JPH09166837A - Multilayered silver halide photograph material and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make image tones adequate. SOLUTION: This material includes multilayered compsns. of at least two layers of negative image type silver halide emulsions adjacent to each other on at least one side of a base. In such a case, the emulsion layers nearer to the base contain at least one of the emulsions having the planer emulsion crystals selected from the group consisting of a silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodide, silver bromide and silver bromoiodide having 111} habits and a silver chloride, silver chlorobromide, silver chloroiodide and silver chlorobromoiodide having 100} habits and the adjacent layers furtherer from the base contain at least one of the emulsions having substantial cubic emulsion crystals selected from the silver chloride, silver chlorobromide and silver bromide. The material is so formed that the halide compsns. of the cubic emulsion crystals or the planar emulsion crystals or both contain the chloride.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a light-sensitive silver halide photographic material having a multilayer composition of light-sensitive silver halide emulsion layers containing a negative image type tabular grain emulsion, and a method for producing the material.

[0002]

BACKGROUND OF THE INVENTION Photosensitive silver halide photographic materials containing silver halide emulsion layers with negative-working tabular grain emulsions have become increasingly important in the last decade.

Tabular silver halide grains are crystals having two parallel faces, which have at least a ratio between the diameter of a circle having the same area as these faces and the thickness, which is the distance between the two principal faces. It is 2.

Tabular grains have long been known in the photographic art. 1961 Berry et al. Photograp
Hic Science and Engineering, Vol 5, No. 6 describes the growth and production method of tabular silver bromoiodide grains. For tabular grains, see Duffin, Photographic E
mulsion Chemistry, Focal Press, 1966, 66
-See page 72. Early patent documents include US of Bogg
-A4063951, Lewis US-A40667739.
And Maternaghan, US-A 4150994; 418.
4877 and 4184878 are included. However, the tabular grains described therein cannot be regarded as exhibiting a high diameter to thickness ratio, commonly referred to as the aspect ratio. Some of the US patent applications filed in 1981 and issued in 1984 describe tabular grains with high aspect ratios and their advantages in photographic applications. Also from Wilgus US-A4434
226 is less than 0.2 μm thick, at least 0.6 μm
And an average aspect ratio greater than 8: 1 (these are at least 5 of the total projected area of all emulsion grains).
Tabular silver bromoiodide grains are disclosed. Kofron US-A 4,439,520 discloses similar spectrally sensitized grains. Abbott's US
-A44425425 describes a radiographic material containing tabular grains having an aspect ratio of at least 8: 1; Abbott US-A4425426 describes 5: 1 to 8:
Disclosed are similar particles having an aspect ratio of 1. For a general overview of high aspect ratio silver halide emulsions, see Re.
search Disclosure, Volume 225, 1983 1
Moon, found in Item 22534.

The major photographic advantages of tabular grains compared to conventional spherical grains in radiographic applications are high covering power, high developability and high sharpness, especially at high precuring levels in double-sided coated spectral sensitized materials. Is. The thinner the tabular grains, the greater these advantages.

The literature on tabular grains cited above discloses silver bromide or silver bromoiodide emulsions with particularly high sensitivity, while the use of emulsions with tabular grains rich in chloride, for example, has hitherto been used. It has been considered to be a disadvantage to sensitivity. Due to the chloride-rich emulsions, the applications in the field of less sensitive materials such as graphic arts materials, reproduction materials, radiographic hardcopy materials, diffusion transfer reversal materials and black and white or color print materials are good. Are known. The advantages of crystals with the chloride-rich crystals for high development and fixing rates are well recognized.

[0007] Today, there is a tendency to obtain materials that can be processed in shorter processing times, so that combining the above advantages with high sensitivity for highly sensitive material applications is highly appreciated. The purpose can be realized as described in EP-A0678772.

Notwithstanding these important advantages, tabular grains, those grains rich in chloride and those rich in bromide have two major drawbacks: they are highly susceptible to mechanical stress and development. The resulting silver has an unacceptable reddish brown color when compared to the desired cool black color exhibited by the more spherical particles. Tabular grains rich in silver chloride are inferior in image tone to those grains rich in bromide having comparable dimensions (thickness and aspect ratio) after treatment with conventional processing solutions used in the processing of conventional radiographic materials. May even show.

This reddish brown color can be corrected by increasing the optical density in the red region of the visible spectrum by adding suitable dyes to the subbing layer, to the emulsion layer and / or to the protective layer. Color correction methods that do not follow this image include, for example, JP-A3 / 100645; 1/2983.
8; 1/3112536; 3/103846; 3/942
49; 3/255435; 61/285445; EP-
It is disclosed in documents such as B271309 and US-P4861702. However, this necessarily leads to an undesired overall fog of the photographic material, the sensitivity of which to mechanical stress is obviously not improved by this optical correction method.

A more preferred method is image-based color correction. This can be done by utilizing a color forming developer, which is colored blue in oxidized form. Examples are JP-A3 / 153234; 3/154043;
3/154046. Further JP-A
3/156447 and 3/157645 disclose the absorption of blue colored dyes as a function of exposure.

Another way to overcome these drawbacks is to use tabular grains with increased thickness. A method for making thicker tabular grains is described in US-
P4801522; 5028521 and 5013641.
And EP-A569075. However, the advantages gained by utilizing tabular grains as cited above are eliminated by utilizing this method.

[0012]

The present invention therefore produces tabular grains having a thickness of less than 0.2 .mu.m which overcomes the above disadvantages of unacceptable image tone and susceptibility to mechanical stress. The aim is to coat them in negative image type silver halide photographic materials. Other purposes will be apparent from the description below.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a multilayer negative image-type material comprising a multilayer composition of at least two layers of a negative image-type silver halide emulsion adjacent to each other on at least one side of a support. And the emulsion layer closest to the support has a {111} crystal habit, silver chloride, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, silver bromide and silver bromoiodide and {100} A tabular emulsion crystal selected from the group consisting of silver chloride having a crystal habit, silver chlorobromide, silver chloroiodide and silver chlorobromoiodide, wherein the adjacent layer farther from the support is silver chloride, chloroodor. A multilayer negative image type comprising substantially cubic emulsion crystals selected from the group consisting of silver bromide and silver bromide, wherein the halide composition of said cubic emulsion crystals or of said tabular emulsion crystals or both comprises chloride. This is accomplished by providing the material.

The invention further provides a method of making the light-sensitive silver halide photographic negative image-type material by coating the multilayer composition on at least one side of a support and overcoating the composition with at least one protective layer. Also describe.

[0015]

DETAILED DESCRIPTION OF THE INVENTION From silver chloride, silver chlorobromide and silver bromide, preferably for use in layers adjacent to layers containing tabular {100} or {111} grains in multilayer materials according to the present invention. In the process of preparing silver halide crystals selected from the group consisting of, the pH range for the precipitation is such that the emulsion coated in the emulsion layer furthest from the support is such that the emulsion has a substantial cubic habit. To be selected. "Substantially cubic" means (a) preferably cubic, or (b) cubic with rounded corners, or (c) as small as the (111) face so that an actually tetradecahedral emulsion is obtained. Means a particle having any of the following formulas (however, the total area of these (111) planes is smaller than the total area of (100) planes). Furthermore, the cubic octahedral shape is not excluded and is determined by the effective pAg value applied during the precipitation of the selected silver chloride, silver chlorobromide or silver bromide crystals.

The precipitation of such cubic crystals can in principle be carried out by a single double jet step; or it can consist of a series of nucleation steps and at least one growth step. In the latter case, preferably 0.5 of the total silver halide precipitated during the nucleation step, which preferably consists of the addition of approximately equimolar amounts of silver and halide salt.
~ 5.0 mol% is formed. The balance of silver and halide salt is then added during one or more continuous double jet growth steps. The different steps of precipitation can be changed by the physical aging step. During the growth process, the silver salt and halide solution flow rates can be kept constant; or the silver salt and halide ion solution flow rates can be increased. For example, the flow rate can be increased temporarily. Typically the end flow rate is about 3-5 times greater than that at the beginning of the growth process. These flow rates can be controlled, for example, by magnetic valves.

In a preferred embodiment of the invention, the substantially cubic emulsion has a pAg maintained at a constant value of 7 to 10, more preferably 7 to 9, without a separate nucleation step, at a constant flow rate, and only 1 It is formed by one double jet process. Constant pAg is the so-called "bypass solutio
n) ", the addition of which is alternately switched on and off. The concentration of the main silver salt and halide solution is typically 0.5 to 3 mol, most preferably 1 to 3. It is in the range of 2 mol.

Preferably substantially cubic emulsion crystals have a grain size of 0.
It has an average crystal diameter of 1 to 0.8 μm, more preferably 0.2 to 0.6 μm.

The silver halide crystals used in the light-sensitive layer closer to the support of the multilayer material produced according to the present invention have at least 50 mol% chloride, more preferably at least 75 mol% chloride and if iodide. Have 0.1 mol% to 3 mol% iodide, if present,
It is a tabular silver chlorobromide, silver chlorobromoiodide or silver chloroiodide emulsion or tabular silver bromide or silver bromoiodide containing grains rich in chloride.

The halide distribution in the tabular grains can be homogeneous over the entire crystal volume. The crystals are said to have a core-shell structure when the different phases in the silver halide composition are present throughout the volume. One or more shells can be present and it is recommended to have a silver iodide rich phase between the different phases by applying so-called conversion techniques during precipitation.
The iodide ion can be provided by using an aqueous solution of its inorganic salt as potassium iodide, sodium iodide or ammonium iodide. The iodide ion is, for example, EP-A0561415, 0563701, 056.
It can also be provided by organic compounds which liberate iodide ions as described in 3708, 0649052 and 0651284. Thin tabular grains bounded by {100} or {111} major faces are used in the adjacent hydrophilic emulsion layers located closer to the support of the material made in accordance with this invention.

Particularly chloride-rich tabular silver halide grains bounded by {100} major faces and / or processes for their preparation and / or materials into which said grains can be incorporated are described, for example, in US-A 5024931; 5264337;
5275930; 5292632; 5310635; 5
314798; 5320938; 5356764 and W
O94 / 022051; published EP-A05343
95, 0569971, 0584815, 058464
4,0602878,0616255,061731
7, 0617320, 06317321, 061732
5, 0618492 and EP-A 06536969.

Further, tabular silver halide grains rich in chloride and / or a method for producing the same and / or a material into which the grains can be mixed, which are bounded by {111} major faces, are described, for example, in US-A 4,399,215; 440046.
3; 4804621; 5061617; 517699.
1; 5176992; 5178997; 517899.
8; 5183732; 5185239; 521785
8; 5221602; 5264337; 527205
2; 5275930; 5286621; 592263.
2: 5298385; 5298387; 529838
8; 5310644; 5320938; 535356
4; published EP-A0481133, 050370.
0, 0532801, 0533189, 0647877
And 0678772.

At least one of the tabular grains may be further doped with any one of the doping agents. For example R
It may be doped with Group VIII metal ions such as h ³⁺ , Ir ⁴⁺ and Co ²⁺ or with Cd ²⁺ , Zn ²⁺ or Pb ²⁺ or mixtures thereof.

EP-A 0569075 is useful for the preparation of tabular silver bromide or silver bromoiodide crystals bounded by {111} major faces and for materials containing said crystals. This document is incorporated here for reference.

In order to achieve the object of the present invention, the tabular silver bromide and silver bromoiodide crystals coated in the emulsion layer close to the material support are cubic silver chloride or silver chlorobromide emulsion crystals (see above). The silver chlorobromide emulsion crystals are overcoated with a layer containing iodide, preferably 50 mol% or more, more preferably 75 mol% or more.

The crystal size obtained at the end of the precipitation of silver halide grains depends on the amount of silver precipitated during the nucleation step, the initial concentration of reagents present in the reaction vessel, the flow rates of the silver salt and halide salt solutions, and the temperature. , PAg, the presence of growth promoters, and many other factors.

Due to the tabular silver halide grains contained in the silver halide photographic material according to the present invention, an average thickness of less than 0.2 μm based on the total crystal population is preferred. 0.15μ
More preferred is a thickness of less than m. Even an ultrathin crystal having a thickness of 0.06 μm can be used. The average aspect ratio, defined as a ratio, calculated from measurements of the diameter and its thickness equivalent to a circle having the same surface area as different individual particles, is preferably higher than 5: 1, more preferably higher than 8: 1. , And even more preferably 12: 1 to 10
0: 1.

A mixture of chloride-rich tabular crystals having {111} and / or {100} major faces is used as a mixture of silver bromide and / or silver bromoiodide tabular grains having {111} major faces. You can also do it.

According to the invention, mixtures of the abovementioned emulsions can be used in adjacent layers of the photographic material according to the invention. Provided that the layer closest to the support contains a mixture of tabular grains, while the layer further from the support contains a mixture of substantially cubic grains, and said cubic or said halogen of said tabular emulsion crystals. The compound composition must always contain chloride. This limitation is due to the fact that the improvement in image tone of developed tabular grains observed for tabular and cubic emulsion crystals containing no chloride-containing layer arrangement is inferior compared to a different layer arrangement. There is no compelling example of having improved image tones for layer arrangements in which both adjacent layers contain silver bromide and / or silver bromoiodide emulsion crystals, so that in the following examples It does not exist. Such a layer arrangement in photographic materials is EP-A008.
Increased sensitivity and maximum density for invariant coverage of silver (efficient use of silver) as compared to materials having only one emulsion layer on one or both sides of the support as disclosed in 4637. Is more suitable for giving

Emulsions having different halide distributions or compositions can be mixed, or emulsions having the same halide composition with different average crystal sizes can be mixed. The emulsions having the same composition but different grain sizes have the same fine silver halide "mother (mo
"ther)" emulsion nuclei. It is possible to obtain such emulsions having crystals of different sizes by the addition of different amounts of silver salt and halide salt solutions or by applying different physical ripening times.

In one embodiment of the invention, at the end of the emulsion making process, the emulsion is washed with conventional washing techniques (eg, after agglomeration with ammonium sulfate or polystyrene sulfonate).
Excess soluble inorganic salts can be eliminated by several washing steps and redispersion). Another well known cleaning technique is ultrafiltration. Extra gelatin can be added to the emulsion to finally obtain the desired gelatin to silver ratio.

According to the invention, the tabular silver halide emulsion in the hydrophilic layer closest to the support is chemically sensitized while the substantially cubic emulsion located in the adjacent layer further from the support is chemically sensitized. Can be sensitized. In this multilayer composition, the substantially cubic grains do not contribute to increasing the speed or sensitivity of the material: it is preferred that the substantially cubic grains be less sensitive than the tabular grains present in the adjacent layers, which is an object of the present invention. It is effective for obtaining a clear black image tone.

The chemical sensitization method is described, for example, in "Chimie et Physique Photographique" by P. Glafkides, G.
“Photographic Emulsion Chemist” by F. Duffin
ry ”,“ Making and Co by VL Zelikman et al.
ating Photographic Emulsion ”and H. Fries
Edited by Akademische Verlagsgesellschaft (1968), “Die Grundlagen der Photographi
schen Prozesse mit Silberhalogeniden ”. Chemical sensitization, as described in the above-referenced document, is a compound containing small amounts of sulfur, selenium or tellurium (eg thiosulfate, thiocyanate, thiourea, selenosulfate, selenocyanate, selenourea, telluro). It can be carried out by ripening in the presence of sulphates, tellurocyanates, sulphites, mercapto compounds, and rhodamines .. The emulsions are either with gold-sulfur ripeners or with reducers (eg GB-P789823). Tin compounds such as amines, hydrazine derivatives,
Formamidine-sulfinic acid, and a silane compound).

Chemical sensitization can be further performed with a sensitizer known to those skilled in the art. It can be carried out with reduction sensitizers, precious metal salts such as gold salts together with reduction sensitizers, sulfur and / or selenium sensitizers, high pH-values and low pAg values. The combination of gold salt, sulfur and selenium compounds can provide a good fog-sensitivity relationship. The reduction sensitization that causes fogging can be performed by reducing with a strong reducing agent that introduces small spots of metallic silver onto silver halide crystals (preferably those having a cubic crystal habit). Examples of particularly useful compounds having reducing properties are thioureum dioxide, tin compounds as described in GB-A789823, amines, hydrazine derivatives, formamidine-sulfinic acid and silane compounds.

Substantially cubic silver chloride, silver chlorobromide or silver bromide emulsions may or may not be spectrally sensitized, {1
A tabular silver halide emulsion crystal having a {00} or {111} major surface is for the same reason as above for chemical ripening,
That is, it is spectrally sensitized for the primary purpose of obtaining a suitable black image tone. It is preferred according to the invention that the substantially cubic crystals do not contribute to speed or sensitivity and are therefore less sensitive than the tabular grains present in adjacent layers.

The spectral sensitization is described by FM Hamer in “The
Cyanine Dyes and Related Compounds ", 196
4, methine dyes such as those described by John Wiley & Sons. Research Disclosure Item for a summary of useful chemical types of spectral sensitizing dyes and special useful examples associated with tabular grains.
22534. A more recent practical summary is EP-Application No. 9 filed August 1, 1995.
No. 52202096, which is incorporated here for reference.

Dyes which can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
For example, particularly suitable green sensitizers in connection with the present invention include anhydro-5,5'-dichloro-3,3'-bis (n-sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide or anhydro-5. , 5'-Dichloro-3,3'-bis (n-sulfopropyl) -9-
There is ethyl oxacarbo-cyanine hydroxide. Other particularly valuable dyes, such as the described cyanine dyes, merocyanine dyes and complex merocyanine dyes, are used only in the ultraviolet and blue regions of the spectrum of the non-spectral sensitized silver halide crystals used in the process for preparing the multilayer materials according to the invention. To be sensitive, the spectral range is extended to the region where the light sensitive silver halide crystals are sensitive to capture the light emitted from the light source. Preferably according to the invention the spectrum of the spectrally sensitized silver halide crystals is between 350 and 500 nm.

As alluded to previously, in conventional emulsion preparation spectral sensitization has traditionally been performed after completion of chemical sensitization. However, in the context of tabular grains, it is specifically believed that spectral sensitization occurs concomitantly with, or entirely precedes, the chemical sensitization step.
Chemical sensitization after spectral sensitization is believed to occur at one or more ordered discrete positions in the tabular grains. This can also be done with the emulsions of the invention, where chemical sensitization is carried out by one or more phenidones and / or derivatives, dihydroxybenzenes such as hydroquinone, resorcinol, catechol and / or their derivatives, one or more stabilizers or antifoggants. Agent, one or more spectral sensitizers or a combination of said components. In particular, 1-p-carboxyphenyl, 4,4'dimethyl-3-pyrazolidin-1-one can be added as a suitable auxiliary agent.

Other dyes, which themselves do not have any spectral sensitizing activity, or certain other compounds which do not substantially absorb visible radiation, have strong effects when they are mixed in the emulsion with said spectral sensitizer. It can have a color sensitizing effect. Suitable supersensitizers include, for example, US-A3457.
Heterocyclic mercapto compounds containing at least one electronegative group, such as those described in US Pat.
A2333390 and nitrogen-containing heterocyclic ring-substituted aminostilbenzene compounds as described in US Pat. No. 3,635,721, for example aromatic organic acid-formaldehyde condensation products, cadmium salts and azaindene compounds as described in US Pat. No. 3,743,510. is there.

Depending on the application for which the silver halide material according to the present invention is used, the emulsion containing silver halide crystals is spectrally sensitized so that it is sensitive to the light source used, whether or not it emits visible radiation. To be done.

At least one non-spectral sensitizing dye can be added as a filter dye to at least one of the adjacent emulsion layers of the material according to the invention or to one or more non-photosensitive hydrophilic layers. The presence of the dye in an amount adapted to the at least one hydrophilic layer is recommended not only for adjusting the sensitivity and the required contrast of the different emulsion layers, but also for reducing the scattering of exposing radiation and enhancing the sharpness.
Suitable dyes are those which are relatively easy to remove in an aqueous alkaline processing liquid and which diffuse sufficiently quickly throughout the hydrophilic colloid layer in said processing. It is clear that the dye is non-diffusible during the coating of the hydrophilic layer containing the dye. Examples of said dyes are eg US-A 356021.
4, 3647460, 4288534, 431178
No. 7,4857446, but not limited thereto. Monomethine dyes are usually required for a second filter dye to block or absorb green light, and a third one is required to absorb longer wavelength radiation (eg red or infrared region radiation). As such, it has a maximum absorption spectrum in the shorter wavelength range of the visible spectrum. Once the filter dye is selected, the problem is how to obtain the filter dye in the coating so as to satisfy all the above conditions. One of the preferred possibilities is EP-A0384633, EP-B
0323729, EP-B0274723, EP-B0
276566, EP-A0351593, EP-A05
86748, 0587230 and 0656401 and U
S-A4900653, 4904565, 494965
4, 4940654, 4948717, 498861
No. 1,4803150 and 5,344,749, utilizing solid particle dispersions of water-insoluble dyes. Another possibility is to prepare said dyes in the form of solid silica particle dispersions as described in EP-A569074.

Another possibility for obtaining ultrafine dye dispersions consists in acidifying the slightly alkaline coating composition "in situ" before coating on a support. This administration (do
It has been found that the application of the sage) technique allows us to obtain the dye in the form of very fine solid particles, in which the solid particles are homogeneously divided in the coating layer so that they are hardly observable even by microscopic techniques.

The non-diffusing dye added to the hydrophilic layer of the photographic material as solid particles is less than 10 μm, more preferably 1 μm.
It has an average diameter of less than m, and even more preferably less than 0.1 μm.

The dispersed filter dye is almost completely removed from the hydrophilic, water-permeable colloidal layer of the photographic silver halide emulsion material by treatment with an alkaline aqueous liquid and dispersed at a pH of at least 10 to leave no residual stain. Filter dyes are easily solubilized. The presence of sulfite in the treatment solution contributes to the faster fading of the filter dye. The dyes incorporated in the emulsion layers of the multi-layer materials produced according to the present invention preferably have the general formula (I):

Embedded image Wherein R ¹ is hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, aralkyl or substituted aralkyl, R ² is carboxy, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, ureido, sulfamoyl or a group represented by R ¹ . One, R
^At least one of ¹ and R ² is or contains carboxy or carbamoyl, R ³ is hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, and when R ³ is alkyl or alkoxy, It is ortho or para to the hydroxy group and itself ortho to the methine group, said merostyryl dye further contains no groups which solubilize the dye in the hydrophilic colloid layer.

It is preferred to be present in at least one emulsion layer of the multilayer material according to the invention, but under certain conditions the same or other dyes may be used in the backing layer, antihalation undercoat layer, intermediate layer and / or protective outermost layer. Can be present.

Silver halide emulsions for use in multilayer materials prepared in accordance with the present invention contain compounds that stabilize photographic properties or prevent the formation of high minimum densities during manufacture or storage of the photographic material or during its photographic processing. Can be included.
Many known compounds can be added to the silver halide emulsion as antifoggants or stabilizers. Suitable examples include, for example, heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminos. Triazole, benzotriazole (preferably 5-methyl-benzotriazole), nitrobenzotriazole, mercaptotetrazole, especially 1-phenyl-5-mercaptotetrazole, mercaptopyrimidine, mercaptotriazine, benzothiazoline-2-thione, oxazoline-thione, tria. The inden, tetraazaindene and pentaazaindene,
In particular, Z. Wiss. Phot. 47 (1952), pages 2-58, published by Birr, GB-A12037.
57, GB-A1209146, JP-B77 / 031.
738 and triazolopyrimidines such as those described in GB-A1500278, and US-P 472701.
7-Hydroxy-s-triazolo-as described in 7
[1,5-a] -pyrimidine, and other compounds such as benzenethiosulfonic acid, benzenethiosulfinic acid, benzenethiosulfonic acid amide. Other compounds that can be used as antifoggants are Research Disclousur
e No. 17643 (1978), there are compounds described in Chapter VI.

To the silver halide emulsion, before its chemical ripening,
Antifoggants or stabilizers can be added during or after aging, and mixtures of two or more of these compounds can be used.

Specially oxidized gelatin or synthetic peptizers can be used in the preparation of the emulsions according to the invention. Conventional lime-treated or acid-treated gelatin can be used. The production of such gelatin type is described, for example, in Academic Press, 1977, edited by AG Ward and A. Courts, The Science and Technology of.
Gelatin, pages 295 and 296.
Gelatin is also Bull. Soc. Sci. Phot. Japan, No. 1
6 (1966), page 30, can also be treated with an enzyme. Prior to or during the formation of silver halide grains, the gelatin concentration is about 0.05-5.
It is common practice to keep at 0% by weight. Additional gelatin is added at a later stage in the emulsion production (eg after washing),
Optimal coating conditions can be established and / or the required thickness of the coated emulsion layer can be established. Preferably the weight ratio of gelatin to silver halide is in the range 0.3 to 1.0.

Gelatin binders in photographic materials are suitable hardeners, such as those of the epoxide type, those of the ethyleneimine type, those of the vinyl sulfone type, such as 1,3-vinylsulfonyl-2-propanol or di- (vinylsulfonyl). ) -Methane, vinylsulfonyl-ether compounds,
Vinyl sulfonyl compounds having soluble groups, such as chromium salts such as chromium acetate and chromium alum, aldehydes such as formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds such as dimethylol urea and methylol dimethyl hydantoin,
Dioxane derivatives such as 2,3-dihydroxy-dioxane, active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine. , And mucohalogen acids such as mucochloric acid and mucophenoxycycloric acid. These curing agents can be used alone or in combination.

The binders can also be cured with fast-curing agents such as those described in US Pat. No. 4,063,952 (for example carbamoylpyridinium salts) and onium compounds such as those described in EP-A 0408143.

The photographic materials of the present invention can contain various surfactants in the photographic emulsion layer or in at least one other hydrophilic colloid layer. Suitable surfactants include saponins, alkylene oxides such as 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 alkyls. Nonionic surfactants such as amines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; acid groups such as carboxy, sulfo, phospho, sulfate or phosphate groups. Anionic surfactant containing; amino acid, aminoalkyl sulfonic acid, a Amphoteric surfactants such as noalkyl sulfates or phosphates, alkyl betaines, and amine-N-oxides; and alkyl amine salts, aliphatic, aromatic or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring-containing phosphoniums. Alternatively, it contains a cationic surfactant such as a sulfonium salt. Such surfactants may be used for various purposes, for example as coating aids, as antistatic compounds,
As compounds that improve lubricity, as compounds that facilitate dispersion emulsification, as compounds that prevent or reduce adhesion, and photographic properties (eg, high contrast, sensitization and development acceleration).
Can be used as a compound for improving

Development acceleration is achieved by various compounds, preferably for example US-A 3038805, 4038075 and 429.
At least 400, such as those described in US Pat.
Can be achieved with the aid of polyalkylene derivatives having a molecular weight of

The photographic material of the present invention further comprises various other additives such as compounds which improve the dimensional stability of the photographic material as described below, UV absorbers, spacing agents, hardeners and plasticizers. Can be included.

Additives suitable for improving the dimensional stability of the photographic material, such as water-soluble or almost water-insoluble synthetic polymers such as alkyl (meth) acrylates, alkoxy (meth) acrylates, glycidyl (meth) acrylates, Polymers of (meth) acrylamide, vinyl ester, acrylonitrile, olefins and styrene, or the above and acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate And a dispersion of a copolymer with styrene sulfonic acid can be added.

Suitable plasticizers for incorporation in the emulsions used according to the invention include, for example, glycols, glycerin, or polyvinyl acetates, lower alkanol acrylates and methacrylates, such as polyethyl-.
There are latexes of neutral film forming polymers including acrylates and polybutylmethacrylate.

Suitable UV absorbers are, for example, US-A3.
Aryl-substituted benzotriazole compounds as described in 533794, US-A3314794 and US
-Thiazolidone compounds as described in A-3352651, benzophenone compounds as described in JP-B80 / 012586, US-A370580.
5 and 3707375, cinnamic acid ester compounds, butadiene compounds as described in US-A 4045229, and benzoxazole compounds as described in US-A 3700455.

Generally, the spacing agent has an average particle size of 0.
It is included in 2 μm to 10 μm. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in photographic materials,
Alkali-soluble spacing agents, on the other hand, are usually removed therefrom in alkaline treatment baths. Suitable spacing agents can be made from polymethylmethacrylate, copolymers of acrylic acid and methylmethacrylate and hydroxypropylmethyl-cellulose hexahydrophthalate. Other suitable spacing agents are US-A46147.
08.

The emulsion of the photographic material according to the present invention forms a multilayer package. There are at least two emulsion layers coated adjacent to each other, but the presence of exactly two adjacent emulsion layers is preferred.

The multilayer material according to the invention may further comprise in at least one of the two adjacent layers a mixture of the light-sensitive emulsions according to the invention having the abovementioned crystal habit. In a preferred example, the number of light-sensitive emulsions used in each emulsion layer in the light-sensitive silver halide photographic material according to the present invention makes its production simple and reproducible, and also has a wide latitude and an undisturbed linear sensitivity. It is kept to a minimum to give the possibility of obtaining a tomometry curve. Differences in halide composition and average grain size of crystals mixed in adjacent layers or in one layer may exist, but for reasons of accuracy and reproducibility during production, only one emulsion was prepared, It is preferred to distribute the emulsion in different parts, apply for different spectral and / or chemical ripening and mix them together.
In addition to the light-sensitive emulsion layer the photographic material according to the invention contains several non-light-sensitive layers. Adjacent to the emulsion layer furthest from the support is a protective layer, which is the topcoat layer if no afterlayer is present. The top coat layer may be double coated. Due to such complex multilayer arrangements, it is recommended from an economical standpoint to coat these layers simultaneously by the slide-hopper or slide-hopper curtain coating method.

The protective layer and the after layer are surfactants,
Various additives such as matting agents, lubricants, thickeners, bactericides and antistatic agents can be included. One or more curing agents may be added to the protective topcoat layer, but is preferably added just prior to coating said layer. The same curing agents as described above can be used. Furthermore one or more non-spectral sensitizing dyes are preferably added to it in the coating,
The sensitivity of the coating material can be controlled.

When the silver halide photographic material is a one-side coating material, one or more backing layers are present to prevent curling of the material. Therefore, the coverage of gelatin and / or matting agent is optimized.

The advantages afforded by the method for producing the multilayer material according to the invention relate to the main purpose of obtaining suitable image tones. Further coverage of silver is expressed as the equivalent amount of silver nitrate, for example 12 g / m less than ^2, more preferably can be reduced to an amount of 3 to 10 g / m ^2. A large amount is particularly preferable for a material exhibiting high sensitivity. From an ecological point of view, this method offers the advantage of lower chemical consumption during replenishment and processing.

In addition to the protective layer and optionally one or more backing layers, some non-photosensitive layers may also include one or more intermediate layers (eg filter layers) and eg hardeners, antistatic agents, for safe light purposes. It may be an after-layer containing a filter dye or the like.

The support of the photographic material can be opaque or transparent, for example a paper support or a resin support. When a paper support is used, it is preferably coated on one or both sides with an α-olefin polymer (eg polyethylene) layer optionally containing an antihalation dye or pigment. Organic resin support such as cellulose nitrate film, cellulose acetate film, poly (vinyl acetal) film, polystyrene film, poly (ethylene terephthalate) film, poly (ethylene naphthalate) film, polycarbonate film, polyvinylidene chloride film, or poly- Alpha-olefin films (eg polyethylene or polypropylene films) can also be used. The thickness of the organic resin film is preferably 0.07 to 0.35 mm. These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.

The photographic material in connection with the present invention can be used in any type of photographic material, for example black and white photographic material, especially for micrographic applications such as reproduction material to provide a copy from the original image. , Low speed photographic materials such as those used for graphic applications.

However, since the aim is to improve the image tone, materials used especially for medical X-ray diagnostic purposes are considered. The multilayer photographic X-ray material produced by the method of the present invention is a double-sided coated X-ray material or a single-sided coated X-ray material coated with at least one backing layer on the side opposite to the side bearing the photosensitive emulsion layer. It is a material.

The photographic material according to the present invention can be image-wise exposed by any convenient radiation source according to its particular application. In a preferred example, X-ray conversion screens are used in film-screen systems in which X-rays are absorbed by the phosphor particles coated within the phosphor layer of the screen. The X-rays are converted to radiation having a wavelength that sensitizes the silver halide crystals coated in the layer of light sensitive silver halide film material. The film-
In a screen system, the screen is brought into close contact with each side of the film material bearing the emulsion layer for good image quality, especially sharpness. The film-screen system can be a symmetrical or asymmetrical system. Symmetric systems are well known and are characterized in that they are in contact with the same phosphor plate, with the same emulsion layers and other auxiliary layers on both sides of the support. Asymmetric film-screen systems may consist of the same emulsion layer on both sides of the support, but with different phosphor plates, such as phosphor composition, phosphor particle size or size distribution, phosphor coverage, and all these measures. Composed of different phosphor plates in the combination of
Thus leading to different screen speeds. Examples thereof are, for example, US-A1925546, 4835396, 506.
9982 and 5259016, JP-A06 / 1305
75 and 06/130577 and EP-A023288.
8 and 0633497. The asymmetric film-screen system creates emulsion layers with different sensitivities because of the different silver halide composition of each layer, due to differences in silver halide grain size or size distribution, differences in coverage etc. and combinations of all these measures. It may consist of the same screen in contact with both film sides, leading to different speeds and / or contrasts of the emulsion layers on both sides of the film support. An example is U
S-A4994355, 5021327, 525244
3, 5380636 and 5399470, JP-B77.
/ 018580, JP-A04 / 235545, 04 /
125626 and 04/145427 and EP-A04
40367, 0449101 and 0530117. Further, in screen-film systems, both film and screen are, for example, DE
1000687, DD00237010, US-A49
78599, 5070248, 5238795, 525
9016, 5354648 and 5380636, and E
P-A0384634, 0437117, 052465
0, 0577027, 0581065 and 062774
It may be asymmetric as shown in FIG.

After exposure of the film, the processing conditions and the composition of the processing solution depend on the particular type of photographic material to which the tabular grains present in multilayer materials prepared according to this invention are applied. For example, in a preferred example of a material for X-ray diagnostic purposes, after exposure of the film-screen system by X-ray, the material may be subjected to rapid processing conditions. Preferably an automatically operated processor equipped with a system for automatic regeneration of the processing solution is used. The pre-cured material may be processed using one-part or three-part packaging chemistries depending on the processing application that determines the degree of cure required for the processing cycle.

The processing of photographic materials produced according to the method of the present invention is usually characterized by the steps of developing, fixing, rinsing and drying, depending on the type of material and the amount of silver coated on it, from 30 to 210 seconds or more. Preferably 38-
Preference is given to a total treatment time of 90 seconds. Any chemical known to those skilled in the art may be used depending on their composition and particular application. To produce black and white images, they are preferably treated with a conventional phenidone / hydroquinone or substituted phenidone / hydroquinone developing solution and a conventional sodium and / or ammonium sulfate containing fixing solution.

The present invention is illustrated by the following examples, but the present invention is not limited thereto.

[0071]

【Example】

Preparation of Emulsion Crystals Preparation of Emulsion A (AgCl cubic) A silver halide emulsion having a cubic habit was prepared by the double jet technique. The silver halide composition is 100 mol
% Chloride and the average particle size was 0.55 μm.
For this purpose at 60 ° C 46 g of inert gelatin and 10 m
Methionine was used as a particle growth promoter in an amount of 37 g per starting volume of 615 ml in the container, containing mol sodium chloride. 3N AgNO ₃ and N respectively
Using a double jet method, a 1 l concentrated solution of aCl was used at a rate of 20 ml / min for 50 minutes for a silver nitrate solution and 20.83 m for a sodium chloride solution.
Flow at a rate of 1 / min for 48 minutes. After 15 minutes of physical aging, the pAg was about 7.9 and the agglomeration process could be started: p
H was adjusted to a value of 3.3 with sulfuric acid, and 4.5 g of polystyrenesulfonic acid was gradually added over 2 minutes. The cleaning method is pA
It was carried out in a discontinuous manner by adding 3 liters of deionized water containing 8 mmol or less of sodium chloride per liter until g reached a value of about 7.3. After adding inert gelatin until the ratio of gelatin to silver nitrate in the emulsion is about 0.35, the emulsion is redispersed and chemically aged at 52 ° C to the best fog-sensitivity relationship, pAg of about 6 It had a value of 0.95. Gold (amount of 0.019 mmol per mol of silver)
And the chemical ripening agents other than sulfur (tetramethylthiodithiocarboxylic acid diamide in an amount of 0.061 mmol) are toluenethiosulfonic acid and iodide ions, both being 0.02 mmol and 8.6 mmol pre-ripening agents, respectively.

Preparation of Emulsion B (AgBr Cubic) A cubic silver bromide (100 mol% bromide) emulsion was prepared by the conventional single jet method in a vessel containing 40 g of phthaloyl gelatin. The ammoniacal silver nitrate solution was held at 42 ° C as was the emulsion container containing the halide salt. 1 at a constant speed of 300 ml / min
After 0 minutes, the precipitation was completed and physical aging was carried out for 40 minutes. After that time an additional 20 g of gelatin was added. The resulting emulsion had an average grain size of 0.59 μm and contained about 90 g silver nitrate per kg dispersion after addition of 3 mol silver nitrate.

After adding sulfuric acid to a pH value of 3.5, the stirring was stopped and the supernatant was removed after settling. The washing method was started after the scraping rubber was installed and after the first addition of polyethylene sulfonic acid to obtain a quantitative agglomerate without silver loss. During redispersion of the emulsion, 150 g of gelatin was added so that the weight ratio of gelatin to silver nitrate was 0.42. The emulsion contained an amount of silver bromoiodide equal to 190 g of silver nitrate per kg.

The emulsion was chemically ripened with sulfur and gold at 47 ° C. for 4 hours to obtain the optimum relationship between fog and sensitivity, and further stabilized with 4-hydroxy-6-methyl-1,3,3a-tetraazaindene. Let

Emulsion C (AgCl {111} tabular crystal)
Preparation of a silver chloride emulsion having a {111} tabular crystal habit was prepared as follows: 3 liters dispersion medium (C) containing 0.444 mol sodium chloride, 75 g inert gelatin and 36 mg adenine. The temperature was adjusted to 45 ° C. and the pH was adjusted to 6.0; −2.94 mol silver nitrate solution (A); −solution containing 4.476 mol sodium chloride and 42 mg adenine (B1).

The nucleation step was carried out by introducing solution A and solution B1 simultaneously into dispersion medium C both at a flow rate of 60 ml / min for 30 seconds. Physical aging was carried out for 20 minutes while increasing the temperature to 70 ° C. Then, the growth step starts the solution A by a double jet for 77.5 minutes (at a flow rate of 5 ml / min and a flow rate of 1 at a final value of 20 ml / min.
Solution B1 (at a constant pAg of 7.25)
(At increasing flow rates to maintain the flow rate). After cooling to about 40 ° C., the pH value of the dispersion medium is adjusted to a value of 3.0 with sulfuric acid and after addition of 55.5 ml of polystyrene sulphonic acid, the agglomerates obtained are decanted and the soluble salts present Was washed 3 times with a volume of 6 l of deionized water in order to remove After adding 50 g of inert bone gelatin to this dispersion medium, 1. mol / mol of silver chloride was added.
An amount of 25 mmol of the dye anhydro-5,5'-dichloro-3,3'-bis- (n-sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide was added.

Tabular silver chloride crystals with {111} major faces and a spherical equivalent mean diameter of 2 μm were obtained with an average thickness of 0.15 μm yielding an average aspect ratio of 13. Prior to the start of chemical ripening, the pAg was adjusted to 7.25 and the pH value was adjusted to 5.5. The chemical ripening agents were gold, sodium thiosulfate and thiocyanate as sulfur sources, and toluenethiosulfonic acid was used as a pre-ripening agent. The optimum fog-sensitivity relationship was achieved after 2 hours at 57 ° C. The emulsion was stabilized with 1-p-carboxy-phenyl-5-mercaptotetrazole.

Emulsion D (AgCl {100} tabular crystal)
The following solutions were prepared: 2 l of dispersion medium (C) containing 20 mmol sodium chloride and 10 g of inert bone gelatin; temperature 5
The temperature was adjusted to 0 ° C. and the pH was adjusted to 6.0; −2.94 mol silver nitrate solution (A); −2.94 mol sodium chloride solution (B1). The temperature of A and B1 was 40 degreeC.

The nucleation step was carried out by introducing solution A and solution B1 simultaneously into dispersion medium C both at a flow rate of 60 ml / min for 30 seconds. Physical aging was carried out for 20 minutes while increasing the temperature to 70 ° C. Then, in the growth step, Solution A (5 ml /
Start with a flow rate of min, increase linearly to a final value of 20 ml / min), and with solution B1 (constant p of 6.75).
Was introduced by increasing the flow rate to maintain Ag). After cooling to about 40 ° C., the dispersion medium p
The H value was adjusted to a value of 3.0 with sulfuric acid and after addition of 37 ml of polystyrene sulphonic acid the resulting agglomerates were decanted and deionized with an amount of 6 l to remove any soluble salts present. Washed 3 times.

The silver chloride tabular emulsion thus obtained had {1
00} main surface was shown. The average circle equivalent diameter d _EM , the average thickness d, and the average aspect ratio AR were obtained from electron micrographs.
Values of 1.58 μm, 0.42 μm and 3.8: 1 were measured. The emulsion was redispersed and chemically ripened at 52 ° C. to an optimum fog-sensitivity relationship. The pAg had a value of about 7.2. The chemical ripening agent is gold (0.019 m per 1 mol of silver)
mol amount) and sulfur (0.061 mmol amount of tetramethylthiodithiocarboxylic acid diamide), as well as toluenethiosulfonic acid and iodide ion, both of which are preaged in 0.021 and 8.6 mmol amounts, respectively. It is an agent.

Emulsion E (AgBr (I) {111} tabular form
Crystals) tabular grains were precipitated using the double jet method with controlled pAg values (the values are defined as the negative logarithm of silver ion concentration). After precipitation, all examples were analyzed using electron-enhanced shadowed carbon replicas. The minimum hundred grains were measured for each example and then the following properties were calculated: -The number of tabular grains was calculated. Tabular grains are defined as grains having two parallel major faces and at least two grain diameter to thickness ratios. -Diameter is the diameter of the circle with the equivalent projected surface area of the particle. -Thickness is the distance between the principal planes of a flat plate crystal.

Characterization of the crystal population of the emulsion was given by: -Average grain size: calculated as the number average from the diameter of the tabular grains. -Coefficient of variation of tabular grains: calculated as the ratio between the standard deviation of the mean diameter and the mean diameter. -Average thickness: calculated as the number average from the distances between the principal planes measured for all crystals. -Aspect Ratio: The ratio of the average calculated diameter and the average calculated thickness described above. -Percentage of total projected surface: Percentage of total projected area covered by tabular grains.

Three solutions were used during the precipitation: Solution 1: 1.5 an aqueous solution containing 500 g of silver nitrate.
l. Solution 2: 1.5 l of an aqueous solution containing 350 g of potassium bromide. Solution 3: 1.5 l of an aqueous solution containing 341 g potassium bromide and 12.2 g potassium iodide.

Nucleation step: 4 of each of solutions 1 and 2
1.3 ml was introduced into the reaction vessel in 28 seconds using the double jet method. The reaction solution initially contained 2.16 l of distilled water at 45 ° C., 12.6 g of potassium bromide and 12.5 g of gelatin. After 1 minute, the reaction temperature of this mixture was raised to 70 ° C. in 20 minutes and 47.5 g of phthalated gelatin in 475 ml of distilled water was added.
Ten minutes later, the neutralization step was started.

Neutralization step: 21.7 ml of Solution 1 was added to the reaction vessel at a rate of 7.5 ml / min to give a pBr of 1.63.
Value, then the first growth step was started.

First growth step: Double jet precipitation was started with solutions 1 and 2, which lasted 40 minutes and 51 seconds. The pBr value was kept constant at 1.63 during this precipitation.
The flow rate of solution 1 was 7.5 ml / min at the start and increased linearly to 26.7 ml / min at the end of precipitation. Thereafter, the second neutralization step was started.

Second neutralization step: 45.8 ml of solution 1 was added at a rate of 7.5 ml / min, thus giving a pB of 2.77.
r was obtained. The precipitation was then continued in the second growth step.

Second growth step (47.0% of the total amount of AgNO ₃ was used during this): 704 ml of solution 1 were introduced into the reaction vessel at a rate of 7.5 ml / min at the start and the end of precipitation. Injections were sometimes linearly increased to 37.5 ml / min. The pBr was kept constant at 2.77 using Solution 2 for the first 8 minutes 51 seconds, followed by the rest of the precipitation time by replacing Solution 2 with Solution 3.

The tabular grains had the following properties, as measured by electron microscopy: average diameter: 1.26 μm, coefficient of variation of tabular grains: 0.37, average thickness: 0.15 μm, Aspect ratio: 8.9, percentage of total projected surface: 99%.

After the emulsion precipitation was finished, the pH value was lowered to 3.5 with dilute sulfuric acid and the emulsion was washed with deionized water at 11 ° C. Add 237 g of gelatin at 45 ° C and add 40
The pH and pAg values at ° C were adjusted to 5.5 and 8.15. This emulsion was optimally sulfur and gold augmented in the presence of sodium thiocyanate and anhydro-5,5'-dichloro-3,3'-bis- (n.sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide. I felt.

Example 1 This example illustrates the improvement in developed silver image tone for AgCl {111} tabular crystals when combined with the AgCl cubic crystals present in adjacent emulsion layers. .

The coating was prepared as follows. 175
On a subbed blue polyester support of μm thickness,
Each side is displayed as g AgNO ₃ / m ² 10.5
Each side was coated by the slide hopper method with Emulsion A, B or C according to Table I to contain g / m ² of silver halide and 5.25 g / m ² of gelatin.

For coating 4, the total amount of silver halide coated on each side of the support was 10.5 g AgNO ₃ /
A 50:50 mixture of Emulsions A and C was used to equal m ² . For coating 5, tabular AgCl {11
1} emulsion (Emulsion C) was coated on both sides of the support with an equivalent weight of 5.25 g AgNO ₃ / m ² . On each layer of AgCl {111} tabular emulsion was coated an equivalent of 5.25 g of AgNO ₃ / m ² of cubic AgCl emulsion (Emulsion A).

1.4 g / m on each side for 5 coatings
² A protective layer containing gelatin was added. It was hardened with resorcinol and formaldehyde to the extent that it absorbed about 2 grams of water per gram of gelatin when soaked in deionized water at 24 ° C for 10 minutes.

Samples of these coatings were placed in close contact with an 8 mm thick copper filter at a distance of 1.50 m at 235 k.
Exposed with a V radiation source. Samples (coatings 2-5) were treated with a developer having the following composition for 35 seconds at 25 ° C .: Hydroquinone 0.18 mol / l 1-phenyl-4-methyl-3-pyrazolidin-1-one 4.6 mmol / l _{^{br - 21mmol / l SO 3 -}} 0.19 mol / l CO 3 - 0.44 mol / l polyglycol (molecular weight = about ^{400) 20 ml / l SCN -} 25.7mmol / l ascorbic acid 0.11 mol / L pH when using: 10.0

Comparative coating 1 was treated with developer G135 sold by Agfa-Gevaert NV at 25 ° C. for 2 minutes. The hue of the developed silver was evaluated qualitatively and quantitatively:

A. Qualitative evaluation: A visual comparison was made by comparing the resulting "HUE" with the standard "HUE" at a density of 2.5 in reflection. The number is "1"
(Brown) to "5" (black). The higher the number, the more preferred the developed silver image tone. This method evaluates the hue reflective properties of the developed material.

B. Quantitative evaluation: The ratio of the densities obtained by measuring the densities at a total density of 2.5 through transparent filters for each of blue and red light was calculated. The lower the value of this ratio "DBR", the less favorable the image tone of the developed silver. This method evaluates the hue transmission properties of the developed material.

Table I illustrates the results obtained by coating a layer closer to the support containing AgCl {111} tabular grains and adjacent to and on top of it a layer containing AgCl cubic grains. (SENS is the relative sensitivity measured at a density of 2.0 above fog level).

[0100]

[Table 1]

The following conclusions can be drawn from Table I: As is well known to those skilled in the art, the flat plate shape {11
The material containing 1} AgCl particles is the above-mentioned tabular {111} A.
Due to the high sensitivity that can be obtained with gCl particles, AgB
A very good alternative to those containing r cubic particles. However, as can be seen from Table I, the developed AgCl {111} tabular grains show a very brownish hue in reflection and transmission (Coating 2).

In many cases AgCl cubic particles are AgCl
It gives lower speeds (lower sensitivity) than {111} tabular grains and is therefore less suitable as a substitute for AgBr cubic grains. However, as can be seen from Table I, the reflective hue observed for the developed AgCl cubic particles is black, even better than the reflective hue of the developed AgBr cubic particles (Coating 3).

If AgCl {111} tabular grains are combined with AgCl cubic grains in one layer, sensitivities are obtained between the sensitivities observed for each emulsion when coated alone. Reflective and transmissive hues are also obtained between two separately coated particles (Coating 4).

If the AgCl cubic emulsion is AgCl {11
1} if coated on a tabular emulsion (Coating 5), the reflected hue for the developed material is cubic and tabular AgCl
Improved compared to the layer in which the mixture of emulsions is being made. The sensitivity remains virtually constant. Most notably, the transmission hue (DBR) is also improved.

Example 2 This example shows AgCl {1 when coated on a layer closer to the support, overcoated with an adjacent layer containing AgCl cubic crystals.
11} illustrates the improved image tone of developed silver for tabular crystals. Moreover, less silver is coated per square meter.

The coating was prepared as follows: Emulsion A
And C are dyes anhydro-5,5′-dichloro-3,
3'-bis (n-sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide and the dye anhydro-5.
Optimum spectral sensitization with a mixture of 5'-diphenyl-3,3'-bis (n-sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide, 1-phenyl-5-mercaptotetrazole and 1-p- Stabilized with an optimally selected mixture of carboxy-phenyl-5-mercaptotetrazole. To a subbed polyethylene terephthalate support having a thickness of 175 μm,
2. Each side was labeled with the equivalent weight (g) of AgNO ₃ / m ² .
Each side was coated by the slide hopper method with emulsions A and / or C according to Table II to contain 5 g / m ² and 1.25 g / m ² of gelatin.

For coating 8, a 50:50 mixture of emulsions A and C was used so that the total amount of emulsion coated on each side corresponded to an equivalent weight of 3.5 g AgNO ₃ / m ² .

For Coating 9, an equivalent of 1.75 g AgNO ₃ / m ² of AgCl {111} tabular emulsion (Emulsion C) was coated on both sides of the support. Onto each layer containing AgCl {111} tabular emulsion grains was coated an equivalent of 1.75 g AgNO ₃ / m ² of AgCl cubic emulsion (Emulsion A).

For four coatings (6-9), a protective layer was added on each side of the support. The protective layer contains 1.4 g / m ² of gelatin and is hardened with formaldehyde and resorcinol to the extent that it absorbs about 0.3 g of water per 1 g of gelatin when immersed in deionized water at 24 ° C. for 10 minutes. Was done. Samples of these coatings were exposed to 540 nm green light for 0.1 s using a continuous wedge, and Agfa-G
33 in Developer G138 sold by evaert NV
It was treated at 22 ° C for 22 seconds. The hue of the developed silver is shown in Example 1.
It was evaluated qualitatively and quantitatively as described in. Table of results
Shown in II.

[0110]

[Table 2]

As can be seen from Table II, the hues of the mixed layers of {111} tabular AgCl emulsion and cubic AgCl emulsion are such that the reflection and transmission when two emulsions are coated adjacent to both upper cubic emulsions. Both can be improved.

Example 3 In this example, the {100} tabular AgCl emulsion was {11}.
1) It is explained that the same preferable effects as those already described can be obtained when used in place of the tabular AgCl emulsion.

The coating was prepared as follows: Emulsion A
And D are dyes anhydro-5,5'-dichloro-3,
3'-bis (n-sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide and the dye anhydro-5.
Optimum spectral sensitization with a mixture of 5'-diphenyl-3,3'-bis (n-sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide, 1-phenyl-5-mercaptotetrazole and 1-p- Stabilized with an optimal mixture of carboxy-phenyl-5-mercaptotetrazole.

A subbed polyethylene terephthalate support having a thickness of 175 μm was coated with AgNO _{3 on} each side.
3.5 g / displayed as equivalents / m ² m ² and 1.
Table II, below, contains 25 g / m ² of gelatin.
Emulsions A and / or D were coated on each side by the slide hopper method according to the data given in I.

For Coating 12, a 50:50 mixture of Emulsions A and D was used so that the total amount of emulsion coated on each side was equal to 3.5 g of AgNO ₃ / m ² . For coating 13, an equivalent of 1.75 g AgNO ₃ / m ² of AgCl {100} tabular emulsion (Emulsion D) was coated on both sides of the support. 1.75 g of AgCl cubic emulsion (Emulsion A) on each layer of AgCl {100} tabular emulsion
An equivalent amount of AgNO ₃ / m ² was coated.

For four coatings (10-13), a protective layer was coated on each side. Each of the layers is 1.4 g / m
^It was hardened with formaldehyde and resorcinol to the extent that it contained about 2 g of gelatin and absorbed about 0.3 g of water per g of gelatin when immersed in deionized water at 24 ° C. for 10 minutes.

Samples of these coatings were exposed and developed as described in Example 2.

The hue of the developed silver was evaluated qualitatively and quantitatively as described in Example 1.

The results are shown in Table III.

As can be seen from Table III, the hue of the mixed layer of {100} tabular AgCl emulsion and cubic AgCl emulsion is both reflective and transmissive when the two emulsions are coated in a layer adjacent to the upper cubic emulsion. Can be improved in.

[0121]

[Table 3]

Example 4 In this example, {100} tabular A was formed in a layer closer to the support.
A containing a gCl emulsion and adjacent layer and above it
It is explained that the same preferable effect as described above can be obtained in a multilayer material including a layer containing a gBr cubic emulsion.

The coating was prepared as follows: Emulsion B
To the dye anhydro-5,5'-dichloro-3,3'-
Bis (n-sulfobutyl) -9-ethyloxacarbo-
Optimum spectral sensitization with cyanine hydroxide,
Further stabilization with hydroxy-6-methyl-1,3,3a-tetrazaindene.

Emulsion D was optimally spectrally sensitized and further stabilized as described in Example 3.

According to Table IV, a 175 μm thick subbed polyethylene terephthalate support contained 3.5 g / m ² and 1.25 g / m ² gelatin, expressed on each side as AgNO ₃ / m ^2. Emulsions B and / or D were coated on each side by the slide hopper method.

For coating 16, a 50:50 mixture of emulsions B and D was used in such a way that the total amount of emulsion coated on each side was equal to the amount of 3.5 g AgNO ₃ / m ² .

For Coating 13, an equivalent of 1.75 g AgNO ₃ / m ² of AgCl {100} tabular emulsion (Emulsion D) was coated on both sides of the support. AgBrI on top of and adjacent to the layer containing the AgCl {100} tabular emulsion.
A cubic emulsion (Emulsion B) was coated with an equivalent weight of 1.75 g AgNO ₃ / m ² .

For four coatings (14-17), a protective layer was added on each side of the support. It contained 1.4 g / m ² of gelatin and when soaked in deionized water at 25 ° C. for 3 minutes it was hardened with formaldehyde and resorcinol to the extent that it absorbed about 0.3 g of water per gram of gelatin.

Samples of these coatings were exposed and developed as described in Example 2.

The hue of the developed silver was evaluated qualitatively and quantitatively as described in Example 1.

The results are shown in Table IV.

[0132]

[Table 4]

As can be seen from Table IV, the hue of layers coated from a mixture of {100} tabular AgCl emulsions and cubic AgBr emulsions is such that if the two emulsions are cubic emulsions on top, they are coated in layers adjacent to each other. Then both reflection and transmission can be improved.

Example 5 This example illustrates when a multilayer material is made with a {111} tabular AgBr (I) emulsion coated in a layer near the support and a cubic AgCl emulsion coated in an adjacent layer above it. To improve the image tone.

The coating was prepared as follows: Emulsion A
To the dye anhydro-5,5'-dichloro-3,3'-
Bis (n-sulfobutyl) -9-ethyloxacarbo-
Cyanine hydroxide and dye anhydro-5,5'-
Diphenyl-3,3'-bis (n-sulfobutyl) -9
Spectrally sensitized with a mixture of -ethyloxacarbo-cyanine hydroxide, 1-phenyl-5-mercaptotetrazole and 1-p-carboxy-phenyl-
Stabilized with an optimal mixture of 5-mercaptotetrazole.

Emulsion E was spectrally sensitized with the dye anhydro-5,5'-dichloro-3,3'-bis (n-sulfobutyl) -9-ethyloxacarbo-cyanine hydroxide, and then 4-hydroxy-6. -Methyl-1,3,3
Stabilized with 3a, 7-tetraazaindene.

To a 175 μm thick subbed polyethylene terephthalate support, 3.5 g / m ² and 1.75 g / m ² expressed on each side as the equivalent of AgNO ₃ / m ^2.
Emulsion A according to Table V to contain m ² of gelatin
And / or E were coated on each side by the slide hopper method.

For coating 20, a 50:50 mixture of emulsions A and E was used such that the total amount of emulsion coated on each side was equal to 3.5 g AgNO ₃ / m ² .

For the coating 21, AgBr (I) {11
1} Tabular emulsion (Emulsion E) 1.75 g AgNO ₃ /
An equivalent of m ² was coated on both sides of the support. AgBr (I)
On each layer of the {111} tabular emulsion was coated an equivalent of 1.75 g AgNO ₃ / m ² of AgCl cubic emulsion (Emulsion A).

For four coatings (18-21), a protective layer was coated on top of each side of the support. The layer is 1.4g
/ M ² of gelatin. Hardening was performed with formaldehyde and resorcinol in such a range that when soaked in deionized water at 25 ° C. for 3 minutes, it absorbed about 0.3 g of water per gram of gelatin.

The coatings were exposed to 540 nm green light for 0.1 s using a continuous wedge and Agfa-Gevae.
Developer G138 sold by RT NV was processed at 33 ° C. for 22 seconds.

The developed silver hue was evaluated qualitatively and quantitatively using the same method as described above.

The results are shown in Table V.

[0144]

[Table 5]

As can be seen from Table V, if cubic AgCl
If the emulsion is coated in a layer above and adjacent to the layer containing the AgBr (I) {111} tabular emulsion (Coating 4), the reflective hue of the developed material is such that the emulsion mixture of said emulsion is It can be seen that there is an improvement compared to the layers that contain it. Quite unexpectedly, cubic AgCl and tabular Ag
The transmission hue (DBR) is also improved when compared to the hue of the layer containing the emulsion mixture of Br (I) emulsion crystals.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G03C 1/76 501 G03C 1/76 501 502 502 (72) Inventor Freddie Andric Belgian moatzel, Septestrat 27 Agfa Gewert Namrose Rose Bennault Chap

Claims (11)

[Claims] 1. A multilayer light sensitive silver halide photographic negative image material comprising a multilayer composition of at least two layers of a negative image type silver halide emulsion adjacent to each other on at least one side of the support, said support comprising: The emulsion layer closer to the body is {11
Silver chloride, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, silver bromide and silver bromoiodide having 1} crystal habit, and silver chloride, silver chlorobromide, and salt having {100} crystal habit. Comprising at least one emulsion having tabular emulsion crystals selected from the group consisting of silver iodide and silver chlorobromoiodide, the adjacent layer further from the support being composed of silver chloride, silver chlorobromide and silver bromide. A multilayered light-sensitive halogen comprising at least one emulsion having substantially cubic emulsion crystals selected from the group and wherein the halide composition of said cubic emulsion crystals or of said tabular emulsion crystals or both comprises chloride. Silver halide photographic negative image type material. 2. The tabular silver chloride, silver chlorobromide, silver chloroiodide or silver chlorobromoiodide emulsion crystals having {111} or {100} major faces have at least 50 mol% chloride. The material according to 1. 3. The tabular silver chloride, silver chlorobromide, silver chloroiodide or silver chlorobromoiodide emulsion crystals having {111} or {100} major faces have at least 75 mol% chloride. The material according to 1. 4. The tabular {111} containing iodide
Or, {100} silver halide emulsion crystals are 0.1 to 3 mo.
A material according to any of claims 1 to 3 having an iodide content of 1%. 5. The tabular silver halide emulsion has an average aspect ratio of at least 5: 1, an average grain thickness of less than 0.2 μm, and the tabular grains present in the emulsion are the total projections of the grains. A material according to any of claims 1 to 4 which describes at least 50% of the area. 6. The tabular silver halide emulsion has an average aspect ratio of at least 8: 1, an average grain thickness of less than 0.2 μm, and the tabular grains present in the emulsion are the total projections of the grains. A material according to any of claims 1 to 4 which describes at least 50% of the area. 7. The substantially cubic emulsion crystals are 0.1 to 10.
A material according to any of claims 1 to 6 having an average crystal diameter of 0.8 m. 8. The substantially cubic emulsion crystals are from 0.2 to
Material according to any of claims 1 to 6 having an average crystal diameter of 0.6 m. 9. The material according to claim 1, wherein the material is a double-sided coated X-ray material. 10. The one-side coated X-ray material according to claim 1, wherein said material is a one-side coated X-ray material having at least one backing layer on the side opposite to the side carrying the photosensitive emulsion layer. material. 11. A method comprising the steps of coating at least one side of a support with the multilayer composition according to claim 1 and overcoating the composition with at least one protective layer.
5. The method for producing a multilayer photosensitive silver halide photographic negative image-type material described in any one of 1.