JPH0418545A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material to be directly observed and having high sharpness and color reproduction performance and superior stability against humidity and temperature at the time of exposure and capable of maintaining high image quality by incorporating a fine solid dispersion of a specified dye in a layer and regulating a total amount of gelatin to a specified value or less. CONSTITUTION:At least one silver halide emulsion layer contains silver chlorobromide but substantially not silver iodide, and an optional photosensitive silver halide emulsion layer and/or a nonphotosensitive hydrophilic colloidal layer contains the fine solid dispersion of the dye having at least one of a carboxy, sulfonamido, and sulfamoyl group. and the total amount of gelatin contained in the photosensitive silver halide emulsion layers and the nonphotosensitive layers formed on the same side of a support is regulated to <=9g/m<2>, thus permitting good sharpness and whiteness to be maintained and fluctuation of photographic performances due to change of conditions at the time of exposure to be reduced.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material (hereinafter also simply referred to as a "color light-sensitive material"). The present invention relates to a color light-sensitive material for direct viewing, which maintains the same properties and exhibits small fluctuations in photographic performance due to changes in exposure conditions.

[Background of the invention]

Color photosensitive materials are usually reproduced by the commonly used subtractive color method, and after imagewise exposure, a color developing solution is used to reproduce the color.
The exposed silver halide grains are developed, and the resulting oxidized color developing agent is reacted with yellow magenta and cyan pigment forming pullers, followed by bleach-fixing, washing with water, or stabilizing treatment to produce color. Get the image.

For color images obtained in this manner, it is important to improve image quality, particularly color reproducibility and sharpness.

The color reproducibility of color photosensitive materials depends on various factors, such as the spectral sensitivity distribution of each light-sensitive emulsion layer, the spectral absorption characteristics of the dye images formed, the degree of color mixing between each dye image during development, etc. It is a factor that affects gender.

It is also very important for color reproducibility that the sensitivity of each silver halide emulsion does not vary due to changes in humidity or temperature during exposure.

On the other hand, in order to improve the sharpness of color photosensitive materials,
Antihalation dyes and antiirradiation dyes are effectively used.

Dyes used for such purposes must have good spectral absorption characteristics according to the purpose of use, be completely eluted or decolorized in photographic processing solutions, and have no residual color contamination due to dyes after processing; It satisfies various conditions such as not having any adverse photographic effects on sensitized photographic emulsions such as increasing or decreasing sensitivity or increasing fog, and also having excellent stability over time in light-sensitive materials and not discoloring or fading. Must.

With the aim of finding a dye that satisfies the above conditions,
A large number of dyes have been proposed to date, including oxonol dyes described in U.S. Pat. No. 506.385, U.S. Pat. Styryl dye represented by No. 2,493,745, U.S. Pat. No. 3,148
, No. 187 and No. 3,282,699, anthraquinone dyes as represented by U.S. Pat. No. 2,865.752, and U.S. Pat. No. 3,540,8.
No. 87, No. 3,544,325, Special Publication No. 31-105
No. 78 and JP-A-51-3623 disclose benzylidene dyes and the like.

The general method for these dyes is to dissolve them in water or an organic solvent that is miscible with water and add them to the photographic constituent layers.
If the dye is water-soluble, it will not stay in the layer you want to dye, but will diffuse throughout the entire layer. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye to the extent that it will diffuse into other layers, resulting in decreased sensitivity and gradation fluctuations in both the white layer and other layers.

In addition, many of these dyes diffuse into the silver halide emulsion layer, causing spectral sensitization in undesirable areas and an increase in fog in the spectrally sensitized silver halide emulsion, or causing problems during exposure. Due to changes in humidity and temperature,
This method has the drawback of causing unfavorable phenomena such as fluctuations in sensitivity, etc.

On the other hand, as is generally known in the industry, silver chlorobromide emulsions are generally used for color photographic materials for direct viewing compared to color photographic materials for photography, etc. due to their development progress and desilvering properties. However, the above-mentioned defects caused by the diffusion of the dye into the silver halide emulsion layer are more pronounced in silver chlorobromide emulsions than in silver iodobromide emulsions, and are particularly noticeable in high-silver chloride emulsions. I found out something.

Even considering that high silver chloride emulsions are favorable for speeding up the development process, it can be seen that for color photographic light-sensitive materials for direct viewing, the silver halide composition and the above-mentioned unfavorable phenomena tend to conflict with each other. .

As described above, in color light-sensitive materials for direct viewing, the diffusion of dye into the emulsion layer in particular can be said to be a phenomenon that hinders improvement in image quality.

In order to prevent dye diffusion, it is known that the dye is present in a hydrophilic colloid layer together with a mordant such as a cationic polymer, as described in JP-A-50-65230. However, although these methods are effective in preventing diffusion within the photographic constituent layers, they tend to bind with dyes and inhibit their elution during processing, resulting in large residual colors after processing and problems with coating. It has been found that problems tend to occur in manufacturing stability, typified by performance.

The coating property problem refers to the occurrence of coating failures such as coating unevenness and coating streaks, which is a fatal problem especially in color photosensitive materials for direct viewing.

A possible solution to the above problem is to increase the amount of gelatin in the coating solution, but the problem cannot be solved unless the amount is significantly increased compared to the amount used in the past. A new drawback arises: deterioration of

On the other hand, International Patent No. 88/04,794, European Patent No. 32
No. 3,728, No. 323,729, etc., disclose that a water-insoluble dye is incorporated into a light-sensitive material by dispersing it in solid fine particles or by dispersing it together with a high boiling point solvent.

The dyes described in the above international patents and European patents are dispersed in solid particles and are insoluble in water, so there is almost no diffusion within the photographic constituent layers, and they are solubilized and eluted during processing. The level of residual color was not sufficient for color light-sensitive materials for direct viewing, which had strict whiteness standards, and was still insufficient to obtain color light-sensitive materials for direct viewing with high image quality.

[Purpose of the invention]

Therefore, the object of the present invention is to have high sharpness and color reproducibility,
An object of the present invention is to provide a color photosensitive material for direct viewing that has excellent stability against humidity and temperature during exposure and can maintain high image quality.

A second object of the present invention is to provide a color photosensitive material for direct viewing that has excellent whiteness after processing.

[Structure of the invention]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support, in which at least one of the halogen The silver halide contained in the silver halide emulsion layer contains silver chlorobromide grains that do not substantially contain silver iodide, and the silver halide contains silver chloride bromide grains that do not substantially contain silver iodide, and is free from any of the above-mentioned photosensitive silver halide emulsion layers and/or non-photosensitive hydrophilic A dye having at least one of a carboxyl group, a sulfonamide group, and a sulfamoyl group is dispersed in solid fine particles in the colloid layer, and the silver halide emulsion layer is coated on the side of the support of the photographic constituent layer. This is achieved by a silver halide color photographic light-sensitive material in which the total amount of gelatin contained in the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer is 9 g/m2 or less.

[Specific structure of the invention]

At least one of the silver halide emulsion layers in the present invention contains a chlorobromide emulsion that does not substantially contain silver iodide. Here, "substantially no silver iodide is contained" means that the silver iodide content in all silver halide grains is 0.01 mol % or less.

The silver chloride content of the silver halide grains of the present invention is preferably 5 mol % or more.

The silver halide grains of the present invention may be used alone or in combination with other silver halide grains having different compositions.

The silver halide grains contained in the silver halide emulsion used in the present invention may have a regular crystal shape, or
It may also have an irregular crystal shape such as spherical or plate-like.

The silver halide grains used in the emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The emulsion is chemically sensitized by conventional methods. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions, a sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, etc. can be used alone or in combination. .

The emulsion can be spectrally sensitized to the desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. In addition, along with the sensitizing dye, a super sensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye, may be added to the emulsion. It may be included.

In the color light-sensitive material of the present invention, a dye having at least one of a carboxyl group, a sulfamoyl group, and a sulfonamide group is contained in any photosensitive silver halide emulsion layer and/or non-photosensitive hydrophilic colloid layer. Contained as fine particles dispersed.

More specifically, the dye having at least one of a carboxyl group, a sulfamoyl group, and a sulfonamide group is, for example, a dye represented by the following general formulas [I] to [■].

General formula [■] In the formula, R, R2 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, -cooRs, COR,
, -5O2R6, -5OR,, -3OJRsRa, -
CONRbRa, NR5Ra, -NRaSO2Ra, -
NR6CORs, -NR6CONRiRr, NR,C5
Represents NR, R7, -0R5, -SR, or a cyano group,
R, , R, is a hydrogen atom, an alkyl group, an alkenyl group,
Represents a cycloalkyl group, an aryl group, or a heterocyclic group.

Ra, Rh, Ry represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, L, ~L,
represents a methine chain. n represents an integer of 0 or l, n,
represents an integer from 0 to 2.

- Formula CI) where R+, RsrL l= L s, n l and R
2 represents the same meaning as - Formula CI), respectively.

E represents the acidic nucleus necessary to form the oxonol dye.

General formula (III) In the formula, R3 + R4, L + - L sin + and n each represent the same meaning as in formula (1), R, , R
, represents the same meaning as R3 and R4.

x, , X2 represent an oxygen atom or a sulfur atom.

- Formula (IV) In the formula, R1, L, and R2 represent the same meanings as in general formula (1), and E represents the same meaning as in general formula (II). R9
゜+ Rl 1 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, an ano group, a halogen atom, -ORs, -5R,, -NR8R, -NR,
5O2R,, -NRsCORa, -CORs or -CO
represents OR. Further, a ring double bond can also be formed between RIO and R1□.

express meaning.

R121R13 represents a hydrogen atom or an alkyl group.

n represents an integer of 1 to 3.

General formula (V) In the formula, R3, R4, L L + L i, L s and nl represent the same meanings as in general formula (I), and E is general formula (II)
expresses the same meaning as Rl11. R11 is the general formula CCV
), and R14 has the same meaning as R1°.

General formula (Vl) represents a lazole nucleus, a phenol nucleus, a naphthol nucleus or a fused heterocycle.

General formula [■] In the formula, Z I, Z 2. Z s represents an electron-withdrawing group,
A2 represents an aryl group or a heterocyclic group.

In the formula, Rs, R4, RIll, R11, Lt~Ls
-X $+ n + and n represent the same meaning as in formula (1), X represents the same meaning as X, and Rls+ R16 represents the same meaning as R1°.

)<9 represents a group having an anion. Also, R4° and RI
I, RIS and R1 can form a ring bilayer bond.

General formula [■] In the formula, A1 is virol nucleus, imidazole nucleus, bi■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ 1■ ■ ■ ■ ■ II+ ■ ■ ■ ■ ■ IV-2 ■ ■ ■ c++2coon ■ ■ ■ IV-11 ■ ■ ■ C1,.

Shi+12 Shiri CUt ■ ■ ] ■-2 ■ l-1 ■ Shi+121. ,t12+,,1JLItl and tl,l,
+12L, υU11 ■ ■ ■ l-6 ■-7 ■ Shii3 r0 Shit13 ■ ■-1 ■-2 ■-3 ■ ■-9 CH2- C, H 7NISO2CI2CH.

■ CH.

C,H,7NIISO2CH,C(CI+3)2■ (i) C3L- c, o, +NI(SO2C)IfC)II-■ Nll5(Jcoshi,.II.

■-6 Nl+SO,C,++,3 The dye compound of the present invention is a compound having a hydrophilic group that is substantially insoluble in water (in water with a pH of 7 or lower) and dissociates at a pH of 9 or higher, and can be processed using a ball mill, sand mill, etc. A solid fine particle dispersion (in the form of collective particles of microscopic size, preferably with an average particle size of l Ot
(i m or less, more preferably 1 μm or less) in gellant or a polymer binder, so that it can be included in any photosensitive emulsion layer or non-photosensitive hydrophilic colloid layer in the photographic constituent layers. I can do it.

The dye solid fine particle dispersion of the present invention is water-insoluble and stably exists in the color photographic light-sensitive material, but after exposure, it can be treated with a color developer (preferably pH 9 or higher) to dissolve the dye compound in the dye compound. Does the hydrophilic group dissociate and become water-soluble?
Alternatively, by decoloring, most of it disappears from the color photographic material.

Two or more kinds of the dyes of the present invention may be used, and some water-soluble dyes may be used in combination depending on the purpose of use.

The content of the dye of the present invention varies depending on the purpose of use and is not particularly limited, but is generally used at 0.001-0.5 g/m''.

As the binder in the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the present invention, gelatin is advantageous and generally used, but gelatin derivatives etc. may also be used as a substitute for gelatin. Gelatin as used in the present invention also includes these alternatives.

The above-defined gelatin contained in the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer on the side on which the silver halide emulsion layer is coated from the support of the photographic constituent layer of the present invention. The total amount is 9 g or less, preferably 5 g or more and less than 8 g per m2 of photosensitive material.

As yellow dye-forming couplers, acylacetanilide couplers are generally used; for example, as disclosed in U.S. Pat.
No. 875,057, No. 3,265,506, No. 3, 4
08.194, 3,551,155, 3,89
No. 1,445, JP-A-48-73147, JP-A No. 50-6
No. 341, No. 50-87650, No. 52-43426
No. 63-123047, etc.

Among these, pivaloylacetanilide couplers can be preferably used.

As magenta dye-forming couplers, 5-pyrasolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolinobenzimidazole couplers, and intazolone couplers are generally used, such as U.S. Pat. No. 2,600,788, Same 3
, No. 061.432, No. 3,062,653, No. 3,
No. 127,269, No. 3,311.476, No. 3.1
No. 52896, No. 3,419,391, No. 3,519
, No. 429, No. 3,555.318, No. 3,684,
No. 514, No. 3,888,680, No. 3, 9075
No. 71, No. 3,928,044, No. 3.930861
No. 3.930866, No. 3,933,500,
JP-A-49-29639, JP-A No. 49-111631,
No. 49-129538, No. 50-13041, No. 5
No. 258922, No. 55-62454, No. 55-11
No. 8034, No. 5638043, No. 57-35858
No. 60-23855, British Patent No. 1,247.49
No. 3, Belgian Patent No. 760,116, Belgian Patent No. 792525
No., West German Patent No. 2,156,111, Special Publication No. 1983-1986
No. 479, JP-A-59-125732, JP-A No. 59-22
No. 8252, No. 59-162548, No. 59-171
No. 956, No. 60-33552, No. 60-43659
No., West German Patent No. 1,070,030, U.S. Patent No. 3,72
5.067 and Research Disclosure No.
17643 etc.

Pyrazolotriazole couplers and pyrazolone couplers are suitable for the present invention, and pyrazolotriazole couplers are particularly suitable.

Cyan couplers used in the present invention include naphthol-based, phenol-based, and imidazole-based compounds, and representative examples of these include U.S. Pat.
2,434.272, 2,474.293, 2゜895.826, 3,253,924, 3
, No. 034,892, No. 3゜311.476, No. 3,
386.301, 3,419,390, 3゜4
58.315, 3,476.563, 3,53
1.383, 4゜052.212, 4,146
, No. 396, No. 4,228,233, No. 4゜296.
No. 200, No. 4,327,173, No. 4,334,0
1.1, 4゜427.767, 4,451.5
No. 59, European Patent (EP) 0,249453A2, JP-A-1-156747, Research Disclosure No. 17643, etc.

Phenol-based and imidazole-based compounds are suitable for the present invention.

The color photosensitive material of the present invention may contain a hardening agent, a color clouding prevention agent, an image stabilizer, an ultraviolet absorber, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, an antistatic agent, etc. Agents can optionally be used.

The color light-sensitive material of the present invention can be used to form an image by subjecting it to a color development process known in the art.

The color developing agents used in the color developer solution of the present invention include aminophenol and p-phenylenediamine derivatives that are widely used in various color photographic processes.

In addition to the above-mentioned primary aromatic amine color developing agent, known developer component compounds can be added to the color developing solution applied to the processing of the color photosensitive material of the present invention.

The pi value of the color developing solution is usually 9 or more, preferably about 10 to 13.

The color development temperature is usually 15°C or higher, and generally,
It is in the range of 20°C to 50°C.

For rapid processing, it is preferable to carry out the treatment at 30°C or higher.

Further, the development processing time is generally 10 seconds to 4 minutes, but preferably in the range of 10 seconds to 1 minute for the purpose of rapid processing.

The color photosensitive material of the present invention is subjected to bleach-fixing treatment after color development.

After the bleach-fixing process, a washing process, a stabilizing process, or a combination of both processes is usually performed.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments are not limited thereto.

Example 1 Each layer of the structure shown in Table 1 was coated on a support laminated with polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side to form a multilayer color. A photographic material was produced.

The coating solution was prepared as follows.

First layer coating liquid Yellow coupler (YI) 26.7g, stain inhibitor (HQ-1) 0.67g, dye image stabilizer (STl) 1Og and high boiling point organic solvent (DBP) 8.5g
60 mC of ethyl acetate was added to dissolve the solution, and this solution was diluted with 10
% sodium alkylnaphthalene sulfonate 15 m (l
A yellow coupler dispersion was prepared by emulsifying and dispersing a 10% aqueous gelatin solution containing 300+++2 using a homogenizer.

This dispersion was mixed into a blue-sensitive silver chlorobromide emulsion (silver chloride 10 mol%,
A first layer coating solution was prepared by mixing silver bromide (90 mol %) and a gelatin solution for coating.

3rd layer coating liquid Magenta coupler (M-1) 30g, dye image stabilizer (ST-2) 20g, (ST-3) 7.5g, stain inhibitor (HQ-)) 0.85g high boiling point organic solvent(
Add and dissolve 59 m of ethyl acetate (!) into 24 g of DBP), and dissolve this solution into 400 m of a 5% aqueous gelatin solution containing 25 m of lO% sodium dodecylbenzenesulfonate <1.
Q was emulsified and dispersed using a homogenizer to prepare a magenta coupler dispersion.

This dispersion was mixed into a green-sensitive silver chlorobromide emulsion (silver chloride 20 mol%,
A third layer coating solution was prepared by mixing silver bromide (80 mol %) and gelatin solution for coating.

5th layer coating liquid cyan coupler (C-1) 7 g, (C-2)
lOg.

8g of dye image stabilizer (ST-4), anti-stain agent (
HQ-1) 0.4g and high boiling point organic solvent (HB-1) 8
Add and dissolve 40 mQ of ethyl acetate to
0% sodium alkylnaphthalene sulfonate 10ml
A cyan coupler dispersion liquid was prepared by emulsifying and dispersing the cyan coupler in 300 m0 of a 10% gelatin aqueous solution containing 2 using a homogenizer.

This dispersion was mixed into a red-sensitive silver chlorobromide emulsion (silver chloride 30 mol%,
A fifth layer coating solution was prepared by mixing silver bromide (70 mol %) and gelatin solution for coating.

The second, fourth, sixth, and seventh layer coating solutions were also prepared in the same manner as the first layer coating solution, as shown in Table 1. Further, the following compound (H-1) was added as a hardening agent for gelatin.

Table-1 (2) C-2 HQ-1 C,Hs BP (dibutyl phthalate) PVP (polyvinylpyrrolidone) ■ T-1 T-3! This coated sample was designated as Sample J, and the same procedure as Sample I was made, except that the solid fine particle dispersion of the dye of the present invention and the comparative dye were added to the fourth layer and second M of Sample 1 as shown in Table 2A. Samples 2 to 9 were prepared.

Next, samples 2 to 9 were prepared in exactly the same manner as samples 2 to 9, except that the total amount of gelatin from the first layer to the seventh layer on the support was reduced as shown in Table 2A. Sample lO~
It was prepared on 17th.

(Dye Solid Fine Particle Dispersion Method) Dye 1-3 was ball milled by the following method.

Surfactant A The dyes of the present invention were added according to the dispersion method shown above, and the comparative dye was added as an aqueous solution. Ball 400g (diameter 3fflll~
1O+nm mixture) was added and the mixture was rotated for 5 days to perform dispersion.

The amount of gelatin is expressed in g/m2.

The obtained sample was subjected to wedge exposure using a photosensitive needle KS-7 (manufactured by Konica Corporation), and processed according to the following color development processing steps.

[Processing step 1 Time temperature color development
3 minutes 30 seconds Temperature 33°C Bleach fixing 1 minute 3
0 seconds Temperature: 33°C Wash with water 3 minutes Color developer formulation N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate Hydroquinylamine sulfate Potassium carbonate Sodium bromide Anhydrous sodium sulfite Add benzyl alcohol diethylene triamine pentaacetic acid l/liethanolamine diethylene glycol water to make lQ, and adjust sodium hydroxide to 10.0.

Bleach-fix solution formulation Ethylenediamine iron(III) tetraacetate Nathiosulfate Ammonium Sodium bisulfite Temperature 33°C 4.9g 2.0g 25.0g 0.6g 2.0g 3m12 3.0g 10.0g 10.0g pH with rum Thorium salt 0g 00g 0g Sodium metabisulfite 3g Add water to make 112, and adjust to pH 7.0 with aqueous ammonia.

The following evaluations were performed on the obtained samples.

(1) Sensitometry Sensitivity and gradation of each processed sample were determined using a PDA-65 densitometer (manufactured by Konica Corporation).

(2) White background property (minimum density) Each sample was pre-processed without being exposed, and
Measure the reflection density using 0TF, each minimum density as D
It was set as min'Dmin'.

(3) Sharpness (R) A resolution test chart is printed on each sample using red light.
After performing the above processing, the density of the obtained cyan image was measured using a microphotometer, and the value expressed by the following formula was defined as the sharpness.

A resolution test chart was burned onto each sample using green light.
After performing the above processing, the density of the obtained magenta image was measured using a microphotometer, and the sharpness (G) was determined in exactly the same manner as the sharpness (R).

The larger this value is, the better the sharpness is.

(5) Humidity dependence during exposure Each sample was measured at 23°C, 85%RH and 23°C, 55%RH.
After wedge exposure under RH conditions, the above processing is performed (1
) was used to evaluate the relative sensitivity ratio (%) when 55%RH was set as 100.

The results of the obtained sharpness, whiteness, and humidity dependence during exposure are also shown in Table 2B.

(Maximum density - minimum density) (4) Sharpness (G) Table 2B From the results in Table 2B, sample 1 without dye has poor sharpness, and samples 2 to 9' containing dye have poor sharpness. will be improved. However, dyes 5 to 9 using the dyes of the present invention
It cannot be said that the whiteness of the samples is satisfactory, and Samples 2 to 4 using comparative dyes show significant sensitivity fluctuations due to humidity fluctuations during exposure.

On the other hand, Samples 13 to 17, in which the dye of the present invention was used and the total gelatin amount was in the range of the present invention, had excellent sharpness and improved whiteness, and also had a small dependence on humidity during exposure. I understand. This is considered to be due to the fact that water-soluble dyes diffuse into the silver halide emulsion layer.

Further, in samples 10 to 17 in which the total amount of gelatin was reduced, no coating failure was observed.

Example 2 Each layer having the structure shown in Table 3 was coated on the same support as in Example 1 in the same manner as in Example 1 to prepare a multilayer color photographic material. The coating solution was prepared as follows.

1st layer coating liquid Yellow coupler (Y-2) 27.2g, stain inhibitor (HQ-1) 0.67g, dye image stabilizer (ST-1) 5g, (ST-4) IOg and high boiling point organic 60 mQ of ethyl acetate was added and dissolved in 8.5 g of the solvent (DBP), and this solution was emulsified and dispersed in 300 mQ of 10% gelatin aqueous solution containing 15 ml of 10% sodium alkylnaphthalene sulfonate using a homogenizer to obtain a yellow coupler dispersion. Created.

This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (silver chloride 99.5 mol%, silver bromide 0.5 mol%) and a coating gelatin solution to prepare a first layer coating solution.

Third layer coating solution Magenta coupler (M-2) 30g, dye image stabilizer (ST-2) 20g, (ST-5) 6g, stain inhibitor (HQ-1) 0.85g, high boiling point organic solvent ( Add and dissolve 50 m of ethyl acetate (2) to 24 g of DBP), and dissolve this solution to 400 g of a 5% aqueous gelatin solution containing 25 m of 10% sodium dodecylbenzenesulfonate.
A magenta coupler dispersion liquid was prepared by emulsifying and dispersing mQ using a homogenizer.

This dispersion was mixed into a green-sensitive chlorobromide emulsion (silver chloride 99.5 mol%).
, silver bromide (0.5 mol %)) and a coating gelatin solution to prepare a third layer coating solution.

5th layer coating liquid Cyan coupler (C-1) 7g, (C-2) lOg.

8g of dye image stabilizer (ST-4), anti-stain agent (
HQ-1) 0.4g and high boiling point organic solvent (HB-1) 8
40 mQ of ethyl acetate was added and dissolved in 4 g of (HB-2), and this solution was emulsified and dispersed in 300 ml of 10% aqueous gelatin solution containing 10% sodium alkylnaphthalene sulfonate LOMF using a homogenizer to disperse the cyan coupler. A liquid was prepared.

This dispersion was mixed with a red-sensitive silver chlorobromide emulsion (silver chloride 99.8 mol%, silver bromide 0.2 mol%) and a coating gelatin solution to prepare a fifth layer coating solution.

The second, fourth, sixth, and seventh layer coating solutions were also prepared in the same manner as the first layer coating solution, as shown in Table 3. In addition, as a hardening agent for gelatin, this coated sample was designated as Sample 2-1, and then the coating sample No. 2 of Sample 21 was used. Sample 2-1 except that solid fine particle dispersions of the comparative dye and the dye of the present invention were added to the fourth layer and the second layer as shown in Table 4A.
Samples 2-2 to 2-15 were prepared in exactly the same manner.

Next, for each of Samples 2-4 to 2-13, the total amount of gelatin from the first layer to the seventh layer on the support was reduced as shown in Table 4A. Samples 2-16 to 2-25 obtained in exactly the same manner as in Example 2-13 were wedge exposed in the same manner as in Example-1, and after being processed according to the following color development processing steps, they were exposed in the same manner as in Example-1. was evaluated.

[Processing step 1 Temperature Development color development
Bleach fixation at 35.0±0.3°C for 45 seconds 35.0 soil 0
．． Stabilize at 5°C for 45 seconds Dry at 30-34°C for 90 seconds Color developer Pure water 800+n12
triethanolamine logN,
N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite
0.3g 1-hydroxyethylidene-11 diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol-3,5-disulfonic acid disodium salt 1.0gN-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 amine aniline sulfate 4.5g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g potassium carbonate
Add 27g water and make the total amount IQ,
Adjust pH to 1O, 1Oi.

Bleach fixer Ferric ammonium dihydrate ethylenediaminetetraacetic acid 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% water fG solution) 100ml12 Ammonium sulfite (40% aqueous solution) 27.5ml12 Add water to make total volume IQ, potassium carbonate or 1 p with glacial acetic acid
Adjust to H=5.7.

Stabilizing liquid 5-di-4-2-methyl-4-inthiazolin-3-one 1.0g ethylene glycol 1. ogl-Hyloquinoethylidene River, 1 Diphosphonic acid Ethylene dianetetraacetic acid Ammonium hydroxide (20% aqueous solution) Ammonium sulfite optical brightener C4,4'-diaminostyl 2, Og 1.0g 3.0g 3, Og Pen Disulfonic acid derivative) Add 1.5 g of water to bring the total amount to if, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

Sharpness, whiteness, exposure humidity-dependent sensitivity ratio of each processed sample (23℃・85%RH/23℃・55%R) ( ) Table 4
From the results of B, sample 2-3.1 using a dye other than the present invention
-4.2-5, 2i6, and 2-17 are as follows:
Furthermore, it can be seen that sensitivity fluctuations with respect to humidity changes during exposure are large.

In contrast, samples 2-6 to 2-1 using the dye of the present invention
It can be seen that in samples 5.2-18 to 2-27, there is almost no sensitivity variation with respect to humidity changes during exposure.

On the other hand, Samples 2-6 to 2-15, which used the dye of the present invention and had a total gelatin composition other than the one according to the present invention, had poor whiteness and could not be said to be satisfactory for ornamental purposes.

On the other hand, dyes 2-18 to 2-27, which are a combination of the dye of the present invention and the total gelatin amount range of the present invention, have considerably improved whiteness and are excellent in both sharpness and whiteness even in rapid processing. , and sensitivity fluctuations with respect to humidity changes during exposure are also small.

Therefore, it has been found that a color photographic material having sufficiently high image quality in terms of color reproducibility can be achieved for the first time with the configuration of the present invention.

The exposure humidity dependence was evaluated for light-sensitive materials using the emulsions of Example 1 and Example 2, and for emulsion layers with large sensitivity fluctuations.

Example 3 The layer structure was the same as in Example 2, but the yellow coupler in the first layer was changed to Y-3, the dye image stabilizer was changed to 5T-6, and the high boiling point organic solvent was changed to TINP. The magenta coupler of the layer is M-3, and the dye image stabilizer is 5T-7, 5T-8.
, 5T-9, the high boiling point organic solvent was changed to TCP, and the fifth
Samples 2-1 to 2 of Example-2 except that the cyan couplers in the layer were changed to C-3 and C-4 and the high-boiling point organic solvent was changed to TCP.
When a sample exactly the same as No. 2-27 was prepared and evaluated in the same manner as in Example 2, the sample having the structure of the present invention obtained the effects of the present invention.

T Q T-7 T-8 Q TINP triisononyl phosphate C.P. tricresyl phosphate

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer provided on a support, at least one silver halide emulsion layer containing The silver halide contains silver chlorobromide grains substantially free of silver iodide, and contains carboxyl in any of the light-sensitive silver halide emulsion layers and/or non-light-sensitive hydrophilic colloid layers. A photosensitive silver halide emulsion containing a dye having at least one of a group, a sulfonamide group, and a sulfamoyl group as solid fine particles dispersed therein, and the side of the support of the photographic constituent layer is coated with a silver halide emulsion layer. The total amount of gelatin contained in the layer and the non-photosensitive hydrophilic colloid layer is 9 g/m^2
A silver halide color photographic material characterized by the following: