JPH0876326A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide color photographic sensitive material for photographing enhanced in a print yield. CONSTITUTION: The silver halide color photographic sensitive material for photographing has photographic constituent layers comprising at least one of each of red-, green-, and blue-sensitive layers and nonphotosensitive layer on a support, and at least one of the photosensitive layers comprises at least 3 layers different from each other in sensitivity and the second highest sensitive layer has a latitude of 50-80% of the total latitude and the photosensitive silver halide grains contained in this layer are formed by using a gelatin having an adenine content of <=0.2ppm and adding a substantially water-insoluble spectral sensitizing dye as an aqueous solid fine particle dispersion containing substantially no organic solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color light-sensitive material, and more particularly to a silver halide color light-sensitive material having improved print yield.

[0002]

2. Description of the Related Art In a laboratory (laboratory) that processes a large amount of negative film taken by general amateur users,
Efforts are constantly being made to minimize printing failures and increase the yield.

Recently, with the spread of high-performance printers,
Although print yields are improving, the shooting conditions and storage conditions for negative film have become more severe due to the diversification of leisure activities on the part of users who take photographs, and there are variations in the development processing level on the lab side. Therefore, the yield is 10
The current situation is that it has not reached 0%.

On the other hand, in a photographic negative photographic material, the latitude is expanded by laminating one color-sensitive layer, which contributes to the improvement of print yield, but it is not sufficient. In addition to simply expanding the latitude, it is required to devise a design for each layer having different sensitivities constituting one color-sensitive layer.

On the other hand, JP-A-60-24546 and JP-A-60-149044
No. 61, No. 61-289349, No. 62-91945, No. 62-210464,
62-262852 and Japanese Examined Patent Publication No. 49-15495 disclose a technique for improving image quality such as sharpness and graininess by defining the maximum density value of each layer for three layers having the same color-sensing layer and different sensitivities. Is disclosed.

Although the individual image quality can be improved simply by defining the contribution ratio of the maximum density, it is difficult to improve the print yield.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide color light-sensitive material having an improved print yield.

[0008]

The object of the present invention has been achieved by the following constitution.

In a silver halide color photographic material for photography having a photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer on a transparent support, at least one of the photosensitive layers is A silver halide color light-sensitive material comprising three or more layers having different sensitivities, and the latitude of the layer having the second highest sensitivity is 50 to 80% of the total latitude.

The present invention will be described in more detail below.

In the present invention, the total latitude means the minimum density (Dmin) +0.10 to the maximum density (Dmin) on the characteristic curve (D-logE) of the entire photosensitive layer having the same color sensitivity and three or more layers having different sensitivities. Dmax) -ΔE value up to -0.15. or,
The ratio of latitude is a numerical value obtained by obtaining the latitude of each layer having different sensitivities constituting the same color-sensitive layer in the same manner as the total latitude and taking the percentage.

In the present invention, the ratio of the latitude of the layer having the second highest sensitivity among the same color-sensitive layers is 50 to 80% of the total latitude, more preferably 55 to 75%, and particularly preferably 55 to 65%. Also, the value of all latitude is 2.
It is 50 to 3.50, preferably 2.80 to 3.40.

In the present invention, the proportion of latitude in the highest sensitivity layer is preferably 10 to 20%, and the proportion of latitude in the lowest sensitivity layer is preferably 10 to 40%.

The constitution of the present invention can be applied to any of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer of a color light-sensitive material, and the effect is particularly large when applied to the red-sensitive layer.

In the present invention, it is preferable to use gelatin having an adenine content of 0.2 ppm or less in the step of forming silver halide grains used in the second most sensitive layer. The adenine content in gelatin is the adenine content (items 19 and 27) described in the photographic gelatin test method (photographic gelatin test method Joint Committee, 7th edition).
~ Page 28) for quantitative analysis.

General gelatin production methods are described in, for example, the Japan Photographic Society, edited by: The Basics of the Photographic Industry, Silver Salt Photography, published by Corona (pages 122-124), and gelatin is the main connective tissue of animals. It is produced from collagen as a component, and examples of raw materials for photographic gelatin include cow bone, cow hide, pig skin, and the like, but it is common to use cow bone and cow hide.

Although there are two types of collagen treatment methods, an acid treatment method and a lime treatment method, the lime treatment method is generally used as photographic gelatin. In the gelatin according to the present invention, Also, it is preferable to use the lime treatment method.

As an example, in the case of producing photographic gelatin from beef bone by lime treatment, it usually undergoes processes of decalcification, lime treatment, extraction, filtration, concentration, gelation and drying. The dried beef bones are soaked in a dilute hydrochloric acid solution for 4 to 8 days for decalcification,
After rinsing with water and neutralization, the skins and bones of cattle are calcined in saturated lime water for 2 to 3 months to remove keratin, and after rinsing with water and neutralization, hot water at about 50-60 ° C for 6-8 hours Extraction (No. 1 extraction) is performed, and then hot water of about 5 to 10 ° C is added, and No. 2 and No. 3 extractions are performed. After extraction, it goes through a filtration process, usually under reduced pressure at 60 ℃
It is concentrated at the following temperature, cooled, gelled, and dried at about 25 ℃.

The gelatin according to the present invention can be obtained by using gelatin having a gelatin extraction temperature of 40 to 60 ° C. specified in the above-mentioned production method and passing the gelatin through a cation and anion exchange resin after the filtration step. . At this time, in the ion exchange treatment, both the treatment with the cation exchange resin and the treatment with the anion exchange resin are performed.

Further, it is preferable to use a hard bone portion of bovine bone as a raw material of gelatin. The deionization step may be performed anywhere after the gelatin extraction step, but is preferably performed after the filtration step.

As the ion exchange resin, a cation exchange group of --H type or --Na type and an anion exchange group of --OH are used.
Type, -Cl type, but -H as a cation exchange group
Type, and the anion exchange group is preferably -OH type. The ion exchange treatment time is sufficient for the ion exchange resin treatment to eliminate the ionic components from the gelatin solution,
It is preferable to determine the amount of the ion exchange resin used and the treatment time so that the pH value of the gelatin solution is about 4.9 to 5.3. In addition, it is preferable that the cation-exchange resin treatment is performed first as the treatment order. Further, the pH value of the gelatin solution subjected to the ion exchange treatment may be adjusted with an ordinary pH adjusting agent, but the pH value of the isoelectric point is preferably kept as it is without adjustment.

The content of adenine in the gelatin of the present invention is preferably 0.1 ppm or less, more preferably 0.05.
ppm or less is good.

In the present invention, the silver halide grains used in the second most sensitive layer are preferably core / shell type. The core of the silver halide grains consists essentially of silver iodobromide, and it is preferable that the core consists essentially of silver iodobromide containing 5 mol% or more of silver iodide. The silver halide grains are constituted by a shell covering the core and consisting essentially of silver iodobromide or silver bromide having a silver iodide content lower than the silver iodide content of the core. The silver iodide content of the core is more preferably 10 mol% or more, and most preferably 20 to 44 mol%. The silver iodide content of the shell is preferably 5 mol% or less, and most preferably 0 to 2.5 mol%.

The core may contain silver iodide uniformly, or may have a multiple structure composed of phases having different silver iodide contents. In the latter case, the silver iodide content having the highest silver iodide content is preferably 5 mol% or more,
More preferably, it is 10 mol% or more. Moreover, the silver iodide content of the shell may be lower than that of the highest silver iodide content phase of the core. In such a core / shell type silver halide grain, the slope due to the difference in content from the layer having a high silver iodide content to the layer having a low silver iodide content may have a sharp boundary, or may have a sharp boundary. It is not always clear that it may change continuously.

The silver iodide content of individual silver halide grains,
And the average silver iodide content is measured by the EPMA method (Electron Probe
It can be determined by using Micro Analyzer). This method is a technique in which a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and elemental analysis of an extremely minute portion is performed by X-ray analysis by electron beam irradiation with electron beam irradiation.

By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensities of silver and iodine emitted from each grain.

If the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average of them.

In order to achieve both high sensitivity and high image quality, as described in JP-A-60-128443, the average silver iodide content of silver halide in all emulsion layers should be 3 mol% or more. Preferably.

In the present invention, a substantially water-insoluble photographic spectral sensitizing dye is added to the second most sensitive layer as an aqueous solid fine particle dispersion containing substantially no organic solvent. Preference is given to using silver halide emulsions.

Here, the substantially water-insoluble spectral sensitizing dye means a spectral sensitizing dye having a solubility of 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / liter at 27 ° C. in an aqueous system in which an organic solvent does not exist. It is a dye. In the present invention, these spectral sensitizing dyes can be added in an amount exceeding the solubility and mechanically dispersed in solid fine particles of 1 μm or less to be added to the emulsion.

A technique for mechanically dispersing an organic dye in an aqueous medium is known from Japanese Patent Laid-Open No. 3-288842.

In the present invention, the aqueous system in which substantially no organic solvent is present is water containing impurities below the extent that it does not adversely affect the silver halide photographic emulsion, and more preferably ion-exchanged water.

The solubility in water of the spectral sensitizing dye in the present invention is a 2 × 10 ^-4 ~4 × 10 ^-2 mol / liter, more preferably 1 × 10 ^-3 ~4 × 10 ^-2 mol / It is a liter.

That is, if the solubility is lower than this range, the dispersion particle size becomes very large and non-uniform, so that the dispersion is precipitated after the dispersion is completed or the dispersion is added to the silver halide emulsion. It was found that the process of adsorbing the dye on the silver halide was hindered.

When the solubility is higher than this range, the viscosity of the dispersion is increased more than necessary, air bubbles are entrapped, and the dispersion is hindered. At higher solubility, dispersion becomes impossible. However, it has become clear from the research conducted by the present inventors.

The spectral sensitizing dye in the present invention means a compound which causes electron transfer to the silver halide when it is photoexcited when adsorbed on the silver halide and does not include an organic dye.

The spectral sensitizing dye added as the solid fine particle dispersion of the present invention has a solubility in water of 2 × 10 ⁻⁴ to 4 ×.
Any dye may be used within the range of 10 ^-2 mol / liter, preferably a cyanine dye. More preferably,
It is a cyanine dye having a hydrophilic group (eg, sulfo group, carboxyl group).

The above-mentioned dispersion of the spectral sensitizing dye of the present invention is
It is added to the emulsion during the process from chemical ripening to coating. Here, the process from the chemical ripening to the coating means during the chemical ripening and thereafter until the coating is performed to form the light-sensitive material.

As a concrete working example, after water is put in a tank whose temperature can be adjusted, a certain amount of the powder of the spectral sensitizing dye is put therein, and a high-speed stirrer is used for a certain time under temperature control. Stir and pulverize and disperse to 1 μm or less. Further, the pH and the temperature at which the spectral sensitizing dye is mechanically dispersed are not particularly limited, but at a low temperature, even if the dispersion is carried out for a long time, the desired particle diameter cannot be reached.
Re-aggregation or decomposition occurs at high temperature, and the desired photographic performance cannot be obtained, and when the temperature is raised, the viscosity of the solution system decreases and the efficiency of solid pulverization and dispersion is greatly reduced. There's a problem. Therefore, the dispersion temperature is more preferably 15 to 50 ° C. Furthermore, the stirring rotation speed during dispersion requires a long time to obtain the desired particle size at low rotation speeds, and at high rotation speeds entrains bubbles and reduces dispersion efficiency, so dispersion at 1000-6000 rpm More preferably.

The fact that the solid fine particles of the spectral sensitizing dye dispersed by the method of the present invention is 1 μm or less means that the particle size according to the volume average diameter of spheres is 1 μm or less, which is measured by a general method. it can.

The dispersion used in the present invention means an aqueous suspension of a spectral sensitizing dye, preferably a spectral sensitizing dye having a weight ratio of 0.2 to 5.0% in the suspension. Used.

The dispersion of the spectral sensitizing dye prepared according to the present invention may be added directly to the silver halide emulsion,
Water may be used as the diluting solution at this time, although it may be appropriately diluted before addition.

The emulsion used in the present invention is preferably one in which fine grain silver iodide is added in the step of grain formation or chemical ripening. Regarding silver iodide, generally cubic γ-AgI and hexagonal β-AgI are known, but the fine grain silver iodide used in the present invention may have any crystal structure, or,
It may be a mixture of these.

The fine grain silver iodide used in the present invention preferably has good monodispersity and can be obtained by the double jet method.
It is preferable to prepare it while controlling temperature, pH and pAg.

The addition amount of fine grain silver iodide is 1 × 10 ^-4 to 1 × 10 ^-2 mol, preferably 5 × 10 ^{-4 to} 5 × 10 ^-3 mol per mol of silver halide added. .

The grain size of fine grain silver iodide is 0.2.
It is preferably not more than μm, and more preferably 0.02 to 0.1 μm.

The fine grain silver iodide may be added in any step from the grain forming step to the chemical ripening step, but it is preferably added in the chemical ripening step. The term "chemical ripening step" as used herein refers to the period from the time when the physical ripening and desalting operations of the emulsion are completed to the time when an operation for adding a chemical sensitizer and then stopping the chemical ripening is performed.

As a method of finishing the chemical ripening, a method of lowering the temperature, a method of lowering the pH, a method of using a chemical ripening stopper, etc. are known. The method using a terminating agent is preferred. Examples of the chemical aging inhibitor include halides (eg, potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (4-hydroxy).
-6-methyl-1,3,3a, 7-tetrazaindene or 1-phenyl-
5-mercaptotetrazole and the like) are known. These are used alone or in combination of a plurality of compounds.

The fine grain silver iodide may be added in several times with a time interval, or another chemical ripened emulsion may be added after the fine grain silver iodide is added.

To form the light-sensitive material of the present invention, an emulsion other than the emulsion of the present invention can be used in combination, if necessary. In this case, the silver halide composition of the emulsion used in combination is arbitrary, and examples thereof include silver bromide, silver iodobromide, silver iodochlorobromide,
Any of silver chlorobromide, silver chloride and the like, or a mixture thereof may be used.

The emulsion of the present invention, the emulsion for obtaining the same, and the emulsions other than the present invention which are optionally used in combination (hereinafter, collectively referred to as "emulsion used in the present invention") are defined below. The monodisperse type is preferred. That is,
The value obtained by dividing the standard deviation of the particle size by the average particle size by 100 (hereinafter referred to as the coefficient of variation) is 16 or less, as defined by the following formula, is called monodispersity. In this sense, a monodisperse emulsion is preferred.

(Standard deviation / average grain size) × 100 ≦ 16% The shape of the silver halide grains in the emulsion used in the present invention, for example, the above monodisperse emulsion, is cubic, octahedral or tetradecahedral. It may be any shape, or may be a spherical shape, a plate shape, or the like, and is arbitrary.

In the case of constituting the light-sensitive material of the present invention, the silver halide emulsion is generally used after physical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No.17643, No.1
8716 and No.308119 (RD17643, RD18716 and R, respectively)
Abbreviated as D308119). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-A, B, C, D, H, I, J 23-24 648-9 Supersensitizer 996 IV-AE, J Section 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Chemistry of emulsions used in the present invention More specifically, the sensitization is performed by a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitizing method using active gelatin, a selenium sensitizing method using a selenium compound, a reduction sensitizing method using a reducing substance, and a gold sensitizing method. The noble metal sensitization method using other noble metal compounds can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizer can be used as the chemical sensitizer, and among them, a sulfur sensitizer and a selenium sensitizer are preferable.

Examples of the sulfur sensitizer include thiosulfate,
Examples thereof include allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine.

Others, US Pat. Nos. 1,574,944 and 2,410,6
89, 2,278,947, 2,728,668, 3,501,313
No. 3,656,955, West German Application Publication (OLS) 1,422,869
The sulfur sensitizers described in JP-A Nos. 56-24937 and 55-45016 can also be used.

The amount of the sulfur sensitizer added varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains.
About 10 ^-7 to about 10 ^-1 mole per mole is preferred.

As the selenium sensitizer, there may be used aliphatic isocyanates such as allyl isoselenocyanate, selenourea, selenides such as dimethyl selenide, diethyl selenide, and the like. ,
U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499 and the like are described. Furthermore, a reduction sensitizer can be used in combination.

Examples of the reducing agent include stannous chloride, thiourea dioxide, hydrazine and polyamine. Further, a noble metal compound other than gold, for example, a palladium compound or the like can be used together.

The silver halide grains of the emulsion used in the present invention preferably contain a gold compound. The gold compound preferably used may have a gold oxidation number of +1 valence or +3 valence, and various kinds of gold compounds are used.

As typical examples, chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold. Examples include sulfide and gold selenide.

The gold compound may be used for sensitizing the silver halide grains, or may be used so as not to substantially contribute to the sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guide, it is 10 ^-8 to 10 ^-1 per mol of silver halide.
It is a molar amount, preferably 10 ⁻⁷ to 10 ⁻² mol.

Further, these compounds may be added at any of the steps of grain formation of silver halide, physical ripening, chemical ripening and after chemical ripening.

Known photographic additives that can be used in the present invention are also described in the above Research Disclosure (RD). The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII -C, XIII C Item 25 to 26 Light absorber 1003 VIII 25 to 26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25 to 26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matte agent 1007 XVI Developer (included in photosensitive material) 1011 XXB Item Also, to prevent deterioration of photographic performance due to formaldehyde gas. In addition, it is preferable to add to the photographic material the compounds described in US Pat. Nos. 4,411,987 and 4,435,503, which can be immobilized by reacting with formaldehyde.

Various color couplers can be used in the present invention, specific examples of which are described in the following RD. The relevant parts are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-D item VIIC-G item Colored coupler 1002 VII-G item VIIG item DIR coupler 1001 VII-F item VIIF item BAR coupler 1002 VII-F item Other useful residues Release coupler 1001 VII-F item Additives used include the dispersion method described in RD308119XIV. Can be added by.

In the present invention, the above-mentioned RD308119VII-
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided.

The light-sensitive material of the present invention is the above-mentioned RD308119VII-
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section K can be adopted.

Suitable supports usable in the present invention are described, for example, in RD17643, page 28 and 18716, page 647, right column to page 648, left column.

As a concrete support, paper laminated with polyethylene or the like, polyethylene terephthalate film, polyethylene naphthalate film, baryta paper, cellulose triacetate film or the like can be used. The thickness of the support is usually 50 to 200 μm.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. .

Further, the present invention can be applied to the "small photographic roll film cartridge and film camera" of Japanese Patent Laid-Open No. 5-210201.

To obtain a dye image using the light-sensitive material of the present invention, a commonly known color development process can be carried out after exposure. That is, RD17643, pp. 28-29, RD1871
Development can be carried out by a usual method described on pages 6,647 and XII of RD308119.

[0077]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A multi-layer color light-sensitive material sample 101 was prepared by sequentially coating each layer having the following constitution from the support side on a triacetyl cellulose support provided with an undercoat layer.

In all the following descriptions, the addition amount in the light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver halide in the same layer.

The emulsion of each photosensitive layer is optimally spectrally sensitized by a spectral sensitizing dye described below and sulfur / gold sensitization.
An appropriate amount of antifoggant is added.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point organic solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer High boiling point organic solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content) Ratio 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD -4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling solvent (Oil-1) 0.53 Gelatin 1.30 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0.62 Odor Silver emulsion (average grain size 0.38 .mu.m, a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD─1) 2.3 × 10 ^-4 Sensitizing dye (SD─2) 1.2 × 10 ^-4 Sensitizing dye (SD ─3) 1.6 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D -1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye ( SD-1) 1.3 × 10 ^-4 sensitizing dye (SD-2) 1.3 × 10 ^-4 sensitizing dye (SD-3) 1.6 × 10 ^-5 cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) ) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer: Intermediate layer High boiling point organic solvent (Oil-2) 0.11 Gelatin 0.80 7th layer: Low sensitivity green sensitive layer Silver iodobromide emulsion ( Hitoshitsubu径0.38 .mu.m, a silver iodide content of 8.0 mol%) 0.61 Silver iodobromide emulsion (average particle diameter 0.27 [mu] m, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD─4) 7.4 × 10 ^{- 5} Sensitizing dye (SD- ⁵ ) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling solvent (Oil-2) 0.75 Gelatin 1.95 Eighth layer: Medium-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 Sensitizing dye (SD-- 7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point Solvent (Oil-2) 0.50 Gelatin 1.00 9th layer: High sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 %) 1.27 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling solvent (Oil-1) 0.27 High boiling solvent (Oil-2) 0.012 Gelatin 1.00 10 layers: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-1) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer: Intermediate layer Formalin scavenger (HS-) 1) 0.20 Gelatin 0.60 Layer 12: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 µm, silver iodide content 3.0 mol%) 0.22 Silver iodobromide emulsion (average grain size 0.27 µm, iodide) Silver content 2.0 mol%) 0.03 Sensitizing dye (SD-8) 4.9 × 10 ^-4 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th Layer: Medium sensitivity blue sensitive layer Iodobromide Emulsion (average grain size 0.59 .mu.m, a silver iodide content of 8.0 mol%) 0.30 Sensitizing dye (SD─8) 1.6 × 10 ^-4 Sensitizing dye (SD─9) 7.2 × 10 ^-5 Yellow coupler (Y─1 ) 0.10 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 10.0 mol%) 0.85 Sensitizing dye (SD- 8) 7.3 × 10 ^-5 Sensitizing dye (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 15th layer: 1st protective layer Iodobromide Silver emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.10 High boiling solvent (Oil-1) 0.07 High boiling solvent ( Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Poly Methyl methacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Su-2, viscosity modifier V-1, hardener Membrane agents H-1, H-2,
Stabilizer ST-1, Antifoggant AF-1, Dye AI-
1, AI-2, two kinds of AF-2 having a weight average molecular weight of 10,000 and 1,100,000, and a preservative DI-1 were added. DI-1
Was 9.4 mg / m ² .

The photosensitive silver halides of the fourth, eighth and thirteenth layers are internal high iodine type core / shell emulsions, all of which are formed by using gelatin having an adenine content of 0.03 ppm.
In addition, fine grain silver iodide was added in an amount of 1.2 × 10 ^-3 mol per mol of silver halide in the chemical sensitization step.

The structures of the compounds used in the above samples are shown below.

Oil-1: dioctyl phthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate SC-1: 2-methyl-5-sec-octadecyl hydroquinone Su-1: dioctyl sodium sulfosuccinate So-2 : Sodium tri-i-propylnaphthalene sulfonate HS-1: Hydantoin H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium H-2: Bis (vinylsulfonylmethyl) ether ST-1: 4 -Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: Poly-N-vinylpyrrolidone

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[Chemical 7]

Sensitizing dyes SD-1, 2, 3, 4 and SD-
6, 7, 8 and 9 were added to the silver halide emulsion during the chemical ripening step as the following aqueous solid fine particle dispersions.

Sensitizing dye 10 parts by weight Ion-exchanged water 190 parts by weight 100 ° C. at 4,000 rpm with a high speed dissolver type agitator at 27 ° C.
Stir for minutes.

The third to fifth red-sensitive layers of Sample 101 were changed as follows, and Samples 102 to 106 having the same sensitivity and gradation as those of Sample 101 were prepared.

-Sample 102- Third Layer: Low Sensitivity Red Sensitive Layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.55 Silver iodobromide emulsion (average grain size 0.27 μm, Silver iodide content 2.0 mol%) 0.23 Sensitizing dye (SD-1) 3.1 × 10 ^-4 Sensitizing dye (SD-2) 2.1 × 10 ^-4 Sensitizing dye (SD-3) 2.1 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.1 × 10 ^-4 Cyan coupler (C-1) 0.53 Cyan coupler (C-2) 0.15 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.022 High boiling solvent (Oil ─ 1) 0.58 Gelatin 1.43 Layer 4: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0.70 Silver iodobromide emulsion (average grain size 0.38 μm, iodine) Silver halide content 8.0 mol%) 0.30 Sensitizing dye (SD-1) 2.6 × 10 ^-4 Sensitizing dye (SD-2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.8 × 10 ^-5 Sensitizing dye dye (SD─4) 1.4 × ^{10 -4} Uncoupler (C-1) 0.14 Cyan coupler (C-2) 0.17 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling solvent (Oil-1) 0.29 Gelatin 0.93 Fifth layer: High sensitivity Red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.3 × 10 ^{− 4} Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91-Sample 103-Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.60 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content rate 2.0 mol%) 0.25 increase sensitive dye (SD─1) 3.4 × 10 ^-4 sensitizing dye (SD─2) 2.3 × 10 ^-4 sensitizing dye (SD─3) 2.3 × 10 ^-5 sensitizing dye (SD─4) 1.2 × 10 ^{- 4} Uncoupler (C-1) 0.58 Cyan coupler (C-2) 0.17 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.022 High boiling point solvent (Oil-1) 0.62 Gelatin 1.30 4th layer: Medium sensitivity Red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content rate 8.0 mol%) 0.78 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.34 Sensitizing dye (SD-1) 2.9 × 10 ^-4 sensitizing dye (SD-2) 1.5 × 10 ^-4 sensitizing dye (SD-3) 2.0 × 10 ^-5 sensitizing dye (SD- ⁴ ) 1.5 × 10 ^-4 cyan Coupler (C-1) 0.11 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.011 High boiling solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: High sensitivity red sensitive layer silver iodobromide emulsion (average grain size 1.00 .mu.m, a silver iodide content of 8.0 mol%) 1.27 sensitizing dye (SD─1) 1.3 × 10 ^-4 sensitizing dye (SD─ ) 1.3 × 10 ^-4 Sensitizing dye (SD─3) 1.6 × 10 ^-5 cyan coupler (C─2) 0.11 Colored cyan coupler (CC─1) 0.013 High-boiling solvent (Oil─1) 0.13 Gelatin 0.91 - Sample 104 -Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 µm, silver iodide content rate 8.0 mol%) 0.62 Silver iodobromide emulsion (average grain size 0.27 µm, silver iodide content rate 2.0) Mol%) 0.25 sensitizing dye (SD-1) 3.4 × 10 ^-4 sensitizing dye (SD-2) 2.3 × 10 ^-4 sensitizing dye (SD-3) 2.3 × 10 ^-5 sensitizing dye (SD- ⁴ ) ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.65 Cyan coupler (C-2) 0.19 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (Oil-1) 0.69 Gelatin 1.40 Layer 4: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content rate 8.0 mol%) 0.78 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) %) 0.34 Sensitizing dye (SD-1) 2.9 × 10 ^-4 Sensitizing dye (SD-2) 1.5 × 10 ^-4 Sensitizing dye (SD-3) 2.0 × 10 ^-5 Sensitizing dye (SD- ⁴ ) ) 1.5 × 10 ^-4 Cyan coupler (C-1) 0.09 Cyan coupler (C-2) 0.11 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.27 Gelatin 0.93 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-- 2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.11 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.13 Gelatin 0.91-Sample 105- Third Layer: Low Sensitivity Red Sensitive Layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.65 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol %) 0.25 sensitizing dye (SD-1) 3.4 × 10 ^-4 sensitizing dye (SD-2) 2.3 × 10 ^-4 sensitizing dye (SD-3) 2.3 × 10 ^-5 sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.65 Cyan coupler (C-2) 0.19 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (Oil-1) 0.69 Gelatin 1.40 4 layers: Medium sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content rate 8.0 mol%) 0.82 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) ) 0.36 Sensitizing dye (SD-1) 3.0 × 10 ^-4 Sensitizing dye (SD-2) 1.6 × 10 ^-4 Sensitizing dye (SD-3) 2.1 × 10 ^-5 Sensitizing dye (SD-4) 1.2 × 10 ^-4 cyan coupler (C─1) 0.09 cyan coupler (C─2) 0.11 colored cyan coupler (CC─1) 0.030 DIR compound (D─1) 0.013 high-boiling solvent (Oil─1) 0.27 gelatin 0.93 the Layer: high sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 .mu.m, a silver iodide content of 8.0 mol%) 1.27 Sensitizing dye (SD─1) 1.3 × 10 ^-4 Sensitizing dye (SD─2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.11 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.13 Gelatin 0.91-Sample 106- Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content rate 2.0 mol) %) 0.21 sensitizing dye (SD-1) 2.8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.40 Cyan coupler (C-2) 0.11 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (Oil-1) 0.51 Gelatin 1.30 Four : Medium sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content rate 8.0 mol%) 0.80 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.6 × 10 ^-4 Sensitizing dye (SD-2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.8 × 10 ^-5 Sensitizing dye (SD-4) 1.4 × 10 ^-4 Cyan coupler (C-1) 0.19 Cyan coupler (C-2) 0.22 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.32 Gelatin 0.93 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 0.64 Sensitizing dye (SD-1) 6.5 × 10 ^-5 Sensitizing dye (SD-2) 6.5 × 10 ^-5 Sensitizing dye (SD-3) 8.0 × 10 ^-6 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.12 Gelatin 0.91 Samples 101-106 Red The proportion of medium-speed red-sensitive layer latitude on sexual layer latitude was as follows.

Sample No. Percentage of total latitude Next, each of the samples 101 to 106 was cut into an ordinary 135 size standard and placed in a cartridge, and 20 shots of 24 images were prepared for each sample, and the samples 101 to 106 were set as one set.

20 people photographed one set at a time, after collecting the negative film, after developing with Konica CNK-4,
Konica SR using Konica NPS CLP-2000L printer
Print exposure was performed on the paper, and a 2 l size print was obtained using the paper treatment process CPK-18 manufactured by Konica.

In this way, the prints obtained from the negative films of Samples 101 to 106 should be judged by a quality inspection technician in the laboratory. A ... OK for one print, B ... Need to be reheated No., C ... Although the result was unsatisfactory even if it was re-tempered, it was sorted into 3 levels and the results shown in Table 1 were obtained.

[0099]

[Table 1]

From these results, it is highly probable that the sample of the constitution of the present invention can obtain a satisfactory print in one printing, and there are few prints which are unsatisfactory even if they are reprinted. It can be seen that A print yield of 1 in a laboratory processing a large number of prints.
% Improvement has a big meaning.

Example 2 Samples 201 and 204 were prepared in the same manner as in Samples 101 and 104 of Example 1, except that the silver halide emulsion of the fourth layer was grained in gelatin having an adenine content of 0.37 ppm. did.

Next, in Samples 101 and 104, Samples 202 and 2 were prepared in the same manner except that the sensitizing dyes SD-1, 2, 3, and 4 of the silver halide emulsion of the fourth layer were added as a methanol solution.
Created 05.

Using Samples 201, 202, 204 and 205, a negative film was printed on a paper after photographing as in Example 1, and the print yield was determined. Table 2 shows the results.

[0104]

[Table 2]

From the above results, in the present invention, silver halide grain formation was carried out in gelatin having a low adenine content, and the sensitizing dye added during chemical ripening was made into a water-based solid fine particle dispersion. It can be seen that the effects of the present invention are more manifested.

[0106]

The use of the color light-sensitive material of the present invention makes it possible to increase the print yield.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/00 530

Claims (5)

[Claims] 1. A red-sensitive layer, a green-sensitive layer, and a transparent support on a transparent support.
In a photographic silver halide color light-sensitive material having a photographic constituent layer composed of a blue-sensitive layer and a non-light-sensitive layer, at least one of the light-sensitive layers is composed of three or more layers having different sensitivities,
A silver halide color light-sensitive material characterized in that the proportion of latitude in the second most sensitive layer is 50 to 80% of the total latitude. 2. The halogen according to claim 1, wherein the photosensitive silver halide contained in the second most sensitive layer is formed into grains by using gelatin having an adenine content of 0.2 ppm or less. Silver halide color light-sensitive material. 3. The photosensitive silver halide contained in the second most sensitive layer is a substantially water-insoluble spectral sensitizing dye for photographic use, and an aqueous solid fine particle dispersion substantially free of an organic solvent. The silver halide color light-sensitive material according to claim 1 or 2, which is obtained by adding it as a substance. 4. The layers having different sensitivities are composed of three layers, and the ratio of the latitude of the high sensitivity layer is 10 of the total latitude.
~ 20%, the proportion of the latitude of the medium sensitivity layer is 50-80% of the total latitude, the proportion of the latitude of the low sensitivity layer is 10-40% of the total latitude, characterized in that
4. A silver halide color light-sensitive material according to any one of 3 above. 5. The silver halide color light-sensitive material according to claim 4, wherein the layers having different sensitivities are red-sensitive layers.