JPH03113440A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve processing stability and aging stability by specifying the silver iodide content of the high sensitivity silver halide emulsion of a blue- sensitive silver halide emulsion layer. CONSTITUTION:Blue-, green- and red-sensitive silver halide emulsion layers are formed and at least one of the three emulsion layers is composed of two or more emulsion layers having different sensitivities. The silver iodide content of the high sensitivity silver halide emulsion of the blue-sensitive silver halide emulsion layer is made higher than that of the low sensitivity emulsion by >=0.3 mol% and the silver iodide content of the high sensitivity silver halide emulsion of the green-sensitive silver halide emulsion layer is made lower than that of the low sensitivity emulsion by >=0.3 mol%. Processing stability and aging stability can be improved without deteriorating color reproducibility.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color reversal photographic light-sensitive material that has excellent stability over time and improved processing variability. Regarding.

[Background of the invention]

Silver halide color photographic light-sensitive materials are required to have various performances, but in response to the recent demand for higher image quality, color reversal light-sensitive materials are required not only to improve color reproducibility but also to improve development stability against physical fluctuations. It is desired to have good stability over time, and this is an important issue.

In color reversal photosensitive materials, the multilayer effect of demons is important as a technology for improving color reproduction.

Regarding the interlayer effect, the higher the iodine content, the greater the interlayer effect on other layers, but the more difficult it is to receive the interlayer effect from other layers. Therefore, in color reversal light-sensitive materials, silver halide grains having a relatively low demon content are used for improving color reproduction. In the case of color reversal photosensitive materials, the processing time of the first development is often varied. Since the black and white development of the first development contains a silver halide solvent, when the iodine content is low, the maximum density (Dmax) due to fogging
The method has drawbacks such as increased deterioration in stability over time, large fluctuations in photographic performance due to changes in the processing time of the first development, and large processing variability, and improvements have been desired.

For example, JP-A-59-64843 describes a color reversal photosensitive material in which the normal content of the high-speed layer emulsion is reduced by 0.3 mol% or more from the normal content of the low-speed layer emulsion, thereby improving color reproduction. However, due to the low legal content of the high-speed layer emulsion, the photographic performance fluctuated greatly in the high-density region, which had the disadvantage of large fluctuations.

Furthermore, JP-A No. 60-61156 describes a color reversal photosensitive material in which the normal content of the high-speed layer emulsion is greater than the normal content of the low-speed layer emulsion to improve color reproduction. had the disadvantage of large fluctuations in photographic performance in the low density range.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a silver halide color reversal photosensitive material that does not deteriorate color reproduction and has improved processing stability and stability over time.

[Structure of the invention]

As a result of extensive studies, the present inventors have found a combination of techniques described below and have accomplished the present invention.

That is, the object of the present invention is to have three silver halide emulsion layers, blue-sensitive, green-sensitive, and red-sensitive, at least one of which is composed of two or more emulsion layers with different sensitivities; The silver iodide content of the high-sensitivity silver halide emulsion in the 10-silver-genide layer is 0.3 mol% or more higher than that in the low-sensitivity layer, and This was achieved by using a λ silver halide color photographic light-sensitive material characterized in that the silver iodide content is 0.3 mol% or more lower than that of the low-speed layer.

In the present invention, the average silver iodide content of the photosensitive silver halide emulsion is less than 7.0 mol%, preferably in the range of 1 to 6.5 mol%, more preferably in the range of 1.5 to 6 mol%.

The difference in legal content between the high-speed layer emulsion and the low-speed layer emulsion may be at least 0.3 mol%, preferably from 0.5 to 3 mol%.

The difference in legal content between the blue-sensitive high-speed layer emulsion and the green-sensitive high-speed layer emulsion is 0.3 to 2.5 mol%, preferably 0.5 to 2.5 mol%.
It is 3 mol%.

Furthermore, the legal content of the blue-sensitive high-speed layer emulsion is 4.5 mol%.
The following are preferred.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any of the conventional silver halide emulsions can be used.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

In addition, it has the effect of color correction, and by coupling with competing couplers and oxidized forms of developing agents, development accelerators, bleaching accelerators, developing agents, silver halide solvents, toning agents, hardeners, capri agents are produced. , antifoggants, chemical sensitizers, spectral sensitizers,
Compounds that release photographically useful fragments such as desensitizers 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 layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

Formalin scavengers, optical brighteners, matting agents, lubricants, image stabilizers, surfactants, color fog preventive agents, development accelerators, development retarders, and bleach accelerators can be added to the photosensitive materials.

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

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

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 → color development → stop → water washing → adjustment bath → water washing → bleaching → water washing → Fixation-
The steps of washing with water → stabilization → drying are used. This step may further include a prebath, a predural bath, a neutralization bath, and the like. 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 adjustment bath can also be omitted.

Further, bleaching, washing with water, 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. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-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, borates, alkanolamines), alkaline agents (e.g. oxides, carbonates), solubilizing agents (e.g. polyethylene glycols, esters thereof)
, pH adjusters (e.g. organic acids such as acetic acid), sensitizers (
For example, it may contain a quaternary ammonium salt), a development accelerator, a surfactant, a toning agent, an antifoaming agent, a hardening agent, a viscosity imparting agent, and the like.

The first developing solution 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.

2S03, Na1SOs, KzS20s in Na5CN1
, Na2S2O5, K, S, O, and Na2S2O3.

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-, 0.0 per 112 of the developer
05 to 0.02 mol, especially 0.05 to 0.02 mol. It is preferable that the amount is 1 to 0.015 mol of O, and when SOs''- is used, it is 0.01 to 0.015 mol.
The amount is preferably 0.5 to 1 mol, particularly 0.1 to 0.5 mol.

Furthermore, antifoggants (e.g., halides such as potassium bromide, sodium bromide, benzimidazoles, benzotriazoles, benzothiazonyls, tetrazoles, thiazonyls, 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.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

〔Example〕

A comparative sample of a multilayer color light-sensitive material was prepared by sequentially coating each layer having the composition shown below on a subbed triacetylcellulose film support from the support side. The coating amount of each component is expressed in g/m''.

1st layer (antihalation layer) Ultraviolet absorber U-10,3 Ultraviolet absorber U-20,4 High boiling point solvent 0-1 1.0 Black colloidal silver 0.24 Gelatin
2.0 Second layer (middle layer) 2.5-di-t-octylhydroquinone 0.
1 High boiling point solvent 0-1 0.2 Gelatin l・0 3rd layer (
Low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-
AgBr1 (Ag
l 4.0 mol%, average grain size 0.25 μm) 0.5 Coupler C-10, 1 mol High boiling point solvent 0-2 0.6 Gelatin 1.3 Fourth layer (high sensitivity red-sensitive silver halide emulsion layer) ) red sensitizing dye (s-1,
AgBr1 (Agl
2.5 mol%, average particle size 0.6 μm) 0.8 Coupler C-10,2 High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer (intermediate layer) 2.5-di-t- Octylhydroquinone 0.
1 High boiling point solvent 0-1 0.2 Gelatin 0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) Green sensitizing dye (S-3
, 5-4) spectrally sensitized by AgBr1 (Agl
3. ．． 5 mol %, average particle size 0.25 μm) 0.6 Coupler M - 10,04 mol Coupler M - 20,011 mol High boiling solvent 0-3 0.5 Gelatin 1.4 7th layer (high sensitivity green sensitive halogenated Emulsion layer) Green sensitizing dye (S-3,5
-4) Spectrally sensitized AgBr1 (Agl 2
．． 5 mol%, average particle size 0.6 μm) 0.9 Coupler M - 10,10 mol Coupler M -20,02 mol High point solvent 0-3 1.0 Gelatin 1.5 8th layer (intermediate layer) 5th 9th layer (yellow filter layer) yellow colloidal silver 0.1 gelatin 0.92.5-sheet t-octylhydroquinone 0.1 high boiling point solvent 0-1 0.2 1st theta layer (low sensitivity blue sensitive halogen Silver emulsion layer) Blue sensitizing dye (5-5)
AgBr1 (Agl 2.5 mol%, average particle size o, 35 μm) spectrally sensitized by 0.6 coupler Y
-10.3 mol High boiling point solvent 0-3 0.6 Gelatin 1.3 11th layer (high sensitivity blue-sensitive silver halide emulsion layer) Blue sensitizing dye (5-5
) Spectrally sensitized AgBr1 (Ag 12.5 mol%, average particle size 0.9 μm) Coupler Y-1 High boiling point solvent 0-3 Gelatin 12th layer: 1st protective layer UV absorber U-1 UV absorber U-2 2,5-di-t-octyl High high boiling point solvent 0-3 Gelatin 13th layer: Second protective layer Average particle size (r) 0.08 μm1 Dorokino silver iodide 0.9 0.5 mol 1. 4 2.1 0.3 0.4 0.1 0.6 1.2 Non-photosensitive fine grain silver halide emulsion consisting of silver iodobromide containing 1 mol%
Silver amount 0.3 Polymethyl methacrylate particles (diameter 1.5 μm) Surfactant 5A-1 Gelatin 0.7 In addition to the above composition, gelatin hardening agent H-1 and surfactant were added to each layer. Added. Also, tricresyl phosphate was used as a coupler solvent.

Ultraviolet absorber U-1 Ultraviolet absorber U-2 Sensitizing dye S- l Sensitizing dye S Sensitizing dye S- Sensitizing dye S-4 Sensitizing dye S Coupler C-1 Coupler M-1 ShiU Coupler M- 2 Coupler y-1 Gelatin hardening agent H-1 Surfactant SA NaOs 5-CHCOOCHx (CF 2 CF
z )s HCH2COOCH! (CF, CF,), H
-1 -2 -3 C2H.

C2H.

Next, the silver iodide contents of the third layer, fourth layer, sixth layer, seventh layer, 1θ layer, and 11th layer of sample 6 were changed as shown in Table 1, and the sensitivity gradation was Samples 2 to 5 were prepared in the same manner as Sample 1 except that the samples were adjusted to be the same.

Samples 1 to 5 thus prepared were subjected to wedge exposure using green light (CC90 filter manufactured by Kodak) and then subjected to the following development treatment.

Further, Samples 1 to 5 were subjected to the following development process after wedge exposure using white light, and the following development process with a first development time of 8'.

Furthermore, after samples 1 to 5 were heat-treated at 55 DEG C. for 7 days, the following development treatment was performed after wedge exposure using white light at the same time as the non-heat-treated samples.

Processing process Processing time Processing temperature First development
6 minutes 38℃ water washing
2/〃Reverse 2tt
//Color development 6〃
〃Adjustment 2//
tt bleach 5
// // established
4 tt ttWash 4 tt
// Stable 1 /
/ Dry at room temperature The composition of the processing solution used in the above processing step is as follows: First developer Sodium tetrapolyphosphate Sodium sulfite g 0 g 0 g Droxymethyl-3 g 2.5 g 1.2 g mQ 1000 mff Hydroquinone monosulfone carbonate Sodium (monohydrate) ■-722-4-Methyl-4-hivirazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water and invert Liquid Nitrilotrimethylenephosphonic acid 6-sodium salt chloride Stannous (dihydrate) p-Aminophenol Sodium hydroxide Add glacial acetic acid water g g 0.1g g 5mQ 1000m (2 Color developer Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium tertiary phosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90mQ Sodium hydroxide 3g Citrazic acid
1.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 1g 2.2-ethylenedithiogetanol Add 1g water and adjust to 000mQ Liquid sodium sulfite Sodium ethylenediaminetetraacetate Bleach by adding thioglycerin glacial acetic acid water Sodium ethylenediaminetetraacetate (dihydrate) g Ammonium 20g 00g 1000mf2 Iron constant ethylenediaminetetraacetate (dihydrate) Add ammonium bromide water and soak solution (III) Ammonium thiosulfate sulfite Stabilized by adding sodium bisulfite water Liquid formalin (37% by weight) 2g (dihydrate) g 0.4m12 mQ 1000+mQ 0g g g 1000+n12 m12 Konidax (manufactured by Konica Corporation) 5n+Q Adding water 1000+of2
Magenta image density of image obtained by green light 0.9
The yellow image density (DB) and cyan image density (Di) at the exposure amount are shown in Table 1 below.

Regarding processing variability, the processing time of the first development was 6
During the change of Dmax (maximum density) of the magenta image of the image obtained by white light varying from minute to 8 minutes (density difference =
ΔDmax).

Furthermore, regarding the stability over time, the density difference in Dmax (△Dmax
).

〔Effect of the invention〕

As is clear from Table 1, the samples of the present invention have excellent processing variability and excellent stability over time.

Further, no deterioration in green color saturation was observed.

It also has excellent green color reproduction.

Claims (1)

[Claims] It has three silver halide emulsion layers: blue-sensitive, green-sensitive, and red-sensitive, and at least one of them is composed of two or more emulsion layers with different sensitivities. The silver iodide content of the silver emulsion is 0.3 mol% or more greater than that of the low-speed layer, and the silver iodide content of the high-sensitivity silver halide emulsion of the green-sensitive silver halide emulsion layer is 0.3 mol% or more than that of the low-speed layer. A silver halide color photographic light-sensitive material characterized in that the silver halide is small by 3 mol% or more.