404,511, and BE-A 691,807.

The sensitizing dyes employed in the present invention are used in a concentration almost equivalent to that used in ordinary negative silver halide emulsions. In particular, it is advantageous that the sensitizing dyes be employed in a dye concentration to a degree that does not substantially cause desensitization in the region of intrinsic sensitivity of the silver halide emulsion.

Other dyes, which per se do not have any spectral sensitization activity, or certain other compounds, which do not substantially absorb visible radiation, can have a supersensitization effect when they are incorporated together with said spectral sensitizing agents into the emulsion. Suitable supersensitizers are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US-A 3,743,510, cadmium salts, and azaindene compounds.

Density-increasing compounds may be incorporated into the photographic light-sensitive direct-positive silver halide material, preferably into an internal latent image-type silver halide emulsion layer thereof, although they may be incorporated also into a hydrophilic colloid layer that stands in water-permeable relationship with the internal latent image-type silver halide emulsion layer e.g. in said protective hydrophilic colloid layer comprising at least 1 g of hydrophilic colloid per m2.

Suitable density-increasing compounds are formic acid, oxalic acid, glyoxylic acid, or salts of these, and polyethylene glycols. When incorporated into the photographic element the density-increasing compound is present in amounts of from 4 to 600 mg/m2, preferably from 40 to 300 mg/m2. When the density-increasing compound is incorporated into a hydrophilic

colloid layer it is present therein in the form of a salt e.g. sodium or potassium formiate or oxalate.

It is also possible to incorporate the density-increasing compound into a hydrophilic colloid layer that does not stand in direct water-permeable relationship with the internal latent image-type silver halide emulsion layer e.g. because an impermeable support constitutes a barrier between said emulsion layer and said hydrophilic colloid layer. In that case the density-increasing compound can during treatment of the exposed material with a developing solution or a prebath diffuse via said developing solution or said prebath towards the silver halide emulsion layer and have its effect there. Such layers are e.g. layers that have been coated on the rear side of the support and which may serve different purposes. Examples of such layers are e.g. a back layer, an anti-curling layer, and an antistatic layer. The density-increasing compound may also be added to the developing solution in amounts of from 0.2 to 30 g/1, preferably from 1 to 10 g/1. The density-increasing compound may also be added to another processing solution e.g. a prebath. When the density-increasing compound is added to the developing solution or to a prebath it is present therein in acid form or in the form of a salt. A preferred density-increasing compound is oxalic acid, because it has the highest density-increasing effect and can thus be used in lower concentrations.

For processing the photographic material of the present invention any of the known methods can be employed. Specifically, the processing method used according to the present invention basically includes a development step and a fixing step. A stopping step and a rinsing step can be included as well, if desired. The processing temperature is usually selected within the range of from 18 ^° C to 50°C. However, temperatures lower than 18°C and temperatures higher than 50 ^° C can be employed, if desired. The processing time may vary within broad ranges provided the mechanical strength of the materials to be processed is r~>t adversely influenced and no decomposition takes place.

The develo, g solution used for developing an exposed, photographic material in accordance with the present invention may comprise at least one alkanolamine, which may be chosen from primary, secondary, and tertiary alkanolamines. Suitable alkanolamines are i.a. N,N,N-triethanolamine,

2-amino-2-hydroxymethyl-propan-l,3-diol, N-methyl-diethanolamine, N-ethyl- diethanolamine, diisopropanolamine, N,N-diethanol-amine, 3,3'-amino- dipropanol , 2-amino-2-methyl-propan-l,3-diol , N-propyl-diethanolamine,

N-butyl-diethanolamine, N,N-dimethyl-ethanola ine, N,N-diethyl-ethanolamine, N,N-diethyl-isopropanolamine, l-amino-propan-2-ol, N-ethanolamine, N-methyl-ethanolamine, N-ethyl-ethanolamine, N-ethyl-propanolamine, 3-amino-propanol , 3-dimethylamino-propanol , 4-amino-butanol, and 5-amino-pentan-l-ol .

The alkanolamine or a mixture of alkanolamines may be present in the developing solution in amounts of from 1 to 100 g/1, preferably 10 to 60 g/1.

In the developing solution used in the method of the present invention, a hydroquinone alone or a combination of a hydroquinone with a secondary developing agent of the class of l-phenyl-3-pyrazolidinone compounds and p-N-methyl-aminophenol can be used as developing agent. Specific examples of hydroquinones include hydroquinone, methylhydroquinone, t-butyl-hydroquinone, chloro-hydroquinone, and bromohydroquinone.

Particularly useful l-phenyl-3-pyrazolidinone developing agents that can be used in combination with a hydroquinone are l-phenyl-3-pyrazol idinone, 1-phenyl-4-methyl-3-pyrazol idinone, 1-phenyl-4-ethyl-5-methyl-3- pyrazol idinone, 1-phenyl-4,4-dimethyl-3-pyrazol idinone, and 1-phenyl- 4- hydroxymethyl-4-methyl-3-pyrazol idinone.

N-methyl-p-aminophenol and 2,4-diaminophenol can be used in combination with a hydroquinone as a developing agent.

When the secondary developing agent used in the processing method of the present invention is one of the class of the l-phenyl-3-pyrazol idinone compounds it is preferably present in an amount of 2 to 20 g per litre. When the secondary developing agent is p-N-methyl-aminophenol it is preferably present in an amount of 10 to 40 g per litre.

The developing solution comprises a preservative such as a sulphite e.g. sodium sulphite in an amount ranging from 45 g to 160 g per litre.

The developing solution comprises alkali-providing substances such as hydroxides of sodium and potassium, alkali metal salts of phosphoric acid and/or silicic acid e.g. trisodium phosphate, orthosilicates, metasilicates, hydrodisil icates of sodium or potassium, and sodium carbonate. The alkali- providing substances can be substituted in part or wholly by alkanolamines.

The developing solution may comprise a buffering agent such as e.g. sodium or potassium carbonate, trisodium phosphate, and sodium metaborate. For the purpose of decreasing the formation of fog (Dmin) the developing solution may further contain an inorganic anti-fogging agent such as a bromide e.g. potassium bromide and/or an organic anti-fogging agent such as a benzimidazole e.g. 5-nitro-benzimidazole, a benzotriazole like benzotriazole

itself and 5-methyl-benzotriazole.

The developing solution may contain other ingredients such as i.a. toning agents, development accelerators, oxidation preservatives, surface-active agents, defoaming agents, water-softeners, anti-sludge agents, hardeners including latent hardeners, and viscosity-adjusting agents.

Regeneration of the developing solution according to known methods is, of course, possible.

The development may be stopped - though this is often not necessary - with an aqueous solution having a low pH. An aqueous solution having a pH not higher than 3.5 comprising e.g. acetic acid and sulphuric acid, and containing a buffering agent is preferred.

Buffered stop bath compositions comprising a mixture of sodium dihydrogen orthophosphate and disodium hydrogen orthophosphate are preferred.

Conventional fixing solutions may be used. Examples of useful fixing agents include organic sulphur compounds known as fixing agents, as well as a thiosulphate, a thiocyanate, etc. The fixing solution may contain a water-soluble aluminium salt as a hardening agent.

The stopping solution may be an aqueous solution having a low pH. An aqueous solution having a pH not higher than 3.5 comprising e.g. acetic acid and sulphuric acid, and containing a buffering agent is preferred. Suitable additives for improving the dimensional stability of the photographic material can also be incorporated therein together with the hydrophilic colloid binder of the silver halide emulsion. Suitable examples of this type of compounds include i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.

Various compounds can be added to the photographic emulsion to prevent the reduction in sensitivity or fog formation during preparation, storage, or processing of the photographic material. A great many compounds are known for these purposes, and they include homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulphonium mercury double salts and other mercury compounds. Other suitable stabilizers are azaindenes, preferably tetra- or penta- azaindenes, especially those substituted with hydroxy or amino groups e.g.

4-hydroxy-6-methyl- l,3,3a,7-tetra-azaindene . Compounds of this kind have been described by Birr in Z. Wiss. Photogr. Photophys. Photochem. 47, 2-27 (1952). Other suitable stabi izers are i.a. heterocyclic mercapto compounds e.g. l-phenyl-5-mercaptotetrazole, 3-methyl-benzothiazole, quaternary benzothiazole derivatives, benzotriazole. Specific examples of stabilizers have been mentioned by K. Mees in The Theory of the Photographic Process, 3rd ed. 1966 by reference to the papers that first reported such compounds.

The silver halide emulsions may comprise other ingredients e.g. development accelerators, wetting agents, and hardeners. The hydrophilic colloid binder of the silver halide emulsion layer and/or of other hydrophilic colloid layers can, especially when the binder used is gelatin, be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl- 2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g. 2,3- dihydroxy-dioxan, active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro- s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid. These hardeners can be used alone or in combination. The binders can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts and the phosphorus compounds described in EP Application N° 90201850.6, which corresponds to the U.S.Serial N°

The photographic light-sensitive direct-positive material of the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for other various purposes such as for the prevention of irradiation or anti-halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Of these, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful. When a hydrophilic colloid layer of the photographic light-sensitive direct-positive material of the present invention contains a dye or an UV-absorbing agent, these compounds may be mordanted by means of a cationic polymer e.g. polymers described in GB-A 1,468,460 and 685,475, US-A 2,675,316, 2,839,401, 2,882,156, 3,048,487, 3,184,309, 3,445,231, and 3,986,875, DE-A 1,914,362.

The photographic light-sensitive direct-positive material of the present invention may comprise various kinds of surface-active agents or plasticizers in the photographic emulsion layer or in at least one other hydrophilic

colloid ^" 'ayer. Suitable surface-active agents or plasticizers include non-ionic agents such as aponins, alkylene oxides e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring-containing phosphonium or sulphonium salts. Such surface-active agents or plasticizers can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast and development acceleration. Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A 3,038,805, 4,038,075, and 4,292,400.

The photographic light-sensitive direct-positive material of the present invention may further comprise various other additives such as e.g. UV-absorbers, matting agents or spacing agents, and lubricants.

Suitable UV-absorbers are i.a. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-A 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-A 3,700,455.

Suitable spacing agents are e.g. finely divided silica particles and polymer beads as described US-A 4,614,708. In general, the average particle size of spacing agents is comprised between 0.2 and 10 urn. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic material, whereas alkali-soluble spacing agents usually are

removed therefrom in an alkaline processing bath. Suitable spacing agents can be made i.a. of polymethyl ethacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropy!methyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.

A matting agent and/or a lubricant may be added to an emulsion layer and/or the protective hydrophilic colloid layer of the photographic light-sensitive direct-positive material of the present invention. Suitable matting agents are e.g. water-dispersible vinyl polymers such as poly(methyl methacrylate) having an appropriate particle size of from 0.2 to 6 pi and inorganic compounds e.g. silver halide and strontium barium sulphate. The lubricant is used to improve the slidability of the photographic material. Suitable examples of lubricants are e.g. liquid paraffin, waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, silicones such as polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes and alkyleneoxide addition derivatives thereof.

The protective hydrophilic colloid layer of the photographic light-sensitive direct-positive material of the present invention preferably is a gelatin layer that also comprises silica as spacing agent and one of the above-mentioned plasticizers.

A variety of photographic supports can be employed for the photographic light-sensitive direct-positive material of the present invention. The silver halide emulsion can be coated onto one side or both sides of the support. Suitable supports are e.g. cellulose acetate films such as cellulose triacetate film and cellulose diacetate film, cellulose nitrate films, polyethylene terephthalate films, and polystyrene films.

In the first step for making a direct-positive image according to the method of the present invention the photographic light-sensitive direct- positive material is exposed image-wise. This exposure can either be a high-intensity exposure such as a flash exposure or a normal intensity exposure such as a daylight exposure, a low-intensity exposure such as an exposure by means of a printer, or an exposure of even lower intensity. The light source used for the exposure should match the wavelength sensitivity of the light-sensitive material. Natural light (sunlight), the light emitted by an incandescent lamp, a halogen lamp, a mercury vapour lamp, a fluorescent tube, an electronic flash lamp, or by a metal-burning flash bulb can be used. Gas-, dye- or semiconductor lasers emitting light in the wavelength ranges from ultraviolet to infrared as well as a plasma light source are also

suitable light sources for exposing the photographic light-sensitive silver halide material for use in the method of the present invention. A line-shaped light source or a planar light source as well as a microshatter arrangement with a fluorescing area (CRT, etc.), the fluorescence of which is produced by fluorescing substances stimulated by means of electron rays, or even a liquid-crystal display (LCD) or a lanthanum-doped lead-titanium zirconate (PLZT) can be used as well as light sources for exposing the photographic light-sensitive silver halide material for use in the method of the present invention. If necessary, the spectral distribution of the exposure light can be controlled by means of a colour filter.

In a second step for making a direct-positive image the image-wise exposed silver halide material is soaked with, e.g. immersed in, a developing solution. For instance, the image-wise exposed silver halide material is conducted through a tray containing a developing solution. The developing agents may be incorporated partially or completely into the photographic light-sensitive silver halide material. They may be incorporated during the preparation stage of the material or at a later stage by means of a processing liquid with which the photographic material is wet prior to the development of the direct-positive image. In this way the surface developer can be reduced to a mere alkaline liquid that is substantially free from developing agents. Such an alkaline aqueous liquid, often called "activator" offers the advantage of having a longer activity i.e. of being less rapidly exhausted. The preliminary processing liquid may contain at least a part of the development nucleator and may also contain other ingredients that otherwise would have been incorporated into the developing solution. Wetting of the photographic material by means of a processing liquid comprising development nucleator and/or density-increasing compound may be performed according to any conventional method such as by soaking or by moistening one single side of the material e.g. by means of a lick roller, by spreading a paste e.g. contained in a pod, or by spraying.

The photographic light-sensitive silver halide material used in the method of the present invention may serve different purposes. Application fields, in which direct-positive images can be made in accordance with the present invention, are i.a. graphic arts recording processes, silver salt diffusion transfer reversal processes, microfilm recording processes, duplicating processes for cinematographic black-and-white negatives, laser recording processes, cathode-ray recording processes, fototype-setting processes, etc. The present invention will be explained in greater detail by reference to

the following example. The present invention should, however, not be construed as being limited thereto.

EXAMPLE

An internal latent image-type direct-positive gelatin silver bromide emulsion was prepared by simultaneously adding equal molar solutions of potassium bromide ans silver nitrate to a stirred aqueous gelatin solution containing 10.2 mg of Na IrClg.6H 0. The precipitation of silver bromide was first performed at 7θ"C in acidic medium (pH = 4) at a pAg of 6.8 consuming 15% of the total amount of silver present and next continued at a pAg of 9.2 consuming 35% of the total amount of silver present.

The silver bromide grains obtained were sensitized chemically by addition thereto of 0.64 mg of sodium thϊosulphate, 2.4 mg of HAuU .4H ₂ 0, and 4.8 mg of ammonium thiocyanate in 90 min at 70°C.

Growth of the chemically sensitized grains was allowed to continue in the same precipitation environment (pAg = 9.2) so that at the end octahedral grains of 0.3 urn (average grain size 0.15 urn) were obtained.

The resulting emulsion was surface-sensitized by addition thereto at pH 5.2 of 0.64 mg of sodium thiosulphate, 0.3 mg of HAuCl .4H ₂ 0, and 0.6 mg of ammonium thiocyanate and heating for 120 min at 50°C.

First, an amount of 167 mg of potassium iodide was added per mol of silver halide (expressed as silver nitrate) and next 459 mg of the spectral sensitizing dye corresponding to the following structural formula (S01) was added per mol of silver halide :

Furthermore, 148 mg of 4-hydroxy-6-methyl-l,3,3a,7-tetraazaindene and 1.1 x 10 ^"3 mol of development nucleator as identified in Table 1 hereinafter were added per mol of silver halide.

The emulsion obtained was coated on a polyethylene terephthalate film support at a silver coverage of 6 mg/m2 and a gelatin coverage of 3 g/m2.

Each emulsion coating was exposed for 10 ^"2 s to flashlight of a EG&G sensitometer Mark VII, sold by EG&G Ing, 45 William street, Wellesley, Ma.02181, USA, through a U525 filter. Each coating was processed at 35°C for 30 s in a developing bath containing the following ingredients and having its pH-value adjusted by addition of sodium hydroxide to the value listed for each coating in Table 1 hereinafter:

demineral ized water 500 ml ethylenediamine tetraacetic acid tetrasodium salt 1 g sodium carbonate 40 g sodium sulphite 70 g hydroquinone 40 g

4-hydroxyr.ethyl-4'-methyl-3-pyrazol idinone 0.4 g sodium bromide 3 g

5-methyl-benzotriazole 0.4 g diethylaminoethanol 40 g

The Dmin and Dmax values were measured and are listed in Table 1.

TABLE 1

Dmin Dmax

The above results show that high Dmax values can be obtained according to the method of the present invention, even so when the developing bath has a pH-value lower than 12. No unevenness of development was observed in any of the developed coatings.