JPH03116042A - Image forming method for silver halide color reversal photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and processing stability by setting the ratio of the iodine in a high-sensitivity silver halide emulsion layer to total halogen smaller by 0.3mol% than that in a low-sensitivity emulsion layer, incorporating a monodisperse silver halide emulsion into at least one of blue-sensitive silver halide emulsion layers, specifying the total silver amt. and incorporating a silver halide solvent into a 1st developing soln. CONSTITUTION:The ratio of the iodine in the high-sensitivity silver halide emulsion layer to the total halogen is set smaller than by 0.3mol% than that in the low-sensitivity emulsion layer in the case of the development processing of the color reversal photographic sensitive material having at least >=2 layers of the blue sensitive silver halide emulsion layers varying in sensitivity. The monodisperse silver halide emulsion is incorporated into at least one of the blue sensitive silver halide emulsion layers and the total silver amt. is confined to <=2.0g/m<2> in terms of silver. In addition, the silver halide emulsion is incorporated into the 1st developing soln. The color reproducibility and the processing stability are simultaneously improved in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing a silver halide color reversal photographic light-sensitive material, and more specifically, a silver halide color reversal photographic light-sensitive material having improved color reproduction and suitability for running processing. The present invention relates to an image forming method.

[Background of the invention]

Silver halide color photographic materials are required to have various performances, but in response to recent demands for higher image quality, not only improved color reproducibility but also suitability for running processing is desired for color reversal materials. This is an important issue.

Since it is not possible to improve color reproduction using a DIR compound in color reversal photosensitive materials, the interlayer effect of iodine becomes important as a color reproduction improvement technique. In recent color reversal photographic materials, in order to improve graininess, they are coated in two or more layers, a high-speed layer and a low-speed layer. On the other hand, by making the ratio of iodine to total halogen in the emulsion of the high-speed layer (hereinafter referred to as the legal content) smaller than the legal content of the low-speed layer, the interlayer effect from other color-sensitive layers can be reduced to a high sensitivity. In JP-A-5, it was discovered that the design should be designed so that one layer receives more light and the other layers have a low-sensitivity layer with a high iodine content to fully produce the multilayer effect.
No. 9-64843.

The technique described above improves the saturation of red, green, and blue at the same time, resulting in excellent color reproduction. however,
In the actual market, color reversal photographic light-sensitive materials are developed using processing solutions in various states, and in that case, the above-mentioned technique is applied. It has become clear that the gradation is significantly different between the newly prepared first developer and the developer that has been subjected to some development processing.

This change is particularly remarkable in silver halide color reversal photographic materials in which the total silver content in the blue-sensitive layer located at the top layer is 2.0 g/ffi'' or less in terms of silver, and an improvement has been desired.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide an image forming method of a silver halide color reversal photographic light-sensitive material, which has improved color reproduction and optical stability.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a method for developing a color reversal photographic light-sensitive material having at least two or more blue-sensitive silver halide emulsion layers having different sensitivities. At least one monodisperse silver halide emulsion is present in at least one blue-sensitive silver halide emulsion layer, and the ratio of the total halogen in the emulsion layer to the total halogen is 0.3 mol % or more lower than that in the low-speed emulsion layer. and the total silver amount is 2.0 g/m2 or less in terms of silver,
This has been achieved by an image forming method for a silver halide color reversal photographic material, characterized in that the first developer contains a silver halide solvent.

The details of the present invention will be explained below.

The present invention is composed of a plurality of silver halide emulsion layers having substantially the same blue sensitivity but different sensitivities. The above-mentioned "substantially the same blue sensitivity" means that when a general color multilayer photosensitive material is sensitive to a blue wavelength region among the spectral wavelengths to which it can be exposed, the sensitivity range is higher for a certain wavelength region. The photosensitive layers are considered to be substantially the same even if their spectral sensitivities are slightly different. The same applies to green sensitivity and red sensitivity other than blue sensitivity.

When the layers with different sensitivities are composed of two layers, it is preferable that the high-sensitivity silver halide emulsion layer and the low-sensitivity emulsion layer are coated in this order from the far side when viewed from the support, and the composition is composed of three or more layers. In the case where the silver halide emulsion layers are coated in the same manner, it is preferable that the silver halide emulsion layers are coated in order of sensitivity from the side farthest from the support.

When the color-sensitive layer is composed of two layers, the sensitivity difference between the high-sensitivity silver halide emulsion layer and the low-sensitivity silver halide emulsion layer is determined by a well-known method, taking into account gradation, etc. You can find it, but - for boat fishing, △QogE (E is the exposure amount) is 0.2 to 1.
．． 5 is preferable, and C is particularly preferably 0.3 to 1.0. Δ(log E is adjusted to the optimum value depending on the grain size of the silver halide emulsion grains, the degree of chemical ripening, and the inhibitor added. Also, the concentration of the high-sensitivity silver halide emulsion layer and the low-sensitivity silver halide emulsion layer The respective holdings are preferably in the range of 10 to 90%, more preferably 25 to 75%.

Even when the color sensitivity is composed of three or more layers, the optimum value can be determined by the same method.

In the present invention, it is particularly preferable that the blue-sensitive layer has two layers.

In the present invention, the difference in legal content between an emulsion with a low legal content and an emulsion with a high legal content may be 0.3 mol% or more, preferably 0.5 to 3 mol% or less.

Further, it is preferable that the emulsion of the silver halide emulsion layer with a low legal content is 0.5 to 5.7 mol%,
1.5 to 4.5% is more preferable. Further, the silver halide emulsion layer having a relatively high content is preferably 0.8 to 6 mol%, more preferably 2 to 5 mol%.

In the present invention, a monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ±20% around an average grain size of 7 is 60% or more of the weight of all silver halide grains. It is particularly preferably 70% or more, and even more preferably 80% or more.

Here, the average particle size d is the frequency ni of particles having the particle size r1.
Define the grain size ri when the product niX ri3 of and r13 is maximum.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above.

A method for obtaining a monodisperse emulsion is to add a water-soluble silver salt and a water-soluble halide solution to a gelatin solution containing seed particles.
It can be obtained by adding by double jet method under the control of pl (.
No. 60-122935, No. 59-46640, etc. can be referred to.

The average grain size of the silver halide emulsion of the present invention is 0.05 to 1O
The range is preferably 0θμm, more preferably 0.1 to 5.0μl.

In the present invention, it is particularly preferred that the monodispersed silver halide grains have a (1,1,1) crystal habit.

Even if the silver halide grains used in the silver halide emulsion of the present invention have a uniform silver halide composition distribution, they may be core/shell grains in which the halogen composition differs between the inside of the grain and the surface layer. It is preferable that the silver iodide content on the grain surface is low. Preferably they are core/shell particles.

The silver halide emulsion of the present invention may be used by mixing two or more separately formed silver halide emulsions having different grain sizes or compositions after completion of chemical sensitization.

In the present invention, the monodisperse silver halide emulsion is contained in either or both of the blue-sensitive high-speed layer and the low-speed layer. Preferably (1, 1, 1
) plane, and when it is contained in a low-speed layer, it is preferable that the surface ratio of the (111) plane is 50% or more, preferably 75% or more.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, by adding metal ions using complex salts, these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, they can be added to the inside of the particles and/or on the particle surfaces. Can provide reduction-sensitized nuclei.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method using a sulfur-containing compound or activated gelatin that can react with silver ions, a selenium sensitization method, a reduction sensitization method using a reducing substance, a gold or other noble metal sensitization method, etc. may be used alone or in combination. It can be used as

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes can be used alone or in combination of two or more.

The sensitizing dyes may be used alone or in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. You can.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion of the present invention. As a binder for the emulsion,
It is advantageous to use gelatin. The emulsion layer and other hydrophilic colloid layers can be hardened and can contain plasticizers and dispersions (latexes) of water-insoluble or water-soluble synthetic polymers.

Couplers are used in the emulsion layer of color light-sensitive materials.

Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, etc.
Compounds that release photographically useful fragments such as antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, a formalin scavenger, an ultraviolet absorber, a fluorescent whitening agent, a surfactant, a development accelerator, and a development retardant can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, a commonly known color reversal process can be performed after exposure.

That is, after monochrome development of the silver 110 exposed in the first development, the unexposed silver halide is fogged in a light fog or a fog bath, and then a dye image is obtained by color development. It is.

Processing of a color reversal light-sensitive material according to an embodiment of the present invention usually involves the following steps: black and white development (first development) - stop → water washing - reversal - water washing one color development one stop one water washing one adjustment bath one water washing → bleaching → water washing → Establishment →
The steps of washing with water → stabilization → drying are used. This step may further include a pre-bath, a pre-hardening bath, a neutralization tower, etc. Also, stop, reverse,
Washing with water after color development, conditioning bath or bleaching may be omitted. Reversal may be performed in a fogging bath or by re-exposure. It is also possible to omit the fogging agent by adding it to the color developing bath. Furthermore, the conditioning bath can also be omitted.

In addition, bleaching→washing and fixing may be carried out using only a bleach-fixing bath.

A known developing agent can be used for the first developer used in the present invention. Examples of developing agents include dihydroxybenzene (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazoline. ascorbic acid, and 1.2 as described in U.S. Pat. No. 4,067.872.
A heterocyclic compound in which a 3.4-tetrahydroquinoline ring and an intrene ring are condensed can be used alone or in combination.

The black and white developer used in the present invention may also include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, @ acid salts, alkanolamines), alkaline agents (e.g., hydroxides, carbonates), solubilizing agents (e.g. polyethylene glycols, esters thereof)
, pH adjusters (e.g., organic acids such as acetic acid), sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, toning agents, antifoaming agents, hardeners, viscosity imparting agents, etc. It can be included.

The first developer used in the present invention must contain a compound that acts as a silver halide solvent, and the above-mentioned sulfite added as a preservative usually plays this role. The sulfite and other usable silver halide solvents include KSCN.

Na5CNSK, SO,, Na2sO3, K, S, O,
, Na, S, O,, K2S, O,, Na, 5103, and the like.

If the amount of these silver halide solvents used is too small, the progress of development will be slowed down, and if it is too large, it will cause fog in the silver halide emulsion, so there is a preferable amount to use, but it is difficult to determine the amount. can be easily accomplished by a person skilled in the art.

For example, when using 5CN-, it is 0.00 per 1Q of developer.
5 to 0.02 mol, especially 0.02 mol. It is preferable that it is O1 to 0.015 mol, and when using 5O1-, 0.05 mol
~1 mol, especially 0.1-0.5 mol is preferred.

Furthermore, antifoggants (e.g., halides such as potassium bromide and sodium bromide, benzimidazoles, benzotriazoles, benzothyanonyls, tetrazoles, thiazoles, etc.), chelating agents (e.g., ethylenediaminetetraacetic acid, alkali metal salts, polyphosphates, nitriloacetates).

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, but is preferably in the range of about 8.5 to about 11.5.

〔Example〕

Examples of the present invention are shown below, but the present invention is not limited thereto. In each example, the coating amount of each component is expressed as g/+a''. However, for silver halide, the coating amount is expressed in terms of silver.

Example 1 The following layers 1 to 11 were coated on a paper support coated with polyethylene on both sides (center line average roughness SR, -2.0 μm).
Color reversal photosensitive material sample 5 was prepared by providing layers. The coating amount of each component is expressed in g/ra2. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (haleshitane prevention layer) Black colloidal silver gelatin 2nd layer (1st red-sensitive layer) Cyan coupler (C-2) Cyan coupler (C-3) Antifading agent (A-1) Antifading agent (A- 2) Third layer of AgBr 1 (Agl 4.5 mol%, average particle size 0.4 μm) gelatin spectrally sensitized with a high boiling point solvent (0-4) and a red sensitizing dye (S-1, 5-6) (Second red-sensitive layer) Cyan coupler (C-2) Cyan coupler (c-3) Anti-fading agent (A-1) Anti-fading agent (A-2) High boiling point solvent (0-4) Red sensitizing dye ( S-1, S-6) 0.10 1.5 0.08 mol 0.16 mol 0.12 0.06 0.06 0.14 0.81 0.20 mol 0.10 mol 0.064 0. 032 0.097 Spectrally sensitized AgBrl (Agl 4.5 mol%, average particle size 0.8 μm) Gelatin 4th layer (first intermediate layer) Gelatin color mixing prevention agent (AN-1) Color mixing prevention agent (AN -2) High boiling point solvent (0-2) 5th layer (first green sensitive layer) Magenta coupler (M-3) Antifading agent (A-3) Antifading agent (A-4) High boiling point solvent (0- 4) AgBrl (Agl 4.5 mol%, average particle size 0.4 μm) gelatin 6th layer (second green sensitive layer) spectrally sensitized with green sensitizing dye (S-3) Magenta coupler (M-3) ) Antifading agent (A-3) 0.16 0.98 0.9 0.02 0.06 0.13 0.25 mol 0.067 0.12 0.19 0.15 0.93 0.15 mol 0.040 Antifading agent (A-4) High boiling point solvent (0-4) AgBrT spectrally sensitized with green sensitizing dye (S-3) (Agl 4.5 mol%, average particle size 0.7 μm) Gelatin 7th layer (second intermediate layer) Yellow colloidal silver color mixing inhibitor (AN-1) Color mixing inhibitor (AN-2) High boiling point solvent (0-1) Gelatin 8th layer (first blue sensitive layer) Yellow coupler (Y-2) Antifading agent (A-1) Antifading agent (A-5) High boiling point solvent (0-6) AgBr 1 (Agl 4. 5 mol%, average particle size 0.4 μm.

0.070 0.11 0.15 0.83 0.2 0.014 0.046 0.096 0.90 0.24 mol 0.096 0.04 & 0.048 Width of distribution 28%) 0,15 Gelatin 9th layer (second blue-sensitive layer) Yellow coupler (Y-2) Anti-fading agent (A-1) Anti-fading agent (A-5) High boiling point solvent (O-6) Blue sensitizing dye (S-5) ) Spectrally sensitized AgBrl (Agl 4.5 mol%, average particle size 0-8 μmq distribution width 30%) Gelatin 10th layer (UV absorbing layer) UV absorber (U-1) UV absorbing layer ( U-2) Color mixing inhibitor (AN-1) High boiling point solvent (0-3) Gelatin 11th layer (protective layer) Gelatin 0.95 0.32 mol 0.13 0.064 0.064 0.13 1. 3 0.2 0.2 0.033 0.037 587 0.50 However, in addition to the above, it contains an anti-fading agent, a surfactant, a hardening agent, and an anti-irradiation dye.

Sensitizing dye S- Sensitizing dye S- Coupler M-2 -1 -2 -3 2Hi Sensitizing dye S- Kabra-C-2 Coupler C-3 ShiU Coupler Y-2 -1 2 -3 − Color mixing prevention agent AN Color mixing prevention agent AN- H υH 〇　− Di-2-ethylexyl fucray to hmm stomach sodecylftale to Ji Monononyl 7-thaletate - -2 For each sample, cormorant After exposure, perform the following development process. went.

Processing process First development (black and white development) 1 minute 15 seconds (38°C) Washing with water 1 minute 30 seconds Light fog 10 Hux or more Second development (color development) 2 minutes 15 seconds (38°C) Washing with water 45 seconds Bleach fixing Wash with water for 2 minutes (38℃)
2 minutes 15 seconds 1st developer Potassium sulfite 3.0g Sodium thiocyanate 1.0g Sodium bromide 2.4g Potassium iodide
8.0w+g potassium hydroxide (48
%) 6.211M potassium carbonate
14g sodium bicarbonate
12gl-7enyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
1.5g hydroquinone monosulfate 23.3g (
pH = 9.65) Color developer Benzyl alcohol 14.6+1 ethylene glycol 12.6 mfi Potassium carbonate (anhydrous) 26 g Potassium hydroxide 1.4 g Sodium sulfite 1.6 g 3,6-cythiaoctane-1.8-diol 0.24 g Hydroxylamine Sulfate 2.684-N-ethyl-N-β-(methanesulfonamidoethyl-2-methyl-p-phenylenediaminecessal 7ate
5.0 Add water 100
0m12 Bleach-fix solution Iron ethylenediaminetetraacetate (I
-Mercapto-1.2.4- Triazole 0.4
gAdd water to 1000mff
(pH - 6.5) Samples were prepared in the same manner as Sample 1, except that the silver halide emulsions in the 8th and 9th layers were replaced with those having the specter content and distribution width as shown in Table 1. 2 to 9 were created.

Next, each sample was exposed to blue light through a sensitometric wedge, and then subjected to the reversal process described below. The yellow density (Dy) for each sample is 1. O
The magenta density DM (B) at the point was measured. Similarly, green exposure was performed through a wedge, and the following reversal process was performed to measure the yellow density DY (G) when the magenta density (DM) of each sample was 0.7. D, (B), D
The higher the density of both Y (G), the better the reproducibility of blue and green. The results are shown in Table 2. In addition, white exposure was performed through a wedge, and immediately after the first developer was newly prepared, reversal processing was performed. (New solution treatment) Next, the exposed sample l is continuously replenished with new solution at a ratio of 0.33Q/Ig'' to the first developer, and when the entire amount has been replaced, a second reversal treatment is performed. (Running liquid treatment) Based on the sensitometry results of the new liquid thus obtained and the running treatment, the running characteristics were evaluated as follows.

The running characteristics are the same concentration (
The difference in exposure to give 0, 5, 1, 0, 2, 0) is expressed as △ (log E), and this is taken as the running characteristic.
child .

The smaller the absolute value at each density, the better the running characteristics are, and the more the ΔαogE at each density is the same, the better there is no change in gradation. The results obtained are shown in Table 2. From the results in Table 2, comparative sample 1 has poor color reproducibility, and sample 2 has good color reproducibility, but the running characteristics result in a gradation with a large difference in exposure amount at a density of 1.0, which is not preferable.

On the other hand, the sample of the present invention has excellent color reproducibility, and the running characteristics are also good, with no gradation disturbance in the halftone area, and a small change width. [Effects of the Invention] It has been possible to provide a color reversal photographic material that has improved reproducibility and processing stability at the same time.

Claims (1)

[Claims] In a method for developing a color reversal photographic light-sensitive material having at least two blue-sensitive silver halide emulsion layers having different sensitivities, the iodine concentration in a high-sensitivity silver halide emulsion layer among the emulsion layers is At least one blue-sensitive silver halide emulsion layer contains at least one monodisperse silver halide emulsion whose proportion to the total halogen is 0.3 mol% or more smaller than that in the low-speed emulsion layer, and the total silver An image forming method for a silver halide color reversal photographic light-sensitive material, characterized in that the amount is 2.0 g/m^2 or less in terms of silver, and the first developer contains a silver halide solvent.