JPH03110549A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and processing stability by respective ly specifying the silver iodide content of a high-sensitivity silver halide emulsion constituting a blue sensitive silver halide emulsion layer and a high-sensitivity siver halide emulsion constituting a green sensitive silver halide emulsion layer. CONSTITUTION:This photosensitive material consists of the three blue sensitive, green sensitive and red sensitive silver halide emulsion layers, at least one of which consist of >=2 layers of the emulsion layers varying in sensitivity. The silver iodide content of the high-sensitivity silber halide emulsion constituting the blue sensitive silver halide emulsion layer is set smaller by >=0.3mol% than the silver iodide content of the low-sensitivity layer and the silver iodine content of the high-sensitivity silber halide emulsion constituting the green sensitive silver halide emulsion layer is set larger by >=0.3mol% than the silver iodide content of the low-sensitivity layer. Any of ordinary silver halide emulsions are usable as the silver halide emulsions to be used for the photosensitive material of this case. The silver halide color reversal photosensitive material improved in color reproducibility and processing stability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color reversal photographic light-sensitive material having improved color reproduction and processing variability.

[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 maintain stability against fluctuations in the development process. is desired and is an important issue.

In color reversal photosensitive materials, the multilayer effect is an important technique 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 content are used in order to improve color reproduction. In the case of a color reversal photosensitive material, it is processed in the first development (black and white development containing a silver halide solvent), so if the iodine content is low, the processing conditions of the first development (for example, the iodine content in the developer Since it is easily affected by fluctuations in the content (content), it has the drawbacks of large fluctuations in photographic performance and large processing variability, and improvements have been desired.

For example, JP-A No. 59-64843 describes a color reversal photosensitive material in which the iodine content of the high-speed layer emulsion is reduced by 0.3 mol% or more compared to the iodine content of the low-speed layer emulsion, thereby improving color reproduction. However, due to the low legal content of the high-speed layer emulsion,
It has the disadvantage of large fluctuations in photographic performance in high density areas.
−.

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 light-sensitive material with improved color reproduction and processing stability.

[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;・High-sensitivity layer constituting the silver halogenide emulsion layer ・The silver iodide content of the silver halogenide emulsion is 0 compared to that of the low-sensitivity layer.
．． Halogenation characterized in that the silver iodide content of the high-speed layer silver halide emulsion constituting the green-sensitive silver halide emulsion layer is 0.3 mol% or more smaller than that of the low-sensitivity layer. This was achieved using a silver color photographic material.

In the present invention, the average silver iodide content of the photosensitive silver halide emulsion is less than 7 mol%, preferably in the range of 1.0 to 6.5 mol%, more preferably 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 preferable that the legal content of the blue-sensitive high-speed layer emulsion is as low as 3 mol %.

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 a conventional method and can be optically sensitized by about 1 wavelength in 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.

Furthermore, by coupling with a competing coupler and an oxidized form of a developing agent, which has a color correction effect, a development accelerator, a bleach accelerator, a developer, a /10 silver genide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, 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 layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

For photosensitive materials, formalin scavenger-fluorescent brightener,
A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added.

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 photosensitive 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, one stop, one water washing, one adjustment bath, one water washing, one bleaching, one constant water washing. The steps of wearing, washing, stabilizing, and 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.

Further, the bleaching-washing and fixing may be performed 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 dihydroxybenzenes (for example, λ hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), l-phenyl-3- Pyrazolines, ascorbic acid, and 1.2 as described in U.S. Pat. No. 4,067.1372.
, 3. Heterocyclic compounds such as a 4-tetrahydroquinoline ring and an intrene ring condensed together can be used alone or in combination. The black and white developer used in the present invention may also contain other preservatives (e.g. , sulfites,
bisulfites, etc.) buffers (e.g. carbonates, boric acid, borates, alkanolamines), alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (e.g. polyethylene glycols, esters thereof), pH Regulators (e.g.
Organic acids such as acetic acid), sensitizers (eg, quaternary ammonium salts), development accelerators, surfactants, toning agents, antifoaming agents, hardeners, viscosity-imparting agents, and the like can be contained.

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.

Na5CN, K, So,, Na2SO3, l[2S,
O,, Na25zOs, KxSxOs, Na, S
, 0. etc. can be mentioned.

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

For example, when using 5CN-, it is 0.00 per developer IQ.
It is preferably 5 to 0.02 mol, especially 0.01 to 0.015 mol, and when so, "- is used, 0.0
Preferably it is 5 to 1 mol, especially 0.1 to 0.5 mol.

Furthermore, antifoggants (e.g., halides such as potassium bromide and sodium bromide, benzimidazoles, benzotriazoles, benzothiazonyls, 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 in g/m2. However, for /10 silver generide, the coating amount is expressed in terms of silver.Example 1 A multilayer color photosensitive material was prepared by sequentially coating each layer of the following composition on a subbed triacetylcellulose film support from the support side. Sample 1 was prepared as a comparison sample.

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-1
, 5-2) spectrally sensitized by AgBr1 (Agl
4.0 mol%, average particle size 0.25 μm) 0.5 Coupler C-10, 1 mol High boiling point solvent 0-2 0.6 Gelatin 1.3 4th layer (high sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-1
, 5-2) spectrally sensitized by AgBr1 (Agl
2-5 mol%, average particle size 0.6uII+) 0.8 Coupler C-10,2 High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer (intermediate layer) 2.5-sheet t-octyl Hydroquinone 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 8gBrl (8g1
3 mol %, average particle size 0.25 μm) 0.6 Coupler M - 10,04 mol Coupler M - 20,01 mol High boiling point 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 - to, to mol Coupler M - 20,02 mol High boiling point solvent 0-3 1.0 Gelatin l.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 (L22 10th (low sensitivity blue sensitive silver halide) Emulsion layer) Blue sensitizing dye (5-5)
AgBr1 (Agl 2,5
Mol%, average particle size 0.35 μm) 0.6 coupler Y
-10.3 mol High boiling point solvent O-30.6 Gelatin 1.3 No. 11
layer (high sensitivity blue-sensitive silver halide emulsion layer) blue sensitizing dye (
AgBr1 (Agl
2.5 mol%, average particle size 0.9 μff1) 0.9 Coupler Y -10.5 mol High boiling point solvent 0-3 1.4 Gelatin 2.l 12th layer: 1st protective layer UV absorber U -10 ,3 Ultraviolet absorber IJ-20,4 2,5-di-t-octylhydroquinone 0.
1 High boiling point solvent 0-3 0.6 Gelatin 1.2 13th layer:
Second protective layer Average grain size (r) 0.08 μm Non-photosensitive fine-grain silver halide emulsion made of silver iodobromide containing 1 mol% of silver iodide
Silver amount 0.3 Polymethyl methacrylate particles (diameter 1.5 μm) Surfactant 5A-1 Gelatin 0.7
In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer. Also, tricresyl phosphate was used as a coupler solvent.

Ultraviolet absorber U-1 Ultraviolet absorber U-2 Sensitizing dye S- 1 Sensitizing dye S Sensitizing dye S- Sensitizing dye S Sensitizing dye S Coupler C-1 Coupler M-1 ShiQ Coupler M Coupler Y- ■ Gelatin hardening agent H Surfactant SA- Na0) S-CI (COOCH*(CF*CFJsHC
tbCOOCHt (CF xcF !) J-2 C, Hs C, +1° Next, the content of silver iodide in the 3rd layer, 4th layer, 6th layer, 7th layer, 1st O layer, and 11th layer of sample 1 Samples 2 to 4 were prepared in the same manner as Sample 1, except that the sensitivity was changed as shown in Table 1 and the sensitivity gradation was adjusted to be the same for each sample.

Samples 1 to 4 thus prepared were subjected to wedge exposure using green light (Kodak CC90 filter) and then subjected to the following development treatment A.

In addition, after wedge exposure using white light for samples 1 to 4, treatment A and potassium iodide of the first developer of treatment A were added to 811Q.
The process was completely the same as process A except that the process was changed to .

After each sample was exposed to light, it was subjected to a lubrication process in the following order.

Processing process Processing time Processing temperature First development
6 minutes 38℃ water washing
2 〃 〃Reversal
2〃l/color development 5tt
//Adjustment 2〃ll
Bleach 5tt
tt fixation
4 tt ttWash
4 tt //
Stable 1 tt
Drying at room temperature The composition of the processing solution used in the above processing step is as follows (Processing A) First developer Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone
Monosulfonate 30g sodium carbonate (l hydrate)
30g l-phenyl-4-methyl-4-hydroxymethyl-3
Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0,
1% solution) Add 2IIIQ water
1000 + e12 inversion liquid nitrilotrimethylenephosphonic acid 6-sodium salt stannous chloride (dihydrate) g g O, Ig g 15m (2 1000 mi2 p-amin) phenol sodium hydroxide Add glacial acetic acid water Color developer Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium tertiary phosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 9011a Sodium hydroxide
3g citradinic acid
1.5g N-ethyl-N-β-phthamensulfonamidoethyl 3-methyl-4-aminoaniline sulfate 1
g 2.2-ethylenedithiogetanol Add 1g water and adjust to 100100O Liquid sodium sulfite Sodium ethylenediaminetetraacetate Thioglycerin Add glacial acetic acid water and bleach Liquid ethylenediaminetetraacetic acid Constant ethylenediamine (dihydrate) Ammonium bromide water Add solution ammonium thiosulfate sodium sulfite iron tetraacetate Sodium bisulfite water and add 2g (dihydrate) g O,4raQ mQ 1000m12 Thorium (dihydrate) g (DI) ammonium 20g 00g 1000m12 0g g g 1000m (1 Stable liquid formalin (37% by weight) 5g Konidax (manufactured by Konica Corporation) Add 5g water and magenta image density of image obtained with 10100O green light Yellow image density (D8) at an exposure amount of 0.9 and Cyan image density (D,
) are shown in Table 1 below. It can be said that the larger these values, the better the saturation.

Regarding process variability, in images obtained by exposing to white light and varying potassium iodide in the first developer, the sensitivity difference ( ΔffogE) was determined and shown in Table-1. The smaller these values, the better.

As is clear from Table 1, the samples of the present invention have excellent processing variability and excellent green color reproduction.

Example 2 Color reversal photosensitive material sample 5 was prepared by providing the following 1st to 11th layers on a paper support coated with polyethylene on both sides (center line average roughness SR, -2.0 μl 111).

The application amount of each component is given in g/m2. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (antihalation layer) Black colloidal silver o, i.

Gelatin 1.5 second layer (
Ml red sensitive layer) Cyan coupler (C-2) 0.14 Cyan coupler (C-3) 0.07 Anti-fading agent (A-1) 0.12 Anti-fading agent (
A-2) 0.06 high boiling point solvent (0
-4) 0.06 red sensitizing dye (S-
1,5-6) spectrally sensitized with eight girls (Agl
2.5 mol%, average particle size 0.4 μm) 0.14 Gelatin 0.81 Third layer (second red-sensitive layer) Cyan coupler (C-2) 0.20 Cyan coupler (C-3) 0.10 Antifading agent (A, 1) 0.064 Antifading agent (A2) 0.032 High boiling point solvent (0-4) 0.097 Spectrally sensitized with red sensitizing dye (S-1, 5-6) ThisAgRr
l (Agla, o mol %, average particle size 0.8 μm) 0.
16 0.98 Gelatin 4th layer (first intermediate layer) Gelatin color mixing inhibitor (AN-1) Color mixing inhibitor (AN-2) High boiling point solvent (0-2) 5th layer (first green sensitive layer) Magenta coupler -(M-3) Anti-fading agent (A-3) Anti-fading agent (A-4) High boiling point solvent (0-4) 0.9 0.02 0.06 0.13 0.25 0.067 0. 12 0.15 AgBr1 spectrally sensitized with green sensitizing dye (5-3)
(Agl 2.5 mol%, average particle size 0.4μ111) Gelatin 6th layer (second green sensitive layer) Magenta coupler (M-3) Anti-fading agent (A-3) Anti-fading agent (A-4) High Boiling point solvent (0-4) AgBr1 spectrally sensitized with green sensitizing dye (5-3)
(Agl 3.5 mol%, average particle size 0.7μ+a) 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 (1st*sensitive layer) Yellow coupler (Y-2) Antifading agent (A-1) 0.15 0.93 0.15 0.040 0.070 0.11 0.15 0 .83 0.02 0.014 0.046 0.096 0.90 0.24 0.096 Antifading agent (A-5) High boiling point solvent (0-6) Spectroscopy with blue sensitizing dye (5-5) Sensitized AgBr1
(Agl 2.5 mol%, average particle size 0.4 μm) 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 (0-6) AgBr1 spectrally sensitized with blue sensitizing dye (5-5)
(Agl 2.5 mol%, average particle size 0.8 μm) Gelatin 10th layer (ultraviolet absorption layer) Ultraviolet absorber (U-1) Ultraviolet absorption layer (U-2) Color mixing prevention agent (AN-1) High boiling point Solvent (0-3) Gelatin 11th layer (protective layer) 0.048 0.048 0.15 0.95 0.32 0.13 0.064 0.064 0.13 1.3 0.2 0.2 0.033 0.037 1.87 Gelatin 0.50 However, in addition to the above, it contains an anti-fading agent, a surfactant, a hardening agent, and an anti-iragecin dye.

Sensitizing dye S- Coupler C Coupler C Coupler M- ShiQ Coupler Y- -1 -3 - - Color mixing inhibitor AN- Color mixing inhibitor AN-2 0-4 Di-2-ethylexyl phthalate 0-5
Di-isodecyl 7 tallate 0-6 Di-nonyl 7 tallate Then the second layer of sample 5, the first! , except that the silver iodide content of the fifth, sixth, eighth, and ninth layers was changed as shown in Table 2, and the sensitivity gradation was adjusted to be the same for each sample. Samples 6 to 9 were created in the same manner as Sample 1.

Samples 5 to 9 thus prepared were subjected to wedge exposure using green light (CC90 filter manufactured by Kodak) and then subjected to the following development treatment A.

In addition, after wedge exposure using white light for Samples 5 to 9, 12 mg of potassium iodide in the first developer of Process B and Process B was added.
The process was completely the same as process B except that the process was changed to .

After exposing each sample to light, the following treatments were performed.

(Processing B) First development (black and white development) 1 minute 15 seconds (38°C) Washing with water
1 minute 30 seconds Light fog 100 (lux or more 1 second or more Second development (color development) 2 minutes 15 seconds (38°C) Wash with water
Bleach fix for 45 seconds, wash with water for 2 minutes (38°C)
2 minutes 15 seconds 1st developer Potassium sulfite 3.0g Sodium thiocyanate 1.0g Sodium bromide
2.4g potassium iodide
8.0mg potassium hydroxide (48%)
6.2m12 potassium carbonate
14g storium hydrogen carbonate 1
2g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5゜hydroquinone monosulfo-t-23.3g (pH-9
, 65) Color developer Benzyl alcohol 14.6 m (2 ethylene glycol 12.6 m (potassium dicarbonate (anhydrous)) 26 g Potassium hydroxide 1.4 g Sodium chloride 1.6 g 3.6-cythiaoctane-1.8-diol 0. 24g hydroxylamine sulfate 2.6g N-ethyl-N
-β-Methanesulfonamidoethyl 3-methyl-4-aminoaniline sulfate 0.5g Add water
1000I11 (1 Bleach-fix solution 1.56 molar solution of ethylenediaminetetraacetic acid iron (I [
-1-Riazole-3-thiol Add 0.4g water to 1000+512 (pH
= 6.5) Reflected green light density of image obtained by green light exposure 0.7
The reflected blue light density (D, ) and reflected red light density (DI) at the exposure amount are shown in Table 2 below. It can be said that the larger these values, the better the saturation.

Regarding process variability, in images obtained by exposing to white light and changing potassium iodide in the first developer, the sensitivity difference ( ΔffogE) was determined and shown in Table-2.

As is clear from Table 2, the samples of the present invention have excellent processing variability and excellent green color reproduction.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide color reversal photosensitive material with improved color reproduction and processing stability.

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 sensitive silver halide emulsion is 0.3 mol% or more lower than that of the low-speed layer, and the silver iodide content of the high-sensitivity layer silver halide emulsion constituting the green-sensitive silver halide emulsion layer is low. A silver halide color photographic material characterized in that the silver halide color is 0.3 mol% or more larger than that of a sensitive layer.