JPH0456850A - Silver halide color photographic sensitive material and development processing method for same - Google Patents

Abstract

PURPOSE:To enhance sharpness and graininess by arranging at least 2 layers of blue-, green-, and red-sensitive emulsion layers having maximum sensitivity at the positions farthest from a support and specifying color development process. CONSTITUTION:At kleast 2 layers of the blue-, green-, and red-sensitive silver halide emulsion layers having the maximum sensitivity are arranged at the positions farthest from the support, and the average silver chloride content in the silver halide emulsion contained in the silver halide color photographic sensitive material is controlled to >=20mol%, and production of developed silver is 15 - 90mol% of the total photosensitive silver halide in the color development, thus permitting both of graininess and sharpness to be enhanced even under rapid processing conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material suitable for rapid processing. The present invention relates to a possible silver halide color photographic light-sensitive material and a color development processing method thereof.

[Background of the invention]

Currently, the so-called negative-positive method, in which color photographs are taken with color negative film and printed on color paper, is widely used. The reason for this is that color negative film has a very wide exposure latitude, has a very low chance of failure during shooting, and allows even general users without specialized knowledge to easily take color photos.

Against this background, the emergence of color photographic materials that can be processed more rapidly is awaited as a requirement of the times.

Currently, silver iodobromide emulsions are generally used as the silver halide used in color negative films for photography. The reason for this is that silver iodobromide emulsions have high sensitivity, rich gradation properties, and appropriate antifogging properties.

However, it has a development inhibiting effect based on iodide ions or bromide ions, and has the fatal drawback of significantly deteriorating rapid development processing properties.

On the other hand, silver chloride or silver chlorobromide emulsions, which are advantageous in terms of rapid processing, are mainly used in photosensitive materials for printing, which have relatively low sensitivity, and are now capable of rapid color processing in about 60 seconds. There is.

However, while improving speedy processing in this way,
The gradation becomes hard, high developability tends to cause high fogging, and furthermore, the image characteristics such as sharpness and graininess are disadvantageous.

For example, JP-A-62-205334 is known as a method for improving the color reproducibility and image characteristics of color photographic materials using emulsions containing high silver chloride. However, there is no mention of the suitability for rapid processing, which is a feature of emulsions containing high silver chloride.

On the other hand, one method for increasing the sensitivity of a light-sensitive material using a high silver chloride-containing emulsion, which has relatively low sensitivity, is to devise the order of the layers coated on the light-sensitive material. The following is known as a layer structure for achieving this high sensitivity. For example, the above-mentioned order layer structure of each light-sensitive silver halide emulsion layer, such as a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, which are sequentially coated on a support. A high-sensitivity silver halide emulsion containing a diffusion-resistant coupler that develops substantially the same color-sensitive layers in substantially the same hue with respect to some or all of the light-sensitive silver halide emulsion layers. (hereinafter referred to as a high-sensitivity emulsion layer) and a low-sensitivity silver halide emulsion layer (hereinafter referred to as a low-sensitivity emulsion layer), which are layered adjacently (normal layer configuration). be.

According to this normal layer structure, during exposure, the light-sensitive silver halide emulsion layer located closer to the support absorbs the amount of exposure light by another light-sensitive silver halide emulsion layer located farther away. However, there is a problem in that it takes time for the developer to diffuse during development.

In other words, in such a normal layer structure, the high sensitivity of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer located lower (on the support side) is affected by exposure loss and development delay. This creates a disadvantage in terms of development.

On the other hand, a technique for changing the lamination order of each photosensitive silver halide emulsion layer (reverse layer structure) is known.

For example, U.S. Pat. No. 3,663,228 states that (a)
Each low-sensitivity emulsion layer (RGB low-sensitivity layer unit) of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer is coated in order from the support side, and (b ) On the RGB low-sensitivity layer unit, each high-sensitivity emulsion layer (RGB high-sensitivity The RGB high-sensitivity layer unit and the RGB low-sensitivity layer unit are separated by a neutral density (neutral density) filter. The current configuration is described. As is clear from the need for an ND filter, this technique does not have any problem with increasing sensitivity, and is insufficient to achieve high image quality.

Next, U.S. Patent No. 3,658. No. '536 describes - a green-sensitive silver halide emulsion layer that has a large effect on visibility;
By positioning it on the surface side farther from the support,
A technique has been disclosed that attempts to eliminate the exposure loss of the green-sensitive silver halide emulsion layer. However, this interlayer structure (reverse layer structure) alone is insufficient to improve graininess.

On the other hand, the following technology is known as an inverted layer structure that achieves high sensitivity.

CA) First, in Special Publication No. 55-34932, (,)
Each low-sensitivity emulsion layer (RG low-sensitivity layer unit) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer is coated in order from the support side, and (b) on the RG low-sensitivity layer unit. , coat each high-sensitivity emulsion layer (RG high-sensitivity layer unit) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer in order from the support side, (c) on the RG high-sensitivity layer unit. describes a structure in which high-speed and low-sensitivity emulsion layers (B high and low-speed layer unit) of a blue-sensitive silver halide emulsion layer are coated like a normal layer structure.

In addition, [B] Special Publication No. 61-22294 includes the above (A)
In the silver halide color photographic light-sensitive material having the structure, RG
A configuration is described in which each of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer of the low-speed layer unit is coated separately into medium sensitivity and low sensitivity.

Furthermore, (C) Japanese Patent Application Laid-open No. 59-177551 describes RGB
A configuration in which a low-sensitivity layer unit and an RGB high-sensitivity layer unit are sequentially coated on a support, or CD) JP-A No. 63-193148 describes the above-mentioned (
In the layer structure of A), the functional silver halide emulsion layer containing the development inhibitor-releasing coupler or the development accelerator-releasing coupler is replaced with any of the R-G-B photosensitive silver halide emulsion layers. There is a description of a configuration provided adjacent to the .

The silver halide color photographic light-sensitive material having the configurations [A], CB), [CD and CD) has a green-sensitive λ silver halide emulsion layer with high sensitivity and the high-sensitivity green-sensitive halogen Between the green-sensitive silver halide emulsion layer having lower sensitivity than the silver halide emulsion layer, at least the red-sensitive silver halide emulsion layer having high sensitivity is provided.
Although this paper has a silver gendeide emulsion layer and is an effective means for achieving the objectives of high sensitivity and high image quality, it is essentially a report on silver iodobromide emulsions. Furthermore, no description has been found regarding the suitability of any of these techniques for rapid development processing.

As described above, it can be said that silver iodobromide emulsions that have been mainly used in color light-sensitive materials for photography have been unsuitable for rapid processing, although they have excellent sensitivity, image quality, and gradation.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material which has high sensitivity and excellent image characteristics such as sharpness and graininess by using a silver halide emulsion containing high silver chloride and which has excellent rapid processing properties. and a processing method thereof.

Other objects will become apparent from the description below.

[Structure of the Invention] As a result of intensive studies, the inventors of the present invention have found that the above object can be achieved by the following, and have accomplished the present invention.

That is, at least one blue-sensitive silver halide emulsion layer, at least two green-sensitive silver halide emulsion layers with different sensitivities, and at least two red-sensitive silver halide layers with different sensitivities are formed on the support. In a silver halide color photographic light-sensitive material having an emulsion layer, at least two of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers having the highest sensitivity among the color-sensitive silver halide emulsion layers are The two layers furthest from the support are arranged as photosensitive silver halide emulsion layers, and the average silver chloride content of the silver halide emulsion contained in the silver halide color photographic light-sensitive material is 2.
0 mol % or more, and color development is carried out so that the production rate of developed silver in the maximum color density region is 15 to 90% of the total amount of photosensitive silver halide contained in the light-sensitive material. This was achieved by a silver halide color photographic light-sensitive material and a development processing method for the silver halide color photographic light-sensitive material.

The present invention will be explained in detail below.

The silver halide color photographic light-sensitive material of the present invention has a plurality of light-sensitive silver halide emulsion layers on a support. It refers to multiple layers having substantially the same color sensitivity but different photographic sensitivities, such as a high-speed layer, a medium-speed layer, and a low-speed layer. The term "substantially the same color sensitivity" as used herein means that the spectral sensitivity characteristics need not be exactly the same, for example, in terms of blue sensitivity, green sensitivity, and red sensitivity.

In the present invention, the dry film thickness of the entire photographic constituent layer is 22
The dry film thickness is preferably 10 to 18 μm or less in order to most effectively demonstrate processing stability and rapid processing suitability.
It is particularly preferable to set it to m.

If the dry film thickness is greater than 22 μm, it becomes difficult to obtain sufficient effects in terms of suitability for rapid processing, which is the objective of the present invention. Furthermore, when the dry film thickness is less than 10 μm, it becomes difficult to control the processing stability and it becomes difficult to obtain the photographic density required for a color negative film for photography.

A major feature of the present invention is that the silver halide emulsion used, particularly the composition of the halogen contained in the silver halide grains, and the light-sensitive material coated with the emulsion are prepared so that the composition is as shown in the claims. It is the level of "silver development rate" that occurs as a result of color development processing.

The term "silver development rate J" as used herein refers to the ratio of developed silver to the total amount of coated silver in the maximum color density region in the color development step I of a color negative light-sensitive material.

Here, the maximum color density area and silver development rate refer to the following. The maximum color density refers to the area on the characteristic curve that includes the minimum exposure amount required to obtain the highest density. In a typical silver halide color photographic light-sensitive material composed of three color-sensitive layers: blue, green, and red, it is necessary to maximize the color image density of each color-sensitive layer. This area corresponds to the area in which the minimum separation exposure of each of the three colors or the white exposure required for this is performed.

Further, the silver development rate is calculated as follows. After the sample has been exposed to light so as to obtain the maximum color density area for a predetermined period of time, it is brought into a fixing step without going through a bleaching step to remove silver halide that did not contribute to color development. The amount of silver remaining in the maximum color density region of the sample processed in this way (B) [Amount of silver that contributed to color development] before processing (
The ratio to A), (B)/(A) X100, is defined as the silver development rate. The amount of silver in each sample can be measured by X-ray fluorescence.

In the present invention, the value of the silver development rate in this color development step is preferably 15 to 85%, more preferably 15 to 75%.

The average silver chloride content contained in the silver halide color photographic light-sensitive material according to the present invention may be 20 mol % or more, and the chloride content of the light-sensitive material as a whole may be 20 mol % or more. However, preferably each of all silver halide emulsion layers has this chloride content. The preferred chloride content is 50 mol% or more, more preferably 70 mol% or more.

It is preferable that all silver halides other than chloride are bromine, but the silver halide is not limited thereto, and for example, iodide may be included as long as the effects of the present invention are not impaired.

The silver chloride content of silver halide can be determined by a commonly used fluorescent X-ray method.

The grain size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 3 μm in view of image characteristics such as graininess, developability due to the difference in grain size, processing suitability, etc.
It may be I, more preferably in the range of 0.2 to 2 μm.

The structure of the silver halide grains is preferably a core/shell type silver halide grain.

The core/shell type refers to silver halide grains in which the interior and surface of silver halide grains have different compositions.

Further, the grains of the silver halide emulsion according to the present invention are preferably monodisperse, and the degree of this is determined by the ratio of the standard deviation (S) of the grain size (S) to the average grain size Cr) of each silver halide grain as a whole. The coefficient of variation defined by r is preferably 0.4 or less, more preferably 0.33 or less, further preferably 0.25 or less, and particularly preferably 0-20 or less.

The average grain size (r) referred to here refers to the grain size (in the case of cubic silver halide grains, the length of one piece thereof, and in the case of non-cubic grains, one piece when converted to a cube having the same volume). ) When the number of particles in ri is ni, it is defined by the following formula.

The above-mentioned monodisperse core/shell type silver halide emulsions are disclosed, for example, in JP-A-59-177353 and JP-A-60-138.
No. 538, No. 59-52238, No. 60-14333
No. 1, No. 60-35726 and No. 60-258536
It can be manufactured by a known method disclosed in, for example, No.

As the shape of the silver halide grains, normal crystal grains, twin crystal tabular grains, epitaxial bonded grains, etc. can be used.

The silver halide emulsion according to the present invention is produced by controlling the pAg, pH, temperature, stirring, etc. in a liquid phase in which silver halide grains are generated and grown in a predetermined pattern, so that sodium chloride, potassium bromide, potassium iodide, etc. The emulsion can be produced using a double-jet emulsion production apparatus that controls the addition of halides and silver nitrate.

As the layer structure of the silver halide color photographic light-sensitive material according to the present invention, a substantially non-photosensitive fine grain emulsion having a silver halide grain size of 0.01 to 0.2 μm is used in the intermediate layer or the protective layer. I can do it.

Substantially non-photosensitive refers to a sensitivity of 1150 or less of the lowest sensitivity grain present in the light-sensitive emulsion layer.

In the present invention, in order to obtain a wide exposure latitude,
Emulsions having different grain sizes or silver halide compositions can be mixed and used in the same constituent layer in any proportion. The particles to be mixed with different grain sizes include silver halide grains having a maximum average grain size of 0.2 to 2.0 μm and silver halide grains having a maximum average grain size of 0.05 to 1.0 μm.
A combination of silver halide grains having a minimum average grain size of m is preferred, and one or more types of silver halide grains having an intermediate average grain size may also be combined.

Further, the average grain size of the silver halide grains having the maximum average grain size is 1.5 to 4% of the average grain size of the silver halide grains having the minimum average grain size.
Preferably, it is 0 times.

Furthermore, in conventional photosensitive materials using silver halide emulsions containing high silver chloride, such as color papers, due to the high developability of silver halide itself, photographically useful residues are released upon coupling. However, according to the light-sensitive material and processing method of the present invention, it has been difficult to use couplers that release development inhibitors (e.g., development inhibitor-releasing couplers, development accelerator-releasing couplers, etc.). The R coupler can be effectively incorporated into the light-sensitive material in the same manner as in color negative films composed of silver iodobromide emulsions. In particular, it is an effective means for improving image characteristics such as interimage effects.

Examples of old R couplers that are effective in the present invention include British Patent No. 953,454, U.S. Patent No. 3,227.554, U.S. Patent No. 3,615.506, U.S. Pat.
, No. 701,783, No. 3゜933.500, No. 4,
No. 095,984, No. 4,149,886, No. 4゜2
No. 86.054, No. 4,359.521, Japanese Unexamined Patent Publication No. 1973
-90932, 56-116029, 57-1
51944, etc., and U.S. Patent No. 4,24
No. 8.962, No. 4,409.323, JP-A-57-
No. 154234, No. 58-162949, No. 5g-2
No. 05150, No. 59-195643, No. 59-20
No. 6834, No. 59-206836, No. 59-210
The old timing R coupler described in No. 440, No. 60-7429, etc. can be preferably used.

Furthermore, in a light-sensitive material using a silver halide emulsion containing high silver chloride, the yellow filter layer can be omitted due to the characteristic of silver chloride inherent sensitivity, and therefore, any layer structure is possible. This is the layer structure mentioned in the present invention.

Furthermore, since a silver halide emulsion containing substantially no silver iodide is used, common processing with color paper is possible, contributing to resource and energy savings.

In the present invention, the silver halide emulsion used is Research Disclosure 308119 (hereinafter referred to as RD30).
8119) can be used. The table below shows the locations.

[Item] (RD308119 (7) Heishi) Production method Item 993I-A and Item 994E Epitaxial halogen conversion // Substituted metal-containing monodisperse solvent added sensitive material Desalination using mixed negative emulsion Item 9941-C Section 994I-D Section 995I-F Section 9951-H//I-J Section ttfl-A In the present invention, the silver halide emulsion used is one that has undergone physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643. No. 18716 and No.

308119 (each hereinafter referred to as RD17643.R
D18716 and RD308119).

The table below shows the locations.

[Item] [Page of RD308119] Chemical sensitizer 996 I [[-A item Spectral sensitizer 996
IV-A-A, B, C, D, H, H, I, J Section Supersensitizers 996 rV-A-E, J Section Antifoggants 998■ Stabilizers 998■ Known substances that can be used in the present invention Photographic additives are also described in the Research Disclosure above. Bottom (RD1764
3) (RD18716) 23-24 648-9 23-24 648-9 24-25 649 [Item] (Page of RD308119) (RD17643) (RD18716) Color clouding prevention agent
1002 ■-I term 25 6
50 Dye image stabilizer 1001 Item ■-J
25 Ultraviolet absorber 1003 ■-c,
xmc term 25-26 filter dye 1003
■ 25~26 binder
1003II 26
651 Antistatic agent 1006 1111
27 650 Hardener 1
004X 26 651 Plasticizer 1006II 2
7 650 Lubricant 10061N
27 650 activator/coating aid
1005 II 26-27
650 Mer 7 Agent 1007 1VI A variety of couplers can be used in the present invention, specific examples of which are described in the Research Disclosure above. The relevant entries are shown in the table below.

[Item] (page of RD308119)
(RD17643)I:RD18716)
Yeo-coupler 1001 ■-D section
VIC-G term magenta coupler 1001 ■-
Item ■C-G term cyan coupler 10
01 ■-D section ■C-G section Colored coupler 1002 ■-G section ■G
Item DIR Coupler 1001 ■-F Item
■ Section F BAR coupler 1002 ■- Section F Other useful residue-releasing couplers 1001 ■- Section F alkali-soluble coupler fool ■- Section E Complete The additives used in the present invention are the dispersion method described in RD308119X rV. It can be added by etc.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119--.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic light-sensitive material is expressed in grams per 1112 unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver. Further, the sensitizing dye is expressed in moles/mol of silver.

Example 1 Multilayer color photographic materials Sample-1 and Sample-2 were prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample = 1 (comparison) 1st layer: Antihalation layer (HC) Black colloidal silver UV absorber (UV-1) Colored cyan coupler (CC High boiling point solvent (Oil 1) High boiling point solvent (Oiff-2) Gelatin 2nd Layers: Intermediate layer (IL-1) Gelatin third layer - low sensitivity red-sensitive emulsion layer (RL) Silver bromide emulsion (Em-1) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitization Dye (S-3) Cyan coupler (C-1) Cyan coupler (c-2) Colored cyan coupler (CO DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oiff-1) ■ ) 0 .15 0.20 0.02 0.20 0.20 1.6 1.3 0.7 1, OX 10-' 1.0X 10 6.2X 10-' 0.50 0.13 1) 0. 07 0.006 0.01 0.55 Additive (SC-1) Gelatin 4th layer; high sensitivity red-sensitive emulsion layer (RH) Silver bromide emulsion (Em-2) Sensitizing dye (S-1) Sensitization Dye (S-2) Sensitizing dye (S-3) Cyan coupler (C-2) Colored cyan coupler (CG- DIR compound (D-2) High boiling point solvent (Oi12-1) Additive (SC-1) Gelatin 5th layer: Intermediate layer (IL-2) 6th gelatin layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver bromide emulsion (E+m-1) Sensitizing dye (S-4) Sensitizing dye (s-5) Magenta coupler (M-1) 0.003 1.2 0.9 'IOX 10-' 7, OX 10-' 4.2X 10-' 0.23 1) 0.03 0.02 0.25 0.003 1.0 0.8 0.8 2, lX 10-' 2.5X 10-' 0.17 Magenta coupler (M-2) Colored magenta coupler (CM DIR compound (D-3) High boiling point solvent (Oi12-2) ) Additive (SC-1) Gelatin 7th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver bromide emulsion (Em-2) Sensitizing dye (s-6) Sensitizing dye (S-7) Sensitizing dye (S-8) Magenta coupler (M-1) Magenta coupler (M-2) Colored magenta coupler (CM DIR compound (D-3) High boiling point solvent (Oif2-2) Additive (sc-1) Gelatin 8th layer Yellow filter layer (yc) Yellow colloidal silver 0.43 1) 0.10 0.02 0.70 0.003 1.0 0.9 4.5X 10-5 8.2X 10-' 1.2X 10- ' 0.03 0.13 1 ) 0.04 0.004 0.35 0.003 1.0 0.03 Additive (H5-1) Additive (H5-2) Additive (SC-2) High boiling point Solvent (Oi12-2) Gelatin $9 layer; low sensitivity blue-sensitive emulsion layer (BL) Silver bromide emulsion (Em-1) Sensitizing dye (S-9) Yellow coupler (Y-1) Yellow coupler (Y-2) ) High boiling point solvent (Oi12-2) Additive (SC-1) Gelatin 10th layer; High sensitivity red-sensitive emulsion layer (BH) Silver bromide emulsion (E
m-2) Sensitizing dye (S-9) Sensitizing dye (S-10) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (D-1) 0.07 0.07 0, ■ 2 0.15 1.0 0.6 1.8X 10-' 0.60 0.32 0.18 0.004 1.3 0.6 1.3X 10-' 5, OX 10-' 0.18 0 .10 0, Ol High boiling point solvent (Oi (2-2) Additive (SC-1) Gelatin 11th layer; 1st protective layer (Pro-1) Fine grain silver chloride emulsion (average particle size 0.08 μm) Ultraviolet absorption Agent (UV-1) Ultraviolet absorber (UV-2) High boiling point solvent (Oi12-1) High boiling point solvent (Oi+2-3) Additive (H5-1) tt (H52) Gelatin 12th layer: 2nd protection Layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) Polymethyl methacrylate (average particle size 3 μm) Sliding agent (WAX-1) Charge control agent (SU-1) tt (SU-2) 0.05 0 .002 1.0 0.3 0.07 0.10 0.07 0.07 0.2 0.1 0.8 0.13 0.02 0.04 0.004 0.02 Gelatin sample-2 (comparison) ) 1st layer: 2nd layer that is the same as the 1st layer of sample-1; 3rd layer that is the same as the 2nd layer of sample-1; 4th layer that is the same as the 3rd layer of sample-1; Intermediate layer (IL-2 ) Gelatin 5th layer; 6th layer same as the 6th layer of Sample-1; Intermediate layer (IL-3) Gelatin additive (SC-2) High boiling point solvent (Oi(2-2) 7th layer: Sample 8th layer that is the same as the 9th layer of Sample-1; Intermediate layer (IL-4) 9th layer that is the same as the 6th layer of Sample-2; 10th layer that is the same as the 4th layer of Sample-1; Intermediate layer (IL-4) 5) Gelatin additive (SC-2) High boiling point solvent (Oiff 2) 0.5 0.8 0.8 0.03 0.03 11th layer: 12th layer same as the 7th layer of sample-1: Intermediate layer (IL-6) 13th layer that is the same as the 1st O layer of sample-2; 14th layer that is the same as the 1st O layer of sample = 1; 15th layer that is the same as the 11th layer of sample-1; Same as the 12th layer Next, the chemical structures of the additive compounds used in each layer are shown.

In addition to the above, each layer also contains a dispersing aid 5U-3, a coating aid SU-4, a hardening agent H-1, H-2, H-3, and a stabilizer 5T.
-1, preservative DI-1, dyes AI-1 and AI-2, and antifoggants AF-1 and AF-2 were added as necessary.

0,8 0,05 0,05 CM ■ ■ C,H.

Js H U- NaO,5-CHCOO(CF2CFri1HCHzCO
O(CF2CFz) iH U- U U- S- ■ S- V-2 AX - CCCHx-CH5OzCHz'hCCH,5(hcH
zcHx)zNcHzcHxsOsK Weight average molecular weight M
w-30,000 (co!=CH3O, CH, 0 T-I-F-F-I- Next, the emulsions used in each layer are shown in Table 1 below.

In the table, E+n-1 and E+o-2 are the emulsions used in Example 1, and E+a-3 to Em-16 are pAgsp in the liquid phase when producing and growing silver halide grains.
It is an emulsion whose average grain size and halide content are varied by controlling conditions such as u and by controlling the addition of halides such as sodium chloride and potassium bromide and silver nitrate. Each emulsion was optimally subjected to spectral sensitization and chemical sensitization so that it had almost the same spectral sensitivity as the emulsion of Sample-1.

Using the obtained emulsion of E+-1-Em-16,
Multilayer color photographic material SO having the structure shown in Table 2,
The granularity measurement was carried out by exposing each sample thus prepared to solid light to obtain an appropriate negative density using filters for exposure light (B), green light (G), and red light (R). and a pattern wedge for MTF measurement. Each sample was subjected to color development processing as shown below.

Processing-A Processing process Temperature ('C) Time (seconds) Color development 35.0±0.3 45 Bleach-fixing 3
5.0±0.3 45 Stabilization 30-3490 Drying 60-80 6
0 indicates the composition of the processing liquid used.

Color developer pure water
800mQ triethanolamine
legN, N-diethylhydroxylamine
5g potassium bromide 0.02
g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonate ethylenediaminetetraacetic acid Catechol-3,5-disulfonate disodium 4-amino-3-methyl-N=ethyl N-(β-hydroxyethyl ) Aniline sulfate optical brightener (4,4'-diaminostilbendisulfonic acid derivative) Add potassium carbonate water to bring the total volume to 14.

Bleach-fix solution Ethylenediaminetetraacetic acid Ferric ammonium dihydrate Ethylenediaminetetraacetic acid Ammonium thiosulfate (70% aqueous solution) Ammonium sulfite (40% aqueous solution) Add water to bring the total volume to IQ, and adjust to potassium carbonate pH -10.10. 1.0g 1.0g 1.0g 3.2g 1.0g 7g 0g g 00m12 27-5mα Adjust to pH=5.7 with rum or glacial acetic acid.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) ) 3.0g optical brightener (4,
4'-diaminostilbendisulfonic acid derivative)
Add 1.5 g of water to bring the total volume to IQ, and adjust the pH to -7.0 with sulfuric acid or potassium hydroxide.

The granularity (RMS) and sharpness (MTF) of yellow, magenta and cyan images of these processed samples were measured.

The RMS value is the concentration of the measured part of the sample with an aperture scanning area of 18
00μmz (slit width 10μm1 slit length 18
Scan with a microdensitometer of 04m), and calculate the value by 1000 times the standard deviation of the fluctuation of the density value with the density measurement sampling number of 100 or more, and calculate the respective values of the yellow magenta and cyan color images of Sample-1. It is shown as a relative value when set to 100. The smaller the RMS value, the better the granularity.

Also, for the MTF value, calculate the value of 10 pieces/■1 part of each color image,
The values are expressed as relative values when the MTF values of the yellow, magenta and cyan images of Sample-1 are set to 100.

The larger the MTF value, the better the sharpness.

In addition, the silver development rate (%) in the table is a value obtained by performing the following process-B after performing normal wedge exposure.

Processing-B Processing process Temperature (°C) Processing time (seconds) Color development
35.0±0.3 45 (same as process A) Stop 20~30 10
(1% Vinegar #) Fixation 35.0±0.5 45
(Ordinary thiosulfate photocoating solution) The amount of silver remaining after processing was measured using fluorescent X-rays, and the proportion of silver that contributed to color development was calculated from the density measurement after desilvering.

The obtained results are shown in Table 3 below.

From the results shown in Table 3, it can be seen that the present invention has a large improvement effect, especially in magenta and cyan images.

Further, the higher the average silver chloride content of the silver halide emulsion in the light-sensitive material, the greater the effect of the present invention. Furthermore, in a sample containing only one blue-sensitive silver halide emulsion layer, it was found that the layer structure of the present invention had a very large effect of improving the sharpness of magenta and cyan images in particular. It has been found that when the color layer is composed of three layers having different photosensitivity, the effect of improving granularity is greater than expected.

Example 2 Regarding the two samples 6 and 17 of Example 1, the couplers contained in the green-sensitive silver halide emulsion layer were changed as shown in Table 4 below, and Samples 21 and 22 were prepared. Obtained. Table 4 shows only the changes.

Regarding these two types of samples, the same evaluation table as in Example 1 sample Compound used in 22 C 2 A much improved photographic image can be obtained.

Claims (1)

[Claims] On the support, at least one blue-sensitive silver halide emulsion layer, at least two green-sensitive silver halide emulsion layers with different sensitivities, and at least two red-sensitive silver halide emulsion layers with different sensitivities. In the silver halide color photographic light-sensitive material, at least two of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers having the highest sensitivity among the color-sensitive silver halide emulsion layers are light-sensitive. The silver halide emulsion layer is arranged in the two layers furthest from the support, and the average silver chloride content of the silver halide emulsion contained in the silver halide color photographic light-sensitive material is 20 mol% or more. Silver halide color photographic photosensitive material, characterized in that color development is carried out so that the production rate of developed silver in the maximum color density region is 15 to 90% of the total amount of photosensitive silver halide contained in the photosensitive material. A material and a method for developing the silver halide color photographic light-sensitive material.