JP2816611B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a high-speed processing, high sensitivity, small change in sensitivity and gradation over time of a coating solution, and development after exposure. The present invention relates to a silver halide color photographic light-sensitive material having improved sensitivity and gradation change (latent image preservability) due to fluctuations in processing time.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials have been widely used because of their excellent features of high density recording properties, simplicity and low cost as compared with electrophotography and the like. At present, further desired properties of the silver halide color photographic light-sensitive material include faster processing, supply of a stable image, and excellent storage stability of the processed image. It is easily conceivable to increase the silver chloride content of silver halide emulsion grains used in a light-sensitive material for the purpose of rapid processing. A method using an emulsion having a high silver chloride content is described in, for example,
Nos. 95345, 59-232342 and 60-
There are many descriptions such as No. 19140, and in practice, high silver chloride emulsions used in color photographic papers have been developed in the market. The intrinsic absorption range of these high silver chloride emulsions is
It is necessary to perform spectral sensitization in order to absorb and sensitize visible light and / or infrared light in a short wavelength region and a longer wavelength region. However, in high silver chloride emulsions,
When a sensitizing dye that is normally used for silver bromide-based emulsions is used, its adsorption is weak, and when the time until coating is changed after preparing a coating solution, the sensitivity seems to be due to desorption of the sensitizing dye. In addition, there is a problem that a change in gradation is large. This is a serious problem since a photosensitive material having stable performance cannot be supplied.

It is also easy to think that the grain size of the silver halide emulsion is reduced for the purpose of rapid processing, but this method has the disadvantage of lowering the sensitivity. For the purpose of supplying prints of stable quality, it is difficult to be affected by fluctuations in processing conditions such as processing liquid components, and the effects of fluctuations in ambient atmosphere during exposure, such as exposure sensitivity and humidity. It is necessary to solve various factors, such as making the material less susceptible to light and reducing changes in sensitivity and gradation during storage of the photosensitive material. Among them, the influence of changes in sensitivity and gradation that occur when the time from exposure to development processing fluctuates is great. This time may fluctuate in a photo lab due to processing steps, and changes in sensitivity and gradation at that time are a serious problem from the viewpoint of stability of print quality. By setting the coating pH to a specific value, it is possible to suppress an increase in fogging that occurs during long-term storage of the photosensitive material, and it is preferable to supply a stable print.
-6940, U.S. Pat. No. 4,917,994,
JP-A-135338 and JP-A-3-1133. However, there is no known effect of the coating pH on the latent image stability.

[0004]

As described above, the desire to obtain stable quality prints quickly is very important in the development of color photographic materials in the current market. Is an important task. Therefore, an object of the present invention is to provide a print of stable quality promptly to the user, which is excellent in rapid processability, high in sensitivity, and in which the change in sensitivity and gradation over time of a coating solution of a high silver chloride emulsion. An object of the present invention is to provide a color photographic light-sensitive material which is small and has improved sensitivity and gradation change when the time from exposure to development varies.

[0005]

As a result of repeated studies, the present inventor has found that in a system of a reflection type color photographic light-sensitive material using a high silver chloride emulsion, a high silver chloride emulsion can be obtained by adding a thiocyanate. It has been found that the stability of the coating solution over time is improved, and that the stability of the latent image is improved by adjusting the coating pH of the photographic material containing thiocyanate to a specific range.

The use of rhodanammon in combination with gold sensitization of a high silver chloride emulsion is described, for example, in Japanese Patent Application Laid-Open No. 64-6941, but the knowledge of the present invention as described above is taught. Absent. Regarding the addition of a thiocyanate to a silver halide emulsion, see JP-A-63-2236.
No. 34, the use of a 6,6'-dichlorobenzothiacarbocyanine dye in combination with a green deficiency improving agent such as rhodanammon improves high sensitivity and green deficiency. By adding a sensitizing dye and a thiocyanate before chemical sensitization, fog can be suppressed and high sensitivity can be obtained, and graininess can be improved. Furthermore, JP-A-2-153345 specifies a chemical ripening However, it is described that high sensitivity can be obtained by suppressing fog by using a pAg increasing agent such as thiocyanate, and the storage stability of an unexposed photographic material is also improved. However, the knowledge of the present invention described above is not taught.

An object of the present invention is to provide a reflective support having at least one yellow-color-forming silver halide emulsion layer, at least one magenta-color-forming silver halide emulsion layer, and at least one cyan-coloring silver halide emulsion layer. The silver halide grains contained in at least one of the silver halide emulsion layers are silver chlorobromide or silver chloride having a distribution sensitized silver chloride content of 90 mol% or more. And the silver halide emulsion layer comprising silver chlorobromide or silver chloride contains at least one thiocyanate compound, and the photosensitive material has a coating pH of 4.0 to 4.0.
The problem was effectively solved by a silver halide color photographic light-sensitive material characterized in that the photographic material was 6.5. The present invention will be described in more detail below.

The thiocyanate compound used in the present invention may be either an inorganic salt or an organic salt. Examples thereof include alkali metal salts such as potassium thiocyanate and sodium thiocyanate, alkaline earth salts such as potassium thiocyanate and magnesium thiocyanate, and ammonium salts such as silver thiocyanate and ammonium thiocyanate. Can be The amount of the thiocyanate compound to be added varies depending on the shape and size of the silver halide grains, but it can generally be used in an amount of 2.5 × 10 ⁻⁵ to 2 × 10 ⁻² mol per mol of silver halide. . For example, when the size of the silver halide grains is 0.
In the case of 2 to 1.3 μm, the amount is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol per mol of silver halide. The thiocyanate compound used in the present invention is preferably dissolved in water and added. The timing of the addition may be during the preparation of the silver halide emulsion or during the preparation of the coating solution, and is not particularly limited, but is preferably after the formation of the silver halide grains.

The coating pH of the silver halide color photographic light-sensitive material in the present invention is the pH of all the photographic constituent layers obtained by coating a coating solution on a support.
Does not always match. The pH of the coating is disclosed in
It can be measured by the following method as described in No. 45153. That is, (1) 0.05 cc of pure water is dropped on the surface of the light-sensitive material on which the silver halide emulsion is coated. Next, (2) After leaving for 3 minutes, a film pH measuring electrode (TOA
Measure the coating pH at -165F). The light-sensitive material of the present invention has a coating pH of 4.0 to 4.0 obtained by such a measuring method.
6,5. Preferably, it is 5.0 to 6.5. pH
Is less than 4.0, the desensitization when the time until the post-exposure to development processing is increased becomes large. On the other hand, when it is 6.5 or more, the sensitization when the time from the exposure to the development processing is increased is large. Coating
pH can be adjusted with acids (eg, sulfuric acid, citric acid) or alkalis (eg, sodium hydroxide, potassium hydroxide). The method of adding these acids and alkalis is not particularly limited, but it is an easy method to carry out when preparing a coating solution. The coating solution for this addition may be one or more of the photographic constituent layers.

The silver halide color photographic light-sensitive material of the present invention comprises a cyanuric chloride-based hardener, in particular, a compound represented by the following formula (Ha) and / or a hardener represented by the following formula (Hb): Preferably, the film is hardened by a film agent.

[0011]

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[0012]

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The general formula (Ha) and / or the general formula (H
The hardener represented by b) will be described in detail below.
The alkyl group represented by R ₁ and R _{2 in} the general formula (Ha) is, for example, a methyl group, an ethyl group, a butyl group or the like, and the alkoxy group represented by them is a methoxy group, an ethoxy group, a butoxy group, or the like. Further, M of the -OM group represented by R ₁ and R ₂ is, for example, a sodium atom or a potassium atom. Also, cyanuric chloride-based hardeners represented by the general formula (Ha) are described in U.S. Pat. Nos. 3,645,743, JP-B-47-6151, JP-B-47-33380, and 51-
No. 9607, JP-A-48-19220 and JP-A-51-78.
No. 788, No. 52-60612, No. 52-12813
Nos. 0, 52-130326, and 56-1043, and among them, those having a structure represented by the general formula (Ha) can be used.

Next, the hardener represented by the formula (Hb) will be described. The alkyl group represented by R ₃ and R _{4 in} the general formula (Ha) is, for example, a methyl group, an ethyl group, a butyl group, and the like, and the alkoxy group represented by them is a methoxy group, an ethoxy group, a butoxy group, and the like. Furthermore M of -OM group represented by R _3, R ₄ is sodium atom or a potassium atom, for example. The alkylene group represented by L is, for example, a methylene, ethylene, propyleneene group or the like, and the arylene group is, for example, a p-, o- or m-phenylene group.

The dimer type cyanuric chloride hardener represented by the general formula (Hb) is described in Canadian Patent 895,808, JP-B-58-33542 and JP-A-57-40244. Yes, you can select and use them. The general formula (H) according to the present invention
The compounds represented by a) and (Hb) may be used by diffusing them in all layers to be coated, or may be localized in a specific layer. These compounds may be added by selecting at least one or a plurality of layers from the emulsion layer or the auxiliary layer. These additives are dissolved in water or alcohol (eg, methyl alcohol, ethyl alcohol, etc.), and 1 g of gelatin is added.
1 to 100 mg, preferably 5 to 50 mg is added per 1 mg. The addition method may be either a batch method or an inline method, but inline addition is preferred. Next, typical specific examples of the compound represented by formula (Ha) or (Hb) will be given, but the present invention is not limited thereto. Compound represented by general formula (Ha)

[0016]

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[0017]

Embedded image Compound represented by general formula (Hb)

[0018]

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[0019]

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As the silver halide used in the present invention, silver chloride or silver (iodo) chlorobromide can be used. Particularly for the purpose of rapid processing, silver iodide is added to all silver halide emulsion layers. 90 mol% silver chloride content substantially free of
It is preferable to use a silver chlorobromide or silver chloride emulsion of 95% or more, especially 98% or more.

In the light-sensitive material according to the present invention, the hydrophilic colloid layer can be decolorized by a process described in EP 0,337,490 A2, pp. 27-76, for the purpose of improving the sharpness of the image. Dyes (among which are oxonol dyes) are added so that the optical reflection density at 680 nm of the photographic material is 0.70 or more, and dihydric alcohols (2 to 4) are added to the water-resistant resin layer of the support. Titanium oxide surface-treated with, for example, trimethylolethane)
It is preferable that the content be at least 10% by weight (more preferably at least 14% by weight).

The photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are preferably used by dissolving them in a high boiling organic solvent. The high boiling organic solvent has a melting point of 100 ° C. or less and a boiling point of 140 ° C. Any of the above water-immiscible compounds and a good solvent for the coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. Alternatively, cyan, magenta or yellow couplers can be impregnated with a loadable latex polymer (eg, U.S. Pat. No. 4,203,716) in the presence or absence of the high boiling organic solvent described above, or with a water-insoluble and organic solvent. It can be dissolved together with a solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, columns 7 to 1 of U.S. Pat. No. 4,857,449.
Column 5 and the first of International Publication WO 88/00723.
The homopolymers or copolymers described on pages 2 to 30 are used, and more preferably a methacrylate-based or acrylamide-based polymer, particularly an acrylamide-based polymer, is preferred from the viewpoint of stabilizing a color image.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in EP 0,277,589 A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred. That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

As a support used in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment for a display is provided on a support having a silver halide emulsion layer. A support may be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.3 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 5 to 0.8.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

Also, upon exposure, US Pat.
It is preferable to use the band and stop filter described in No. 0,726. This removes light mixing,
The color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional color development processing, but it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. The pH of the bleach-fix solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied for processing this light-sensitive material As the additives for treatment and processing, those described in the following patent gazettes, in particular, EP 0,355,660 A2 (JP-A-2-139544) are preferably used.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan couplers described in US Pat. No. 33,144, EP 0,333,185 A2
3-hydroxypyridine-based cyan couplers described in (1), (4) couplers of the couplers (42) listed as specific examples, which have been converted to 2-equivalent couplers with a chlorine leaving group, and couplers (6) and (9) Are particularly preferred) and the use of cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are also preferred.

A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to upper right, page 34. The method described in the column is preferably applied.

[0037]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Example 1 (Preparation of emulsion A) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidin 2-thione (1% aqueous solution) was added. To this aqueous solution, an aqueous solution containing 0.5 mol of silver nitrate and an aqueous solution containing 0.5 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.45 mol of silver nitrate and an aqueous solution containing 0.45 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. Then 4
At 0 ° C., a copolymer of inbutene-maleic acid was added, and desalting was carried out by settling and washing. Further, 90.0 g of lime-processed gelatin was added, and the pH and pAg of the emulsion were each adjusted to 6.
It was adjusted to 2,6.5. This emulsion has a grain size of 0.05
The silver bromide fine grain emulsion of 0.005 mol
After adding at 0 ° C. to form a silver bromide-rich layer on the grain surface, the following red-sensitive sensitizing dye (1 × 10 ⁻⁴ mol / mol Ag) and potassium thiocyanate (1 × 10 ⁻³ mol / mol Ag) were added. ,
Further, 1 × 10 ⁻⁵ mol / mol Ag of sulfur sensitizer (triethylthiourea) and 0.2 g / mol Ag of nucleic acid were added, and the mixture was added at 50 ° C.
Optimized chemical sensitization. The silver bromide fine particles contained potassium hexachloroiridate (IV) at a concentration of 0.8 mg per 0.005 mol of silver in the fine particles during the formation of the fine particles.

With respect to the obtained silver chlorobromide emulsion (A) having a silver chloride content of 99.5 mol%, the grain shape, grain size and grain size distribution were determined from an electron micrograph. The silver halide grains were cubic with a grain size of 0.50μ and a coefficient of variation of 0.08. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution used was a value obtained by dividing the standard deviation of the particle size by the average particle size. Emulsions BF as shown in Table 1 were prepared by changing the type and amount of thiocyanate in the preparation method of Emulsion A. Further, by changing the temperature at the time of forming silver halide grains, emulsions having different grain sizes are prepared, and a blue-sensitive sensitizing dye or a green-sensitive sensitizing dye is added to these emulsions to prepare an emulsion for blue-sensitive or green-sensitive as described below. Was prepared. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0039]

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[0040]

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After corona discharge treatment on the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing dodecylbenzenesulfonic acid was provided, and various photographic constituent layers were further applied to form a multilayer color having the following layer constitution. A photographic paper and a sample (O) were prepared. The coating solution was prepared as follows. Preparation of Coating Solution for Fifth Layer 9.6 g of cyan coupler (ExC), 0.6 g of color image stabilizer (Cpd-2), color image stabilizer (Cpd-6)
5.4 g, 12 g of color image stabilizer (Cpd-7), 1.5 g of color image stabilizer (Cpd-8), color image stabilizer (Cpd-4)
0.4 g of ethyl acetate (25.0 cc) and a solvent (Solv
-6) 4.2 g was added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate containing 20.0 cc.
Emulsified dispersion C
Was prepared. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0.50 μm, coefficient of variation of grain size distribution 0.08, silver bromide 0.5 mol% localized on grain surface by the method described above) ) Was prepared. The above-mentioned emulsified dispersion C and this silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the following composition. During the preparation of the coating solution, the following red-sensitive sensitizing dye was added in an amount of 2.7 × 10
^-4 mol was added to perform spectral sensitization. Coating solutions for the first to seventh layers were prepared in the same manner as for the fifth layer. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s
- using a triazine sodium salt (I-1), the total coating amount was 0.097 g / m ^2. Also, Cpd-10 is added to each layer.
And Cpd-11 in a total amount of 25.0 mg / m ² and 5 respectively.
0.0 mg / m ² was added.

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on first layer side contains white pigment (TiO2) and blue dye (ultra blue)] First layer (blue-sensitive yellow coloring layer) Silver chlorobromide emulsion (A) 0.30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) ) 0.06

Second layer (color mixture preventing layer) Gelatin 0.64 Color mixture inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green light sensitive) Magenta color developing layer) Silver chlorobromide emulsion (A) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0 .16 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-9) 0.02 solvent (Solv-2) 0.40 fourth layer (ultraviolet absorbing layer) gelatin 1.41 ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth layer (red-sensitive cyan coloring layer) Silver chlorobromide emulsion (A) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 colors Image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv) -6) 0.14 Sixth layer (ultraviolet ray absorbing layer) Gelatin 0.48 Ultraviolet ray absorbent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seven layers (protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0055]

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In order to prevent irradiation, the following dyes were added to the emulsion layer (the coating amount is shown in parentheses).

[0057]

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Emulsion and coating in fifth layer in sample (O)
The pH was changed as shown in Table 1 to prepare samples (1) to (16). The coating pH was adjusted by adding sulfuric acid and sodium hydroxide when preparing the coating solutions for the second and fourth layers. The samples shown in Table 1 were subjected to gradation exposure for sensitometry through blue, green, and red filters using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second. Ten minutes after exposure, the sensitivities of the samples subjected to the following development processing and those subjected to the development processing 6 hours later were compared, and a latent image storability test was performed. The stability test when the coating solution was aged was performed by preparing the above coating solution and then performing the coating at a temperature of 40 ° C. for 30 minutes and then applying the coating solution at 40 ° C. for 4 hours. The sensitivity was compared with that when coating was performed later. The results are shown in Table 2.

[0059]

[Table 6]

[0060]

[Table 7]

Samples (1) and (2) to (4), Sample (7)
When (8) to (10) are compared, it can be seen that the sensitivity change of the coating solution over time is reduced by including the thiocyanate. However, in the samples (2) to (4) and (14) in which the coating pH is less than 4.0 or more than 6.5, the storage stability of the latent image is remarkably deteriorated, particularly in the emulsion containing thiocyanate. I understand. On the other hand, it contains thiocyanate and the coating pH of the light-sensitive material is 4.0.
It can be seen that Samples (6), (8) to (10) and (12) of the present invention of Nos. To 6.5 had high sensitivity and improved both the latent image preservability and the coating solution aging property. In addition, the sample (1
As can be seen from 5) and (16), the effect of the present invention does not change even if the type of thiocyanate is changed. As described above, it is possible to obtain a color photographic light-sensitive material having high sensitivity only by the present invention, a small change in sensitivity with time of the coating solution, and an improved change in sensitivity when the time until the development processing after exposure is changed. I understand.

(Development) The exposed sample was subjected to continuous processing (running) using a paper processor until it was replenished with twice the tank capacity of color development in the next processing step before use. . Processing process Temperature Time Replenisher ^* Tank capacity (unit: liter) Color development 35 ° C 45 seconds 161ml 17 Bleaching and fixing 30-35 ° C 45 seconds 215ml 17 rinse 30-35 ° C 20 seconds -10 rinse 30-35 ° C 20 seconds -10 rinse 30 to 35 ° C. 20 seconds 350 ml 10 drying 70 to 80 ° C. 60 seconds * replenishment rate (set to 3 tank countercurrent system to rinse →.) per photosensitive material 1 m ² in had the following composition of each processing solution is there.

Color developer tank liquid Replenisher water 800 ml 800 ml ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g potassium bromide 0.015 g-triethanolamine 8.0 g 12. 0 g sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl ) Hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Add water and 1000 ml 1000ml pH (25 ° C) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water is added. 1000ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Deionized water (Calcium and magnesium are less than 3ppm each)

Example 2 Samples (1), (3), (5) to (5) used in Example 1
Samples (1) were obtained by changing the gelatin hardener in (7), (9), (11) to (14) as shown in Table 3.
7) to (28) were prepared. However, the hardener was added in the same amount to the fourth layer coating solution and the sixth layer coating solution. These samples were tested for latent image storability in the same manner as in Example 1.

[0066]

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[0067]

[Table 8]

Table 9 shows the results.

[0069]

[Table 9]

Samples (6), (9), (12), (2)
7) and (28) were compared with Samples (19), (20) and (24), and the latent image storability was determined by using a hardener other than the general formula (Ha) and / or the general formula (Hb). In this case, it can be seen that the sensitization when the time from the exposure to the development processing fluctuates becomes large. That is, the general formula (H
The effect of the present invention becomes remarkable by hardening with the hardener represented by a) and / or the general formula (Hb).

[0071]

According to the present invention, rapid processing is excellent, high sensitivity, small changes in sensitivity and gradation with the passage of time of the coating solution, and sensitivity when the time until development processing after exposure varies. A color photographic light-sensitive material with improved gradation change can be obtained.

Claims (3)

(57) [Claims] 1. A silver halide color photograph comprising a reflective support having at least one layer each of a yellow-color-forming silver halide emulsion layer, a magenta-color-forming silver halide emulsion layer, and a cyan-color-forming silver halide emulsion layer. In the light-sensitive material, silver halide grains contained in at least one layer of the silver halide emulsion layer are spectrally sensitized silver chlorobromide or silver chloride having a silver chloride content of 90 mol% or more; Silver halide, characterized in that the silver halide emulsion layer comprising silver bromide or silver chloride contains at least one thiocyanate compound, and that the photosensitive material has a coating pH of 4.0 to 6.5. Color photographic light-sensitive material. 2. The silver halide color photographic material according to claim 1, wherein said silver halide color photographic material is hardened with a cyanuric chloride compound. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the thiocyanate compound is added after the formation of silver halide grains.