JP2841218B2 - Silver halide color photographic materials - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic material, and more particularly, to a silver halide color photographic material capable of forming a yellow dye image with improved graininess. is there.

[Background of the Invention]

Conventionally, the graininess of color photographic materials has been improved by
Attempts have been made mainly for each of the magenta and cyan color-developing portions, which are visually significant.

However, recently, the use of color photographic light-sensitive materials has become diversified in accordance with the increase in sensitivity and image quality, and for example, the number of machines used to print color negatives on monochrome paper for news reporting purposes, such as newspapers, has also increased. And
In such a case, especially when using ortho-type monochrome paper, when a color negative is conventionally printed on color paper, the yellow coloring portion, which has a small effect on the visual sense, significantly affects the quality of the image, and the graininess of the image is greatly reduced. Has become important.

In addition, with respect to ordinary effects, with the increase in sensitivity of color photographic light-sensitive materials, the chances of taking images under tungsten light at night and the effects of conditions such as morning or evening have been increasing, and such color temperature has been increased. The graininess of the yellow dye is a major problem even in low environmental conditions.

Granularity is one of the factors governing the image quality generated in a color photographic light-sensitive material, and various means have been attempted to improve the granularity.

As one of such means, for example, a method of reducing the grain size of silver halide used in a light-sensitive material is effective for improving graininess, but on the other hand, silver halide grains become smaller. As a result, the sensitivity of the silver halide is reduced, so that reducing the size of the silver halide grains is not always an advantageous method.

Also, a technique for improving the graininess by adding a DIR compound to a color photographic light-sensitive material is well known, but in this method, if the addition amount of the DIR compound increases, the sensitivity and the color developing property are greatly reduced. However, there is a limit in improving the graininess.

Furthermore, the graininess can be improved by forming the same color-sensitive composition contained in the color photographic light-sensitive material into three layers of a high-speed silver halide emulsion layer, a medium-speed silver halide emulsion layer and a low-speed silver halide emulsion layer. Is known (see Japanese Patent Publication No. 49-15495). However, in this method, although the photographic performance other than the graininess is hard to decrease, the amount of the coupler or silver halide added to the above three layers is small. If it is not appropriate, not only the effect of improving the graininess cannot be expected, but also the result that the color developability of the dye image decreases.

Thus, the present inventors have conducted various studies in view of the above-described problems, and as a result, have found that each color-sensitive layer is coated with a low-, medium-, and high-sensitivity silver halide emulsion coated in order from the side closer to the support. Layer 3
Even when the emulsion layer has a layer structure, there may be a case where the granularity of the yellow dye is not improved or the coloration is reduced, but the image formation added to each of the three emulsion layers may be inconvenient. Each amount of the coupler is 20 to 60 with respect to the total amount of these added amounts.
%, It was found that the granularity of the yellow coloring portion of the color photographic light-sensitive material having the above-mentioned layer constitution was improved without a decrease in the coloring property.

[Object and structure of the invention]

The present invention has been made based on the above findings, and has as its object to resist a silver halide color photographic light-sensitive material capable of forming a yellow dye having excellent granularity without lowering the color developability. And a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer coated on the support, respectively. The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer in the light-sensitive layer are coated in the order of the low-speed silver halide emulsion layer, the medium-speed silver halide emulsion layer, and the high-speed silver halide emulsion layer from the side closer to the support. Comprising three silver halide emulsion layers formed
And the red-sensitive layer, green-sensitive layer, high-sensitivity silver halide emulsion layer of each color-sensitive layer when the amount of image forming couplers used in the blue-sensitive emulsion layer expressed in units of g / m ² Medium The ratio of the added amount of the image forming coupler in the silver halide emulsion layer and the silver halide emulsion layer was 20% each based on the total amount of these additives.
To a silver halide color photographic light-sensitive material, characterized by being within the range of 60% to 60%.

[Specific description of the invention]

 Hereinafter, the present invention will be described specifically.

In the present invention, the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer of the silver halide color photographic light-sensitive material are all a high-speed silver halide emulsion layer, a medium-speed silver halide emulsion layer and a low-speed silver halide emulsion layer. In these red-sensitive, green-sensitive and blue-sensitive emulsion layers, the amount of each image forming coupler used in each color-sensitive layer was g / m ²
When the ratio of the added amount of the image forming coupler in any one of the high-speed layer, the medium-speed layer, and the low-speed layer represented by the formula (A) exceeds 60% based on the total amount of these added amounts, In the present invention, since the coloring property of the layer is reduced and the graininess is deteriorated, and when the ratio is less than 20%, the effect of improving the graininess based on the three-layer structure is reduced. The proportion of the image forming coupler contained in each of the three layers was determined to be 20 to 60%.

The distribution ratio of the image forming coupler to the three blue-sensitive silver halide emulsion layers having different sensitivities is preferably 25 to 45% in the high-speed layer and 30 to 45% in the medium-speed layer.
50%, and 30-50% in the low sensitivity layer, and
In the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer, the blending ratio of the image-forming coupler to these layers is preferably in the same range as that in the blue-sensitive silver halide emulsion layer. preferable.

Here, the image-forming coupler used in the blue-sensitive silver halide emulsion layer means any compound capable of reacting with an oxidized form of a color developing agent to finally form a yellow dye, for example, Other than the yellow coupler used exclusively for forming a dye image, a yellow color-forming functional coupler releasing a photographically useful group such as a development inhibitor or a fogging agent is also included in the image forming coupler. These image forming couplers have a high sensitivity layer,
Any one or two of the medium-speed layer and the low-speed layer
Two or more kinds can be used in combination in one or more layers.

Further, based on the total amount of the respective silver halide contents contained in the blue-sensitive high-speed layer, the medium-speed layer and the low-speed layer, the amount of silver halide relative to these three blue-sensitive silver halide emulsion layers was determined. There is no particular limitation on the distribution ratio, but in general, the distribution ratio is preferably 30 to
80%, 10-70% for the middle layer and 5-50% for the low layer.

As the silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention, any conventional silver halide emulsion can be used, and these emulsions can be prepared by a conventional method using a sensitizing dye. Chemical sensitization can be performed in a desired wavelength range.

Antifoggants or stabilizers can be added to the silver halide emulsion, and gelatin is advantageously used as a binder for this emulsion.

Emulsion layers and other hydrophilic colloid layers can be hardened and these layers can contain plasticizers, dispersions (latexes) of water-insoluble or poorly water-soluble synthetic polymers.

Further in the above layer, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, by coupling with a colored coupler having a color correction curing, a competing coupler, and an oxidized form of a developing agent. Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers or desensitizers can be used.

In the light-sensitive material of the present invention, an auxiliary layer such as a filter layer, an antihalation layer or an anti-irradiation layer can be provided. These auxiliary layers and / or emulsion layers may contain a dye which is bleached during the development processing or flows out of the light-sensitive material.

The light-sensitive material of the present invention may further include a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder or a bleaching accelerator. Can be added.

In the light-sensitive material of the present invention, as a support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

To obtain a dye image using the light-sensitive material of the present invention, ordinary color photographic processing can be employed after exposure.

〔Example〕

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

The addition amount of each component used in producing silver halide color photographic light-sensitive material in the following examples, unless another specified, refers to g per 1 m ^2, a silver halide and colloid The amount of silver added was shown in terms of silver.
The addition amount of the sensitizing dye was shown in terms of moles per mole of silver.

Example 1 On a triacetyl cellulose film support, layers having the following compositions were sequentially formed from the support side to produce a multilayer color photographic light-sensitive material.

First layer: Anti-halation layer Black colloidal silver Silver coating amount: 0.2 Gelatin: 0.4 UV-1: 0.3 High boiling solvent (Oil-1): 0.3 Second layer: Intermediate layer Gelatin: 1.0 Third layer : First red-sensitive silver halide emulsion layer AgBrI (AgI: 7 mol%, octahedral cubic equivalent particle size: 0.3 μm) Silver coating amount: 0.6 Gelatin: 1.2 Sensitizing dye (S-1): 8 × 10 ^-4 sensitizing dye (S-2) 5 × 10 ^-4 sensitizing dye (S-3) 3 × 10 ^-5 coupler (C-1) 0.10 coupler (C-3) 0.25 Colored coupler (CC-1) 0.04 DIR coupler (D-2) 0.05 High boiling solvent (Oil-1) 0.45 4th layer: 2nd red-sensitive silver halide emulsion layer AgBrI (AgI 8 mol%) , octahedral equivalent cubic diameter 0.7 .mu.m m) silver coverage ...... 1.0 gelatin ...... 1.3 sensitizing dye (S-1) ...... 3 × 10 -4 sensitizing dye (S-2) ...... 2 × 10 - ⁴ increase Dye (S-3) ...... 2 × 10 -5 coupler (C-1) ...... 0.10 Coupler (C-3) ...... 0.30 colored coupler (CC-1) ...... 0.03 DIR coupler (D-2) ...... 0.07 High boiling point solvent (Oil-1) 0.50 Fifth layer: Third red-sensitive silver halide emulsion layer AgBrI (AgI 6 mol%, particle size in terms of octahedral cube 1.0 μm) Silver coating amount 1.6 Gelatin 1.6 sensitizing dye (S-1) 1 × 10 ^-4 sensitizing dye (S-2) 1 × 10 ^-4 sensitizing dye (S-3) 1 × 10 ^-5 coupler (C -1) 0.20 coupler (C-3) 0.10 colored coupler (CC-1) 0.02 DIR coupler (D-2) 0.05 high boiling solvent (Oil-1) 0.40 6th layer: Intermediate layer Gelatin 0.80 SC-1 0.03 SC-2 0.02 High boiling point solvent (Oil-2) 0.05 0.05 Seventh layer: First green-sensitive silver halide emulsion layer AgBrI (AgI 7 mol%, 8 Body equivalent cubic diameter 0.3 micron m) silver coverage ...... 0.4 Gelatin ...... 0.8 Sensitizing dye (S-4) ...... 6 × 10 -4 Sensitizing dye (S-5) ...... 1 × 10 -4 increase Sensitizing dye (S-6) 1 × 10 ^-4 coupler (M-1) 0.05 Coupler (M-3) 0.25 Colored coupler (CM-1) 0.04 DIR coupler (D-1) 0.06 High boiling point solvent (Oil-2) 0.40 Eighth layer: Second green-sensitive silver halide emulsion layer AgBrI (AgI 8 mol%, octahedral cubic equivalent particle size 0.7 μm) Silver coating amount 0.8 Gelatin 1.1 sensitizing dye (S-4) 3 × 10 ^-4 sensitizing dye (S-5) 5 × 10 ^-5 sensitizing dye (S-6) 5 × 10 ^-5 coupler ( M-1) 0.05 Coupler (M-3) 0.20 Colored coupler (CM-1) 0.03 DIR coupler (D-1) 0.05 High boiling solvent (Oil-2) 0.30 Ninth layer : Third green sensitive halogen Silver emulsion layer AgBrI (AgI 6 mol%, octahedral equivalent cubic diameter 1.0 micron m) silver coverage ...... 1.2 Gelatin ...... 1.1 Sensitizing dye (S-4) ...... 2 × 10 -4 Sensitizing dye (S -5) 5 × 10 ^-4 sensitizing dye (S-6) 5 × 10 ^-4 coupler (M-2) 0.05 Coupler (M-3) 0.10 Colored coupler (CM-1) ... 0.02 DIR coupler (D-1) ... 0.02 High boiling point solvent (Oil-2) ... 0.30 10th layer: Yellow filter layer Yellow colloidal silver ... 0.05 Gelatin ... 1.0 SC-1 ... 0.03 SC-2 0.02 High-boiling point solvent (Oil-2) 0.05 0.05 11th layer: 1st blue-sensitive silver halide emulsion layer AgBrI (AgI 7 mol%, octahedral cubic equivalent particle diameter 0.7 μm) Silver coating amount 0.20 gelatin ...... 1.30 sensitizing dye (S-7) ...... 1 × 10 -3 coupler (Y-1) ...... 0.88 DIR coupler (D-2) ...... 0.10 high boiling solvent (Oil-2) ... 0.28 12th layer: 2nd blue-sensitive silver halide emulsion layer AgBrI (AgI 8 mol%, octahedral cubic equivalent particle size 0.7 μm) Silver coating amount 0.50 gelatin 0.50 sensitizing dye (S-7) 5 × 10 ^-4 coupler (Y-1) 0.48 DIR coupler (D-2) 0.08 High boiling point solvent (Oil-2) 0.25 13th layer: Third blue-sensitive silver halide emulsion layer AgBrI (AgI 6 mol%, octahedral cubic equivalent particle size 1.0 μm) Silver coating amount 0.70 Gelatin 0.70 Sensitizing dye (S-7) 2 × 10 ^-4 coupler (Y-1) 0.24 DIR coupler (D-2) 0.01 High boiling solvent (Oil-2) 0.07 14th layer: 1st protective layer AgBrI (AgI 1 mol%, octahedral cubic equivalent particle size 0.08 μm) Silver coating amount 0.3 Gelatin 1.0 UV absorber (UV-1) 0.1 UV absorber (UV-1) 0.1 Formalin scavenger (HS-1) 0.5 Formalin Scavenger (HS-2) 0.2 High-boiling solvent (Oil-1) 0.1 High-boiling solvent (Oil-3) 0.1 15th layer: 2nd protective layer Gelatin ... 0.7 Alkali-soluble matting agent (average particle size) 0.12 Polymethyl methacrylate (average particle size 3 μm) ... 0.02 Sliding agent (WAX-1) ... 0.04 Charge control agent (Su-1) ... 0.004 In each of the above layers, In addition, coating aid Su
-2, dispersing aids Su-2 and Su-3, hardeners H-1 and H-2, stabilizer Stab-1, antifoggant AF-1 and
AF-2 and preservative DI-1 were added.

 The compounds used in these layers are shown below.

Next, Comparative Sample 2 was prepared in the same manner as Comparative Sample 1 except that the amount of coupler (Y-1) contained in the eleventh to thirteenth layers of Comparative Sample 1 was changed as shown in Table 1. ~ 4
And Inventive Samples 1 to 4 were prepared.

After subjecting the comparative samples 1 to 4 and the inventive samples 1 to 4 prepared as described above to wedge exposure using white light, the exposed samples were subjected to the processing according to the following processing step [I]. gave.

Processing step (I) (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in step [I] is shown below.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g Sodium anhydrous zincate 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Carbonic anhydride Potassium 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to 1 (pH = 10.1).

<Bleaching solution> Ammonium salt of iron (III) ethylenediaminetetraacetate 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to 1 to adjust the pH to 6.
Adjust to 0.

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust the pH to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1

The results of sensitometry and graininess by blue (B) light, which were examined for each sample after the development treatment, are as shown in Table 2. Here sensitivity giving a density of minimum density +0.3 exposure: the inverse of E _1, 1 the sensitivity of Comparative Sample 1
It is shown as a relative value when 00 is set. Further, the exposure amount E ₁
The difference between the color density and the minimum density when given 10 times the exposure amount E ₂ D _2, and the difference between the color density and the minimum density when given 100 times the exposure amount E ₃ of the exposure amount E ₁ Is D ₃ , each exposure amount E ₁ ,
The graininess of the sample in E ₂ and E ₃ were determined as an RMS value. This RMS value is measured by measuring the color density with a Sakura Micro Densitometer Model PDM-5 Type AR (manufactured by Konica Corporation) under an opening area of 250 μm ² and calculating the standard deviation relating to the fluctuation of the density value. The RMS granularity of each of the exposure amounts E ₁ , E _2, and E ₃ of Comparative Sample 1 was defined as a relative value when 100. Therefore, a sample having a lower RMS relative value means that its graininess is superior.

Further, a portion where the exposure amount E ₂ is given in the comparative sample 1, orthochromatic type black-and-white photographic paper drawn down magnification 10 times under the white light using a (Fujiburooruso WP FM-3), which is then Konica tone Black and white development was performed by Konica Corporation to produce a print having a reflection density of 0.7.

Then, from the portion where the exposure amount E ₂ are given in the comparative samples 2-4 and inventive samples 1-4 in the same manner as described above to produce a black and white print, in that case, the 10-fold expansion of the comparative sample 1 seeking magnification of the exposure amount E ₂ portion when same graininess and print is observed, the results second
It is shown in the table. Therefore, the larger the magnification of the black-and-white print shown in Table 2, the better the graininess of the sample.

From the results shown in Table 2, (1) Comparing Comparative Samples 1 to 3 using the same amount of coupler: Y-1 with Samples 1 to 4 of the present invention, the sample of the present invention is more than the comparative sample. since even a large value of D ₂ and D _3, the present invention samples have excellent coloring property than the comparative samples have excellent graininess than (2) the present invention sample comparative samples, high exposed areas the coating It can be seen that the improvement of the graininess of the sample of the present invention is remarkable, and that (3) the graininess when printed on an orthochromatic black-and-white printing paper is significantly improved in the sample of the present invention.

Example 2 Comparative samples 1 to 4 and inventive samples 1 to 4 produced in Example 1 were cut into a 35 mm-size film, and after performing general photography under various conditions using this film,
Developing treatment was performed in the same manner as in Example 1 to produce a negative film. Then, the negative film was magnified at a magnification of 5 times and baked on Konica color paper.
8 (manufactured by Konica Corporation).

When the obtained print image was visually evaluated, the sample of the present invention was more excellent in granularity than the comparative sample in most scenes, and the sample of the present invention was particularly excellent when performing sunset photography or indoor photography using tungsten light. Showed significantly better granularity than the comparative sample.

〔The invention's effect〕

As is apparent from the above description, according to the present invention, there is provided a silver halide color photographic light-sensitive material exhibiting excellent color developability and exhibiting improved granularity in a yellow color-developing portion. Of course, the graininess of the yellow pigment, such as in the morning or evening or under a tungsten light, is generally low in color temperature, or when printed on black and white paper. Thus, a silver halide color photographic light-sensitive material capable of forming an image having particularly excellent image quality even when used under conditions that greatly affect image quality is provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-100456 (JP, A) JP-A-1-304459 (JP, A) JP-A-3-1544051 (JP, A) JP-A-2- 139544 (JP, A) JP-A-1-283560 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 7/20

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material comprising a support, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer respectively coated on the support. In the material, the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer in the color-sensitive layer are preferably a low-speed silver halide emulsion layer, a medium-speed silver halide emulsion layer, and a high-speed halide The amount of the image-forming coupler comprised of three silver halide emulsion layers formed by coating in the order of a silver emulsion layer and used in the red-sensitive layer, the green-sensitive layer, and the blue-sensitive emulsion layer was g / m2. The ratio of the amount of the image forming coupler in the high-speed silver halide emulsion layer, the medium-speed silver halide emulsion layer and the low-speed silver halide emulsion layer of each of the color-sensitive layers when expressed in ² units is Based on the total amount of Both of which lies in the range from 20 to 60%, respectively, the silver halide color photographic light-sensitive material.