DE69028895T2 - Process for developing a reversible material containing silver halide color photograph - Google Patents

Description

FIELD OF INVENTION

The invention relates to a process for developing photographic silver halide color reversal materials with excellent color reproducibility.

BACKGROUND OF THE INVENTION

Usually, a color reversal photographic material has on a support a plurality of silver halide emulsion layers having different color sensitivities, such as a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer. The color reversal photographic material which has been imagewise exposed to a polychromatic object is first subjected to black-and-white silver development in a first development step and then the remaining silver halide is color developed in a second development step through a chemical or optical fogging step to form cyan, magenta and yellow color images. A dye image usually formed on each color-sensitive layer by polychromatic exposure is different from a dye image formed by monochromatic exposure. In the case of the color reversal photographic material, this difference is mainly caused by the transfer of a development inhibitor such as iodine ions which is formed between the emulsion layers having different color sensitivities in the black-and-white development step. The difference in color level The difference in dye image between polychromatic exposure and monochromatic exposure caused by such development is called the multilayer effect or interimage effect, as described in Hudson and Horton, Journal of the Optical Society of America, 42 (No. 9), pp. 663 to 669 (1976), and is known to improve sharpness and color reproducibility.

As a technique for enhancing the multilayer effect, JP-A-51-128528 (the term "JP-A" as used herein means an unexamined published Japanese patent application) discloses a method for enhancing the multilayer effect imparted to a sensitive silver halide emulsion layer by introducing an emulsion in which the surfaces of silver halide grains are fogged into the sensitive silver halide emulsion layer.

Research Disclose, No. 13553 (1975) also discloses a process for applying the preferable multilayer effect by iodine ions in a color reversal photographic material, comprising adding an emulsion containing a silver halide to release the iodine ion such as AgBrI, AgClI or AgBrClI to at least one layer to which the multilayer effect is applied, adding a hydrophilic colloid as well as ordinary emulsion grains to at least one layer to which the multilayer effect is imparted, and further adding another surface fog emulsion. However, the above-described references do not fully disclose the features of the more preferable sensitive silver halide emulsion in enhancing the multilayer effect using the fog emulsion.

In the black-and-white development step of the color reversal photographic material, the sensitive silver halide emulsion is developed depending on the exposure amount. At this time, the undeveloped silver halide emulsion grains are subjected to color development processing via the fogging step. This color development step is required to develop all the remaining silver halide to develop color, so that its development activity is said to be high. For this reason, it is essentially mostly impossible to perform the function of the multi-layer effect in the color development step, and in color reversal photographic materials, the multi-layer effect is largely determined by the black-and-white development step.

At this stage of black and white development, the developing solution has the effect of dissolving the emulsion grains. This solubility is controlled by the iodine ions diffused during development of the other layers, thus obtaining the multilayer effect.

Although the multilayer effect is generated by many mechanisms, the most important mechanism is the above.

The emulsion-dissolving effect of this developing solution is increased as the development time increases. Therefore, when the processing time of the black-and-white development step is short, it is difficult to apply the sufficient multilayer effect to conventional color reversal photographic materials, compared to the case where the processing time is long.

EP-A-0 272 675 describes a silver halide photographic material comprising a support having thereon at least one silver halide emulsion layer composed of one or more layers, wherein the silver halide emulsion which contained in at least one layer of the silver halide emulsion layer is chemically sensitized so that silver halide grains in the emulsion have at least one maximum value for the distribution of the number of latent image inside the silver halide grains and the position where the maximum value(s) exists is at a depth of less than 0.01 µm from the surface of the grains, and the emulsion also has a number of latent image of at least 1/5 of the largest maximum value but less than the largest maximum value on the surface of the grains.

US-A-4 804 616 describes a method for continuously processing a color reversal photographic material. After black and white development, the color reversal photographic material is rinsed in a bath in which the replenishment amount per unit area of the photographic material is 3 to 50 times the amount of the processing solution carried over from the previous bath in terms of volume ratio and the pH is 9.5 or less.

US-A-4 839 268 describes a silver halide color reversal photosensitive material comprising a plurality of silver halide emulsion layers on a support, wherein 50% or more of the total projected area of the silver halide grains contained in at least one of the silver halide emulsion layers is occupied by tabular silver iodobromide grains having an average thickness of 0.5 microns or less, an average diameter of 0.5 microns or more, an average aspect ratio of at least 5/1 and a silver iodide content of 4.0 mol% or less, and the tabular silver iodobromide grains are negative-type silver halide grains which form a latent image mainly within the grains.

CONTENT OF THE INVENTION

It is therefore an object of the invention to provide a method which gives a sufficient multi-layer effect even in a processing in which the black-and-white development time is short.

The object of the invention is achieved by a method for developing a silver halide color reversal photographic material comprising a support having thereon at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, wherein at least one silver halide emulsion layer contains tabular silver halide grains having an aspect ratio of at least 5; which have at least 50% of all silver halide grains present in the same layer as a projection area, and which have an average sphere-corresponding grain size of 0.30 µm or less, comprising developing the color reversal photographic material with a black-and-white developing solution for 100 seconds or less.

DETAILED DESCRIPTION OF THE INVENTION

It is preferable that the average sphere grain size of the silver halide emulsion grains contained in at least one emulsion layer is 0.25 µm or less. The lower limit thereof is preferably 0.1 µm from the viewpoint of sensitivity.

The measuring methods for the mean sphere size of silver halide grains are described in detail, for example, in James, The Theory of Photographic Process, 4th edition, page 100. Such methods include methods which use an optical microscope, an electron microscope and a Coulter counter. When the size of such a degree as the size of the emulsion grains of the invention is measured, a method is preferably used in which the thickness of the grains is determined from the projected area of the grains and the length of shadows obtained by shadowing using an electron microscope, the volume of each grain is determined therefrom, and the average grain size corresponding to a sphere is determined from the average value thereof.

As silver halide grains used in the invention, monodisperse emulsions having a narrow grain size distribution or polydisperse emulsions having a wide grain size distribution can be used.

In the invention, at least one sensitive emulsion layer contains the tabular silver halide emulsion grains having an average sphere-like grain size of 0.30 µm or less and an aspect ratio of at least 5 so that at least 50% of all the silver halide grains in the same layer exist as a projection area. It is further preferred that at least one layer contains tabular silver halide emulsion grains having an aspect ratio of at least 8 so that at least 50% of all the silver halide grains existing in the same layer are occupied as a projection area. The aspect ratio referred to here means the ratio of diameter to thickness of the emulsion grain.

Furthermore, the diameter of the silver halide grain means the diameter of a circle whose area is equal to the projected area of the grain. In general, the tabular silver halide grain has two planes parallel to each other, and the thickness referred to here is represented by the distance between the parallel planes which make up the tabular silver halide grain.

Any of silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and silver chloride can be used for the tabular silver halide grains. However, silver bromide and silver iodobromide are preferably used. In particular, it is preferred that silver iodobromide having a silver iodide content of 0.01 to 30 mol%, preferably 0.5 to 10 mol%, is used.

Methods for preparing the tabular silver halide grains are described below.

The tabular silver halide grains can be prepared by suitable combinations of processes known in the art.

For example, tabular silver halide grains can be obtained by simultaneously adding silver and a halogen solution while keeping the pBr value relatively low at 1.3 or less.

The size of the tabular silver halide grains can be controlled by temperature control, selection of the type or amount of solvent, selection of the type of silver salt used in grain growth and control of the addition rate of the halide.

When preparing the tabular silver halide grains of the invention, solvents for silver halides can be used as required.

Commonly used solvents for silver halides include ammonia, thioethers and thiourea compounds. Regarding the thioethers, reference may be made to U.S. Patents 3,271,157, 3,790,387 and 3,574,628.

In addition, preparation processes for tabular silver halide grains are described in Gutoff, Photographic Science and Engineering, Volume 14, pages 248 to 257 (1970), US-A-4,434,266, 4,414,310, 4,433,048 and 4,439,520 and GB-B-2,112,157.

The above-described at least one sensitive emulsion layer means at least one of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer. Each of the above-described emulsion layers may be composed of a plurality of layers having similar spectral sensitivity as long as at least one of such layers satisfies the above-described requirements. However, a low-sensitivity emulsion layer is preferably used from the viewpoint of sensitivity. If a yellow colloidal silver layer is included, it is preferable that an emulsion layer in closest proximity thereto satisfies the above-described requirements.

This yellow colloidal silver can be produced by various known processes.

S. Inoue, Preparative Experiments of Inorganic Chemistry, page 647, discloses the method for reducing silver nitrate with dextrin under alkaline conditions, the method for reducing silver nitrate with tannin under alkaline conditions, the method for reducing silver nitrate with hydrazine and the method for reducing silver oxide with Sodium carbonate and hydrogen peroxide in the presence of silver sol, reduced with phosphorus.

The silver halide grains used in the invention, which are different from the tabular silver halide grains having an average spherical grain size of 0.30 µm or less and an aspect ratio of at least 5, are described below. The silver halide grains may have a regular crystal form such as a cubic, an octahedral or a tetradecahedral form, an irregular crystal form such as a spherical or a tabular form, crystalline defects such as a twin plane, or a composite form thereof.

The silver halide grains may be fine grains having a grain size of about 0.2 µm or less or large grains having a projected area diameter of up to about 10 µm. The silver halide grains may be used as a monodisperse emulsion or a polydisperse emulsion. A monodisperse emulsion having a variation coefficient of not more than 20% is preferably used.

Such silver halide photographic emulsions can be prepared using the procedures described in Research Disclosure, No. 17643, pages 22 and 23, I. "Emulsion Preparation and Types" (December 1978), ibid., No. 18716 (November 1979), P. Glafkides, Chimie et Physique Photographique, (Paul Montel, 1967), G.f. Duffin, Photographic Emulsion Chemistry (Focal Press 1966), and V.L. Zelikman et al., Making and Coating Photographic Emulsion (Focal Press 1964).

The monodisperse emulsions described in US-A-3 574 628 and 3 655 394 and GB-B-1 413 748 are also preferably used.

The silver halide emulsions used in the photographic materials of the invention are generally subjected to physical ripening, chemical ripening and spectral sensitization and then used. The emulsion grains described above may be of the so-called surface latent image type in which latent images are mainly formed on the surface of the grains; or of the so-called internal latent image type in which latent images are mainly formed in the interior of the grains. The additives used in such steps are described in Research Disclosure, No. 17643 and ibid., No. 18716, and the corresponding parts are summarized in a table below.

The crystal structure may be uniform, or the inside and outside of the grain may be composed of different halogen compositions. The crystal structure may also be a laminar structure. Silver halides that are different in composition may be connected by an epitaxial linkage. Furthermore, silver halides may be connected to compounds other than silver halides, such as silver rhodanine and lead oxide.

Mixtures of grains with different crystal shapes can be used.

Known photographic additives which can be used in the invention are also described in the two Research Disclosure references above, and the corresponding parts are shown in the table given later.

In addition to phenol, phenoxyethanol compounds, p-hydroxybenzoic acid butylate, Proxel (benzoisothiazoline) and sodium salicylate can be used as preservatives.

Various color couplers can be used in the invention. Specific examples thereof are described in the patent specifications cited in Research Disclosure No. 17643, VII-C to G, described above.

As yellow couplers, preferably those described for example in US-A- 3 933 501, 4 022 620, 4 326 024 and 4 401 752, JP-B-58-10739 (the term "JP-B" as used herein means an "examined Japanese patent publication"), GB-B-1 425 020 and 1 476 760.

As magenta couplers, 5-pyrazolone and pyrazobazole compounds are preferably used, and particularly preferred compounds are described in US-A-4,310,619 and 4,351,987, EP-A-73,636, US-A-3,061,432 and 3,725,067, Research Disclosure, No. 24220 (June 1984), JP-A-60-33552, Research Disclosure, No. 24230 (June 1984), JP-A-60-43659, US-A-4,500,630 and 4,540,654.

Cyan couplers include phenol and naphthol compounds, and preferably used are the compounds described in US-A-4 052 212, 4 146 396, 4 228 233, 4 296 200, 2 369 929, 2 801 171, 2 772 162, 2 895 826, 3 772 002, 3 758 308, 4 334 011 and 4 327 173, DE-A-3 329 729, EP-A-121 365, US-A- 3 446 622, 4 333 999, 4 451 559 and 4 427 767 and EP-A-161 626 are described.

As couplers which give dyes with suitable diffusivity, the compounds described in US-A-4 366 237, GB-B-2 125 570, EP-B-96 570 and DE-A-3 234 533 are preferably used.

Typical examples of polymerized dye-forming couplers are described in US-A-3,451,820, 4,080,211 and 4,367,282 and GB-B-2,102,173.

Couplers which release photographically useful residues upon coupling can also be preferably used in the invention. As DIR couplers which release development inhibitors, those described in JP-A-57-151944, JP-A-57-154234, JP-A-60-184248 and US Patent 4,248,962 mentioned in the above-described Research Disclosure, No. 17643, Item VII-F, are preferred.

As couplers which release nucleating agents or development accelerators in the form of images during development, the compounds described in GB-B-2 097 140 and 2 131 188, JP-A-59-157638 and JP-A-59-170840 are preferably used.

Other couplers which can be used for the photographic materials of the invention include the competitive couplers described in US-A-4,130,427, the multiequivalent couplers described in US-A-4,283,472, 4,338,393 and 4,310,618, the couplers which release DIR redox compounds described in JP-A-60-185950, and the couplers which release dyes recolored after separation described in EP-A-173,302.

The couplers used in the invention can be incorporated into the photographic materials by various known dispersion methods.

Examples of high boiling solvents which can be used for the oil-in-water dispersion process are described in US-A-2 322 027.

The steps and effects of the latex dispersion processes and Specific examples of latexes for impregnation are described in US-A-4 199 363, DE-A-2 541 274 and 2 541 230.

The photographic materials used in the invention may preferably include hydroquinones which release the development-inhibiting compound described in US-A-3,379,529 and 3,639,417 and the naphthohydroquinones which release the development-inhibiting compound described in Research Disclosure, No. 18264 (June 1979).

Suitable supports which can be used in the invention are described, for example, in the above-described Research Disclosure, No. 17643, page 28, and ibid., No. 18716, right column, page 647, to left column, page 648.

Process solutions and process steps for the photographic color reversal materials according to the invention are described below.

The first development step (black-and-white development) for the color reversal photographic materials of the present invention is carried out for 100 seconds or less. If this step is carried out for 60 seconds or less, the effect of the present invention becomes more remarkable. It is preferable from the viewpoint of productivity that the first development time is shorter.

Among the process steps for the color reversal photographic materials of the present invention, the steps from black-and-white development (first development) to color development are as follows:

1. Black and white development - washing - color reversal development.

2. Black and white development - washing - optical reversal color development.

3. Black and white development - washing - color development.

Any of the washing steps of processes 1 to 3 can be replaced by the rinsing step described in US-A-4 804 616 to To simplify processing and reduce the amount of waste liquids.

The stages after color development are described below.

4 Color development - compensation - bleaching - fixing - washing - stabilizing.

5. Color development - washing - bleaching - fixing - washing - stabilizing.

6. Color development - compensation - bleaching - washing - fixing - washing - stabilizing.

7. Color development - washing - bleaching - washing - fixing - washing - stabilizing.

8. Color development - bleaching - fixing - washing - stabilizing.

9. Color development - bleaching - bleach-fixing - washing - stabilizing.

10. Color development - bleaching - bleach-fixing - fixing - washing - stabilizing.

11. Color development - bleaching - washing - fixing - washing - stabilizing.

12. Colour development - compensation - Bleach-fix - Wash - Stabilize.

13. Colour development - washing - bleach-fixing - washing - stabilising.

14. Colour development – bleach-fixing – washing – stabilising.

15. Color development - fixing - bleach-fixing - washing - stabilizing.

In processing methods 4 to 15, the washing steps may be eliminated just before the stabilization steps and the final stabilization steps may not be performed. Any of methods 1 to 3 described above is combined with any of methods 4 to 15 to form a color reversal process.

The processing solutions used in the color reversal processes of the invention are described below.

For the black-and-white developing solutions, known black-and-white developing agents can be used alone or in combination. Such developing agents include dihydroxybenzenes such as hydroquinone; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone; aminophenols such as N-methyl-p-aminophenol; 1-phenyl-3-pyrazolin; ascorbic acid; and heterocyclic compounds such as a condensed compound of a 1,2,3,4-tetrahydroquinoline ring and an indoline ring as described in US-A-4,067,872.

The black-and-white developing solutions used in the invention may contain hardening agents such as sulfites and bisulfites; buffers such as carbonates, boric acid, borates and alkanolamines; alkali agents such as hydroxides and carbonates; solubilizing aids such as polyethylene glycol and esters thereof; water softeners such as aminopolycarboxylic acids and organic phosphonic acids; pH Regulators, e.g. organic acids such as acetic acid; sensitizers such as quaternary ammonium salts; development accelerators; surfactants; antifoaming agents; hardening agents; antifogging agents such as potassium iodide, potassium bromide and benzotriazole; and viscosity-imparting agents, if necessary.

Although the black-and-white developing solutions used in the invention are required to contain compounds that act as solvents for silver halides, the sulfites added as preservatives described above generally play their role. Specific examples of sulfites include K₂SO₃, Na₂SO₃, K₂S₂O₅, Na₂S₂O₅, K₂S₂O₃ and Na₂S₂O₃.

In the invention, it is preferred that this black-and-white developing solution contains at least one kind of thiocyanate. Particularly preferred examples of thiocyanate include potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate. The content of these compounds is preferably 0.01 to 50 g/l, and more preferably 0.05 to 10 g/l.

The pH of the black and white developing solutions is selected to provide a desired density and contrast and is in the range of about 8.5 to about 11.5.

Reversal baths used after black and white development may contain fogging agents known in the art. Such fogging agents include tin ion complex salts such as stannous ion-organic phosphoric acid complex salts (US-A-3 617 282), stannous ion-organic phosphonocarboxylic acid complex salts (JP-B-56-32616) and stannous ion-aminopolycarboxylic acid complex salts (GB-B-1 209 050); and boron compounds such as hydrogenated boron compounds (US-A-2 984 567) and heterocyclic amine borane compounds (British Patent 1 011 000). The pH of the fog baths (reversal baths) extends over a wide range from an acidic side to a basic side from 2 to 12, preferably 2.5 to 10 and especially 3 to 9. Instead of using the reversal bath, optical reversal processing by re-exposure can be carried out. Furthermore, the reversal step can be omitted by adding the fogging agents described above to the color developing solutions.

Aromatic primary amine color developing agents can be used in the color developing solutions in the invention. p-Phenylenediamine derivatives are preferred. Typical examples of them are given below, but the p-phenylenediamine derivatives are not limited thereto.

D-1: N, N-diethyl-p-phenylenediamine

D-2: 2-Amino-5-diethylaminotoluene

D-3: 2-Amino-5-(N-ethyl-N-laurylamino)toluene

D-4: 4-[N-Ethyl-N-(β-hydroxyethyl)amino]aniline

D-5: 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline

D-6: 4-Amino-3-methyl-N-ethyl-N-[β-methanesulfonamide)ethyl]anilinine

D-7: N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide

D-8: N,N-Dimethyl-p-phenylenediamine

D-9: 4-Amino-3-methyl-N-ethyl-N-methoxyethyl aniline

D-10: 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline

D-11: 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline

Of the p-phenylenediamine derivatives described above, the compounds D-2, D-4, D-5 and D-6 are particularly preferred.

These p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The above aromatic primary amine developing agents are preferably used in an amount of about 0.1 to about 20 g, in particular in an amount of about 0.5 to 15 g, per liter of developing solution.

In the invention, a color developing solution which is substantially free from benzyl alcohol can be used. The color developing solution substantially free from benzyl alcohol means a color developing solution which contains benzyl alcohol at a concentration of not more than 3 x 10⊃min;2 mol per liter of developing solution, preferably free from benzyl alcohol.

The sulfites contained in the color developing solutions used in the invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite. The amount of the sulfites added to the developing solutions is preferably 1 x 10-5 to 5 x 10-2 mol, more preferably 1 x 10-4 to 5 x 10-2 mol, and most preferably 1 x 10-4 to 2 x 10-2 mol, per liter of the developing solution.

In addition, preservatives, various metals as described in JP-A-57-44148 and JP-A-57-53749, salicylic acids as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, polyethyleneimines as described in JP-A-56-94349, and aromatic polyhydroxy compounds as described in U.S. Patent 3,746,544 may be contained as necessary. In particular, the aromatic polyhydroxy compounds are preferably added.

The pH of the developing solutions used in the invention is preferably 9 to 14, particularly 9 to 13. Other known constituent compounds of the color developing solutions may be added to the color developing solutions.

It is preferable to use different buffers to maintain the pH described above.

Specific examples of buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2hydroxybenzoate (potassium 5-sulfosalicylate). However, the buffers used in the invention are not limited to these compounds.

The buffers described above are added to the color developing solutions preferably in an amount of at least 0.1 mol/l, especially in an amount of 0.1 to 0.4 mol/l.

Various gelling agents can be used in the color developing solutions as suspending agents for calcium or magnesium or to improve the stability of the color developing solutions.

As the gelling agent, organic acid compounds are preferably used. Examples of gelling agents include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenediphosphonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminepropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and N,N'- Bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid are examples of gelling agents. Two or more kinds of these gelling agents may be used in combination if necessary.

These gelling agents can be added in any amount, as long as the amount is sufficient to block metal ions in the color developing solutions. For example, they are added in an amount of about 0.1 to about 10 g/L.

Any color development accelerators may be added to the color development solutions if required. Such development accelerators include p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554, quaternary ammonium salts described in JP-A-50-137726, JP-B-44- 30074, JP-A-56-156826 and JP-A-52-43429, amine compounds described in US-A-2 494 903, 3 128 182, 4 230 796 and 3 253 919 and JP-B-41-11431, US-A-2 482 546, 2 596 926 and 3 582 346, polyalkylene oxides described in JP-B-37-16088, JP- B-42-25201, US-A-3 128 183, JP-B-41-11431, JP-B-42-23883 and 3 532 501, 1-phenyl-3-pyrazolidone compounds and imidazole compounds.

In the invention, any antifoggants may be added if necessary. As the antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants may be added. Typical examples of organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzoimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solutions used in the invention may contain fluorescent brightening agents. As fluorescent brightening agents, 4,4'-diamino-2,2'-disulfostilbene compounds are preferably used. They are added in an amount of 0 to 5 g/l, preferably in an amount of 0.1 to 4 g/l.

Other various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids and aromatic carboxylic acids may be added if desired.

The processing temperature of the color developing solutions of the present invention is 20 to 50°C, and preferably 30 to 40°C. The processing time is 20 seconds to 8 minutes, and preferably 30 seconds to 6 minutes. It is preferable to reduce the replenishment rate of the color developing solutions to a minimum. However, the replenishment rate is 100 to 3,000 ml/m² of the photographic material, preferably 100 to 2,500 ml/m², and more preferably 100 to 2,000 ml/m².

The color developing bath can be divided into two or more baths if necessary, and the front and rear baths can be refilled with the color developing solution to shorten the developing time and reduce the replenishment rate.

Furthermore, the color developing solutions used in the invention can contain so-called competing compounds, such as citrazinic acid, J-acid and H-acid, for the purpose of controlling the gradient, which react with the oxidation product of the color developing agents to form colorless compounds.

In the invention, the photographic materials are subjected to bleach processing or bleach-fix processing after color development. This processing may be carried out immediately after color development without any other processing steps, or after the processing steps such as finishing, compensation and washing after the color development step.

Solutions used for the compensation described above may contain aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; sulfites such as sodium sulfite and ammonium sulfite; and bleach accelerators such as thioglycerin, aminoethanethiol and sulfoethanethiol. For the purpose of preventing foaming, it is preferred that the compensating solutions contain sorbitan esters of fatty acids substituted with ethylene oxide as described in U.S. Patent 4,839,262 or polyethylene compounds as described in U.S. Patent 4,059,446 and Research Disclosure, Vol. 191, No. 19104 (1980).

Bleaching agents used in the bleaching solutions and/or bleach-fixing solutions include ferric complex salts of aminopolycarboxylic acids and peroxide such as sodium persulfate. In particular, the ferric complex salts of aminopolycarboxylic acids are preferably used. Preferred examples of aminepolycarboxylic acids of such ferric complex salts include ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, cyclohexanediaminetetraacetic acid, 1,4-diaminobutanetetraacetic acid, 1,2-propylenediaminetetraacetic acid, thioglycol ether diaminetetraacetic acid, 1,3-butylenediaminetetraacetic acid and methyliminodiacetic acid.

The bleaching agents described above are used in an amount of 0.05 to 1 mole per litre of bleaching solution or bleach-fixing solution and preferably in an amount of 0.1 to 0.5 mole. In addition to the above-described complex salts of iron (III) with the aminopolycarboxylic acids, aminopolycarboxylates may be added to the bleaching solutions and/or the bleach-fixing solutions used in the invention.

The aminopolycarboxylates are preferably added in an amount of 0.0001 mol to 0.1 mol/l and in particular in an amount of 0.003 to 0.05 mol/l.

It is preferred that the aminopolycarboxylates and their remote complex salts are usually used in the form of alkali metal salts. In particular, ammonium salts are preferred because of their excellent solubility and bleaching ability.

Various bleaching accelerators can be added to the bleaching solutions and/or bleach-fixing solutions used in the invention.

As such bleaching accelerators, for example, compounds containing a mercapto group or disulfide group are preferably used, as described in US-A-3 893 858, DE-C-1 290 812, GB-B-1 138 842, JP-A-53-95630 and Research Disdosure, No. 17129 (July 1978).

The bleaching accelerators are added in an amount of 0.01 to 20 g per liter of the solution with bleaching ability, preferably in an amount of 0.1 to 10 g.

The bleaching solutions and/or bleach-fixing solutions used in the invention may contain rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide and ammonium bromide) and chlorides (e.g. potassium chloride, sodium chloride and ammonium chloride) in addition to the bleaching agents and the compounds described above. The concentration of the rehalogenating agents is 0.1 to 5 moles per liter of bleaching solution, preferably 0.5 to 3 moles. In addition, known additives which are usually used in bleaching solutions may be added, e.g. nitrates such as sodium nitrate and ammonium nitrate; and one or more kinds of inorganic acids, organic acids and their salts having a pH buffering ability, such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphoric acid, phosphorous acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.

The bleach-fix solutions and/or fixing solutions used in the invention may contain thiosulfates as fixing agents. The thiosulfates are added in an amount of 0.1 to 3 mol/l, preferably in an amount of 0.3 to 2 mol/l.

The thiosulfate compounds include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate and magnesium thiosulfate. In particular, ammonium thiosulfate is preferably used due to its good solubility and highest fixation rate.

In addition to the thiosulfate compounds described above, thiocyanic acid compounds (particularly their ammonium salt), thiourea, thioether, urea and the like can be used as fixing agents or fixing accelerators for the bleach-fixing solutions and/or the fixing solutions used in the invention. The total concentration of these additional fixing agents or fixing accelerators and the thiosulfate compounds is 1.11 to 3.0 mol/l, preferably 1.4 to 2.8 mol/l.

The bleach-fixing solutions and/or fixing solutions used in the invention may contain sulfites such as sodium sulfite, potassium sulfite and ammonium sulfite, hydroxylamine and hydrazine as preservatives. Furthermore, they may contain various fluorescent brightening agents, antifoaming agents, surfactants and organic solvents such as polyvinylpyrrolidone and methanol. In particular, it is preferred that the sulfinic acid compounds described in JP-A-62-143048 be used as preservatives.

Furthermore, for the purpose of stabilizing the solutions, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the solutions. In particular, 1-hydroxyethylidene-1,1-diphosphonic acid is effective. These compounds are added in an amount of 0.01 to 0.3 mol/l, preferably in an amount of 0.05 to 0.2 mol/l, which is particularly effective in the fixing solutions.

The pH of the bleaching solutions and/or the bleach-fixing solutions used in the invention is generally 1 to 9, preferably 1.5 to 7.5, and especially 2.0 to 7.0. In particular, it is preferred that the pH of the bleaching solutions is 2.0 to 5.0. Within the preferred pH range, little fogging occurs during bleaching, and the silver-removing property is also excellent.

The pH of the fixing solutions used in the invention is usually 5.0 to 9.0, particularly 5.5 to 7.5.

Known additives may be added to the rinse water used in the washing step as desired. For example, water softeners such as inorganic phosphoric acid compounds, aminopolycarboxylic acids and organic phosphoric acid compounds; Disinfectants and antifungal agents to prevent the proliferation of bacteria and duckweed, such as isothiazolone, organic chlorine disinfectants and benzotriazole, may be added; and surfactants to prevent drought stress and unevenness. The compounds described in LE West "Water Quality Criteria", Phot. Sci. and Eng. 9, No. 6, 343-359 (1965) may also be used.

Process solutions for stabilizing color images are used as stabilizing solutions used in the stabilizing step. For example, solutions having a pH of 3 to 6 and a buffering ability and solutions containing aldehydes such as glutaraldehyde can be used. Formalin is unfavorable for environmental pollution reasons. In the stabilizing solutions, ammonium compounds, metal compounds such as Bi and Al, fluorescent brightening agents, gelling agents such as EDTA and 1-hydroxyethylidene-1,1-diphosphonic acid, disinfectants, antifungal agents, hardening agents, surfactants and the like can be used. Thiazolone compounds such as 5-chloro-2-methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one are effective as antifungal agents.

In order to prevent the thiosulfate ions introduced into the stabilizing solutions from forming sulfur with the photographic materials, alkanolamines are preferably added to the stabilizing solutions.

The pH of the stabilizing solutions used in the invention is 3 to 8, preferably 5 to 7. The temperature of the stabilizing solutions is preferably 5 to 45°C, especially 10 to 40°C. It is preferred that a multi-stage countercurrent process is used as the washing step or stabilizing step. The number of steps is preferably 2 to 4.

Two or more kinds of stabilizing solutions can be used in the multiple stage. The replenishment rate is 1 to 50 times, preferably 2 to 30 times, particularly 2 to 15 times the amount of the solution introduced from the previous bath per unit area.

As the water used in the washing step or stabilization step, water that has been deionized with an ion exchange resin to a calcium and magnesium concentration of 5 mg/L or less and water that has been sterilized with a bactericidal halogen lamp or a bactericidal ultraviolet lamp are preferred, in addition to tap water.

The invention is described in more detail with reference to the following examples, which, however, are not intended to limit the invention.

EXAMPLE 1 (Emulsion A)

Cubic silver iodobromide grains (silver iodide: 2.5 mol%) were prepared by the controlled double jet method in the presence of ammonia. The mean sphere-like grain size of the resulting grains was 0.35 µm. The grains were subjected to chemical sensitization using gold and sulfur simultaneously. The resulting emulsion was referred to as Emulsion A. 60 wt.% of the emulsion grains had grain sizes within 18% of the mean grain size.

(Emulsion B)

A cubic grain emulsion having an average sphere-like grain size of 0.27 µm was prepared by adjusting the temperature at which the grains of Emulsion A were formed. The resulting grains were silver iodobromide grains containing 2.5 mol% silver iodide.

60 wt.% of the emulsion grains had grain sizes within 15% of the mean grain size.

(Emulsion C)

To 1 L of water, 30 g of gelatin and 10.3 g of potassium bromide were added, and then solutions I and II shown in Table 1 were added simultaneously while stirring for 15 minutes in a vessel at 60°C.

In the resulting tabular silver halide grains, 53% of all grains in projected area were composed of grains having an aspect ratio of at least 5, and the silver iodide content was 2.5 mol%.

This emulsion was subjected to chemical sensitization using gold and sulfur simultaneously. The silver halide emulsion thus obtained was designated Emulsion C. The grains of Emulsion C had an average sphere size of 0.35 µm. TABLE 1

By adjusting the temperature at which the grains of the emulsion C were formed, the emulsion D was obtained which had an average sphere-like grain size of 0.28 µm, in which 53% of all the grains as a projected area were composed of grains having an aspect ratio of at least 5 and containing 2.5% of silver iodide.

(Emulsion E)

By adjusting the temperature at which the grains of the emulsion D were formed, the emulsion E was obtained which had an average sphere-like grain size of 0.21 µm, in which 53% of all the grains as a projected area were composed of grains having an aspect ratio of at least 5, and which contained 2.5% of silver iodide.

(Emulsion F)

By adjusting the temperature at which the grains of the emulsion E were formed, the emulsion F was obtained which had an average sphere-like grain size of 0.21 µm, in which 55% of all the grains as a projected area were composed of grains having an aspect ratio of at least 8, and which contained 2.5% of silver iodide.

Phenoxyethanol was added to emulsions A to F as a preservative in an amount of 40,000 ppm based on gelatin.

(Production of photographic material)

A paper support laminated with polyethylene on both sides was coated with the following first to twelfth layers to prepare a multilayer color photographic material and designated as Sample 101. The polyethylene on the side of the first layer to be coated contained titanium oxide as a white pigment and a small amount of ultraviolet as a blue dye.

The composition of each sensitive layer is shown below. The numbers for the components show the amounts coated in g/m². The numbers for the silver halides show the amounts coated converted to silver.

First layer (gelatin layer)

Gelatine 1.30

Second layer (antihalation layer)

Black colloidal silver 0.10

Gelatin 0.70

Third layer (red-sensitive layer with low sensitivity)

Silver iodobromide EMI (silver iodide:

4 mol%, average grain size 0.4 µm, cubic), spectrally sensitized with the red sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.06

Silver iodobromide EM2 (silver iodide:

5 mol%, average grain size 0.50 µm, cubic), spectrally sensitized with the red sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.10

Gelatin 1.00

Cyan coupler (ExC-1) 0.14

Cyan coupler (ExC-2) 0.07

Anti-fading agents (Cpd-2, Cpd-3,

Cpd-4 and Cpd-9 in equivalent amounts) 0.12

Dispersion medium (Cpd-5) for the coupler 0.03

Solvents (Solv-1, Solv-2 and Solv-3) for the coupler 0.06

Fourth layer (red-sensitive layer with high sensitivity)

Silver iodobromide EM3 (silver iodide: 6 mol%, average grain size 0.75 µm, twin), spectrally sensitized with the red sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.15

Gelatin 1.00

Cyan coupler (ExC-1) 0.20

Cyan coupler (ExC-2) 0.10

Anti-fading agents (Cpd-2, Cpd-3, Cpd-4 and Cpd-9 in equivalent amounts) 0.15

Dispersion medium (Cpd-5) for the coupler 0.03

Solvents (Solv-1, Solv-2 and Solv-3) for the coupler 0.10

Fifth layer (intermediate layer)

Yellow colloidal silver 0.02

Gelatin 1.00

Color mixing inhibitor (Cpd-6 and Cpd-7) 0.08

Solvents (Solv-4 and Solv-5) for the color mixing inhibitor 0.16

Polymer latex (Cpd-8) 0.10

Sixth layer (low-sensitivity green-sensitive layer)

Emulsion A, spectrally sensitized with the green sensitizing dye (ExS-4) 0.10

Gelatin 0.80

Magenta coupler (EXM-1) 0.05

Magenta coupler (EXM-2) 0.05

Anti-fading agent (Cpd-9) 0.10

Stain inhibitor (Cpd-10) 0.01

Stain inhibitor (Cpd-11) 0.001

Stain inhibitor (Cpd-12) 0.01

Dispersion medium (Cpd-5) for the coupler 0.05

Solvent (Soly-4 and Solv-6) for the coupler 0.15

Seventh layer (green-sensitive layer with high sensitivity)

Silver iodobromide EM4 (silver iodide:

3.5 mol%, average grain size: 0.6 µm, twin), spectrally sensitized with the green sensitizing dye (ExS-4) 0.10

Magenta coupler (EXM-1) 0.05

Magenta coupler (EXM-2) 0.05

Anti-fading agent (Cpd-9) 0.10

Stain inhibitor (Cpd-10) 0.01

Stain inhibitor (Cpd-11) 0.001

Stain inhibitor (Cpd-12) 0.01

Dispersion medium (Cpd-5) for the coupler 0.05

Solvents (Solv-4 and Solv-6) for the coupler 0.15

Eighth layer (yellow filter layer)

Yellow colloidal silver 0.20

Gelatin 1.00

Color mixing inhibitor (Cpd-7) 0.06

Solvents (Solv-4 and Solv-5) for the color mixing inhibitor 0.15 Polymer latex (Cpd-8) 0.10

Ninth layer (blue-sensitive layer with low sensitivity)

Silver iodobromide EMS (silver iodide: 2.5 mol%, average grain size: 0.40 µm, cubic), spectrally sensitized with the blue sensitizing dyes (ExS-5 and ExS-6) 0.07

Silver iodobromide EM6 (silver iodide: 2.5 mol%, average grain size: 0.45 µm, cubic), spectrally sensitized with the blue sensitizing dyes (ExS-5 and ExS-6) 0.10

Gelatin 0.50

Yellow coupler (ExY-1) 0.20

Stain inhibitor (Cpd-11) 0.001

Anti-fading agent (Cpd-6) 0.10

Dispersion medium (Cpd-5) for the coupler 0.05

Solvent (Solv-2) for the coupler 0.05

Tenth layer (blue-sensitive layer with high sensitivity

Silver iodobromide EM7 (silver iodide:

2.5 mol%, average grain size 1.2 µm, twin), spectrally sensitized with the blue sensitizing dyes (ExS-5 and ExS-6) 0.25

Gelatin 1.00

Yellow coupler (ExY-l) 0.40

Stain inhibitor (Cpd-11) 0.002

Anti-fading agent (Cpd-6) 0.10

Dispersion medium (Cpd-5) for the

Coupler 0.15

Solvent (Solv-2) for the coupler 0.10

Eleventh layer (absorption layer for ultraviolet light)

Gelatine 1.50

Absorbers for ultraviolet

Light (Cpd-1, Cpd-3 and Cpd-13) 1.00

Color mixing inhibitor (Cpd-6 and Cpd-14) 0.06

Dispersion medium (Cpd-5) 0.15

Solvent (Solv-1 and Solv-2) for the ultraviolet light absorber 0.15

Irradiation-preventing dye (Cpd-15 and Cpd-16) 0.02

Irradiation-preventing dye (Cpd-17 and Cpd-18) 0.02

Twelfth layer (protective layer)

Fine silver chlorobromide grains

(Silver chloride: 97 mol-%, average

Grain size: 0.2 µm) 0.07

Modified Poval 0.02

Gelatine 1.50

Gelatin hardener (H-1) 0.17

Further, Alkanol XC (Du Pont de Nemours Co.) and sodium alkylbenzenesulfonate were added as emulsifying dispersion aids and a succinic acid ester and Magefac F-120 (Dainippon Ink & Chemical Inc.) as coating aids to each layer. Cpd-19, Cpd-20 and Cpd-21 were used as stabilizers in the silver halide-containing layers and the colloidal silver-containing layers. The compounds used in the example are shown below: Polyethylene acrylate

Solv-1 Di(2-ethylhexyl)phthalate

Solv-2 Trinonyl Phosphate

Solv-3 Di(3-methylhexyl)phthalate

Solv-4 Tricresyl Phosphate

Solv-5 Dibutylphthalate

Solv-6 Trioctyl Phosphate

H-1 1,2-bis(vinylsulfonylacetamido)ethane

Samples 102 to 106 were prepared by replacing Emulsion A contained in the sixth layer of Sample 101 with Emulsion B to F. Furthermore, Sample 107 was prepared by replacing yellow colloidal silver contained in the fifth layer of Sample 104 with black colloidal silver. These characteristics are summarized in Table 2. TABLE 2 Sixth layer emulsion

Two pieces of film were prepared from each of these samples 101 to 107. One was exposed through an optical wedge using a white light source, and the other was exposed through an optical wedge using a green light source. These exposed samples were processed by the following processing method (I): (Processing procedure (I))

(Composition of processing solutions) First development solution

Pentasodium nitrilo-N,N,N-trimethylenephosphonate 0.6 g

Pentasodium diethylenetriamine pentaacetate 4.0 g

Potassium sulphite 30.0 g

Potassium thiocyanate 1.2 g

Potassium carbonate 35.0 g

Potassium hydroquinone monosulfonate 25.0 g

Diethylene glycol 15.0 ml

1-Phenyl-4-hydroxymethyl-4-methyl- 3-pyrazolidone 2.0 g

Potassium bromide 0.5 g

Potassium iodide 5.0 mg

Water to 1 liter

(pH: 9.70)

Color developing solution

Benzyl alcohol 15.0 ml

Diethylene glycol 12.0 ml

3,6-Dithia-1,8-octanediol 0.2 g

Pentasodium nitrilo-N,N,N-trimethylenephosphonate 0.5 g

Pentasodium diethylenetriamine pentaacetate 2.0 g

Sodium sulphite 2.0 g

Potassium carbonate 25.0 g

Hydroxylamine sulfate 3.0 g

N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g

Potassium bromide 0.5 g

Potassium iodide 1.0 mg

Water to 1 liter

(pH: 10.40)

Bleach-fixing solution

2-Mercapto-1,3,4-triazole 1.0 g

Disodium ethylenediaminetetraacetate dihydrate 5.0 g

Ethylenediaminetetraacetic acid Fe(III)-ammonium monohydrate 80.0 g

Sodium sulphite 15.0 g

Sodium thiosulfate (700 g/l) 160.0 ml

Glacial acetic acid 5.0 ml

Water to 1 liter

(pH: 6.50)

After processing, sensitometry was performed for the magenta image formed on the samples described above. For each sample, the sensitivity ratio of the magenta image of the test piece exposed to green light to the magenta image of the test piece exposed to white light was determined. The results are shown in Table 3.

Subsequently, samples 101 to 107 were exposed in the same manner as above and processed by the following processing method (II).

(Processing procedure (II))

This was the same as the processing method (1), except that the time for the first development (black and white development) was 55 seconds.

The results are shown in Table 3. TABLE 3 Processing methods

Since the sensitivity ratio of monochromatic exposure to white light exposure is higher, the multilayer effect becomes larger, resulting in a color reversal photographic light-sensitive material which exhibits color reproducibility with high chroma.

As can be seen from Table 3, the multilayer effect is preferentially enhanced when the shape of the emulsion grains contained in the sixth layer is tabular. The smaller the average spherical grain size and the higher the aspect ratio, the higher the effect obtained.

When the layer adjacent to the emulsion layer contains yellow colloidal silver, the multilayer effect is more enhanced compared to the case where the layer does not contain yellow colloidal silver.

Furthermore, the shorter the time for black and white development, the smaller the multi-layer effect becomes. However, the effect of the invention is remarkable when the time for black and white development is short.

According to the invention, color reversal photographic materials having a sufficient multilayer effect are obtained even in processing in which the time for the first development is short.

Claims (9)

1. A method for developing a silver halide color reversal photographic material comprising a support having disposed thereon at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, wherein at least one silver halide emulsion layer contains tabular silver halide grains having an aspect ratio of at least 5, which occupy at least 50% of all silver halide grains present in the same layer as a projection area and which have an average sphere-corresponding grain size of 0.30 µm or less, comprising developing the color reversal photographic material with a black-and-white developing solution for 100 seconds or less. 2. The method of claim 1, wherein the time for black and white development is 60 seconds or less. 3. The process of claim 1, wherein the aspect ratio of the tabular silver halide grains is at least 8. 4. A method according to claim 1, wherein the black and white developing solution contains a rhodanine. 5. The process according to claim 1, wherein the sphere-corresponding grain size of the tabular silver halide grains is 0.25 µm or less. 6. The process of claim 1, wherein the tabular silver halide grain is a silver iodobromide having a silver iodide content of 0.01 to 30 mol%. 7. The process of claim 1, wherein the silver halide color reversal photographic material contains a silver with yellow colloidal silver. 8. The method of claim 7, wherein the tabular silver halide grain is contained in an adjacent layer to the yellow colloidal silver layer. 9. The method of claim 1, wherein the tabular silver halide grain is contained in the highest low-speed emulsion layer when each of the emulsion layers consists of a plurality of layers having a similar spectral sensitivity.