JPH1055050A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photosensitive material having high sensitivity, suppressing fog without lowering the sensitivity and also suppressing fog even after storage over a long period of time. SOLUTION: This material has at least one red-sensitive layer, at least one green-sensitive layer, at least one blue-sensitive layer and at least one colloidal silver-contg. hydrophilic layer on the substrate. The hydrophilic layer contains a compd. having a wt. average mol.wt. of 50,000-300,000 represented by the formula by 5.00-500g per 1mol colloidal silver. In the formula, R0 is H or alkyl, Q is a group of nonmetallic atoms required to form a 5- to 7-membered ring in combination with N and C=O, each of A and B is a copolymerizable ethylenic unsatd. compd., (x), (y) and (z) show mol%, 10<=x<=100, 0<=y<=90, 0<=z<=90 and x+y+z=100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic material. In particular, the present invention relates to a silver halide color photographic light-sensitive material which is high in sensitivity, has reduced slight fringing with a decrease in sensitivity, and has excellent storage stability.

[0002]

2. Description of the Related Art It is known that colloidal silver is used for an antihalation layer and a yellow filter layer of a silver halide light-sensitive material. However, when the color photographic material contains colloidal silver, fog increases, and there is a problem that the fog further increases due to long-term storage of the photographic material. In recent years, in the case of a high-sensitivity emulsion using a selenium sensitizer and a gold-sulfur sensitizer or a light-sensitive material using a two-equivalent coupler having a high color-forming ratio, the fog is more remarkable. It is considered that the cause of this fogging is that dissolution physical development using colloidal silver as a nucleus occurs to reduce the adjacent silver halide emulsion layer.

On the other hand, as a method of improving fog, when the amount of colloidal silver is reduced, the increase in fog is reduced, but the antihalation effect and the filter effect become insufficient. In addition, a colloidal silver-containing hydrophilic layer or an adjacent photosensitive layer, a non-photosensitive layer to which a fog inhibitor or the like is added,
Immediately and upon storage, a fogging inhibitory effect is observed, but this is not preferred because sensitivity is reduced.

JP-B-59-47305 discloses a method in which iodide ions are contained in a hydrophilic colloid layer containing colloidal silver or an adjacent non-photosensitive layer. However, the method of containing iodine ions is not preferable because the development of the photosensitive silver halide is suppressed, and the iodine ions accumulate in the bleach-fix solution, resulting in a decrease in the bleach-fixing speed. In addition, Japanese Unexamined Patent Application Publication No.
JP-A-143244 discloses a method for improving contact fogging with a two-equivalent coupler and yellow colloidal silver, and a method for improving the storage stability by containing a high boiling point solvent in a colloidal silver-containing layer as disclosed in JP-A-3-113443. In each case, fog reduction was insufficient.

[0005] In addition, a number of yellow dyes have been suggested as alternatives to colloidal silver. These are described in U.S. Pat. Nos. 2,538,008, 2,538,009, 4,420,555, the specification and British Patent 69.
Nos. 5,873,760,739, JP-A-3-20732, JP-A-3-23847, and 4-14.
No. 035, which are incorporated herein by reference. Many of these dyes exhibit the required blue light absorption, but are poorly absorbed and are also prone to contamination problems. Further, as a dye for preventing halation, it cannot be used because of its different absorption wavelength, and there is no method to replace colloidal silver at present, which is a proposition in the industry.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color light-sensitive material having high sensitivity, reduced slight fog with a decrease in sensitivity, and suppressed fog even during long-term storage. is there.

[0007]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide color photographic light-sensitive material containing at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer, and colloidal silver-containing hydrophilic layer on a support, the colloidal silver-containing hydrophilic layer The following general formula (1)
And the weight average molecular weight is from 50,000 to 30.
000 compounds per mole of colloidal silver.
A silver halide color photographic light-sensitive material characterized by containing from 00 g to 500 g.

[0009]

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(In the formula, R ₀ represents a hydrogen atom or an alkyl group. Q represents a group of nonmetallic atoms necessary for forming a 5- to 7-membered ring together with N and CＯO. Represents a polymerizable ethylenically unsaturated compound, where x, y, and z represent mol%, 10 ≦ x ≦ 100, 0 ≦ y ≦ 90, 0 ≦ z ≦ 90, and x + y + z = 100.) 2) The ratio of the coating amount KG (g / m ² ) of the compound represented by the general formula (1) to the colloidal silver-containing hydrophilic layer and the gelatin coating amount EG (g / m ² ) of the colloidal silver-containing hydrophilic layer. Is a ratio of 1: 3 to 1: 100.

(3) A silver halide color photographic light-sensitive material containing at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and at least one hydrophilic layer containing colloidal silver on a support, wherein In the photosensitive layer or the non-photosensitive layer adjacent to the layer, 0.001 g / m ² to 0.10 g of the compound represented by the general formula (1) and having a weight average molecular weight of 50,000 to 300,000. / M ² , a silver halide color photographic material.

(4) The photosensitive layer adjacent to the colloidal silver-containing hydrophilic layer is a green photosensitive layer, which contains a compound represented by the following general formula (2), and The compound represented by 0.001 g / m ² to 0.10 g / m ²
A silver halide color photographic light-sensitive material characterized by comprising:

[0013]

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Wherein R ¹¹ is a hydrogen atom or an aromatic 1
Represents a group capable of leaving by reaction with an oxidized form of a secondary amine color developing agent. R ¹² represents an aryl group. R ¹³ represents a substituent, and n ₁ represents an integer of ₁ to 5. When n ₁ is 2 or more, R
¹³ may be the same or different. Hereinafter, the present invention will be described in detail. The colloidal silver of the present invention can be obtained, for example, from Wiley & Sons, New York.
k, published in 1933, Colloid by Weiser
al Elements (colloidal silver yellow by the dextrin reduction method of Carey Lea) or German Patent 1,096,193 (brown and black colloidal silver)
Or U.S. Pat. No. 2,688,601 (blue colloidal silver) or U.S. Pat. No. 5,246,823 (tabular colloidal silver). Of these, it is preferable to use brown and black colloidal silver for the antihalation layer and to use yellow colloidal silver for the yellow filter layer.

The yellow colloidal silver is disclosed in
It is also preferable to use colloidal silver of No. 73346.

In the present invention, the preferable addition amount of colloidal silver is from 0.001 g / m ² to 1.0 g / m ² . Further, the amount is more preferably from 0.01 g / m ² to 0.5 g / m ² .

Next, the compounds represented by formulas (1) and (2) used in the present invention will be described in detail. First, the compound represented by formula (1) used in the present invention will be described in detail.

The ethylenically unsaturated compounds represented by A and B in the general formula (1) of the present invention include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers , Vinyl esters, vinyl heterocyclic compounds, styrenes, maleic esters, fumaric esters, itaconic esters, crotonic esters, and olefins.

Specifically, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-cyanoethyl acrylate, N-
(Β-dimethylaminoethyl) acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl acrylate: methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 3
-Sulfopropyl methacrylate: allyl butyl ether, allyl phenyl ether: methyl vinyl ether,
Butyl vinyl ether: methoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, (2-dimethylamino ether) vinyl ether, vinyl phenyl ether, vinyl chlorophenyl ether, acrylamide, methacrylamide, N-methylacrylamide,
N- (1,1-dimethyl-3-oxobutyl) acrylamide, N- (1,1-dimethyl-3-hydroxybutyl) acrylamide, N, N-dimethylacrylamide, acryloylhydrazine, N-methoxymethylmethacrylamide, N- (1,1-dimethyl-3-hydroxybutyl) methacrylamide, N-hydroxymethylacrylamide: vinylpyridine, N-vinylimidazole, N-vinylcarbazole, vinylthiophene: styrene, chloromethylstyrene, p-acetoxystyrene, p- Methylstyrene: p-vinylbenzoic acid, methyl p-vinylbenzoate: crotonamide, butyl crotonate, glycerin monocrotonate: methyl vinyl ketone, phenyl vinyl ketone: ethylene, propylene, 1
-Butene, dicyclopentadiene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene: methyl itaconate, ethyl itaconate, diethyl itaconate: methyl sorbate, ethyl maleate, butyl maleate,
Dibutyl maleate, octyl maleate: ethyl fumarate, dibutyl fumarate, octyl fumarate: halogenated olefins such as vinyl chloride, vinylidene chloride and isoprene: unsaturated nitriles such as acrylonitrile and methacrylonitrile.

Preferred specific examples of the compound represented by the general formula (1) include, but are not limited to, the following.

1-1 Poly (N-vinylpyrrolidone) 1-2 N-vinylpyrrolidone-vinyl alcohol copolymer (80:20) 1-3 N-vinylpyrrolidone-vinyl alcohol copolymer (70:30) 1 -4 N-vinylpyrrolidone-vinyl acetate copolymer (70:30) 1-5 N-vinylpyrrolidone-acrylic acid copolymer (90:10) 1-6 N-vinylpyrrolidone-2-hydroxyethyl acrylate copolymer Combined (70:30) 1-7 N-vinylpyrrolidone-acrylamide copolymer (80:20) 1-8 N-vinylpyrrolidone-acrylamide copolymer (60:40) 1-9 N-vinylpyrrolidone-dimethylacrylamide Copolymer (70:30) 1-10 N-vinylpyrrolidone-vinylacetamide copolymer (70:30) ) 1-11 N-vinylpyrrolidone-vinyl acetate-
Vinyl alcohol copolymer (60:30:10) 1-12 N-vinylpyrrolidone-2-hydroxyethyl acrylate-vinyl acetate copolymer (70: 2
0:10) 1-13 poly (N-vinyloxazolidone) 1-14 poly (N-vinylpiperidone) 1-15 poly (N-vinylsuccinimide) 1-16 poly (N-vinylglutarimide) 1-17 N- Vinyl pyrrolidone-2-methoxyethyl acrylate copolymer (70:30) 1-18 N-vinyl pyrrolidone-methyl vinyl ether copolymer (80:20) 1-19 N-vinyl pyrrolidone-N-vinyl piperidone-2-hydroxyethyl Acrylate copolymer (5
0:30:20) 1-20 N-vinyl-ε-caprolactam-acrylamide copolymer (60:40) The preferred addition amount to the colloidal silver-containing hydrophilic layer is from 10 g to 300 g per mol of colloidal silver, and The preferable addition amount of the antihalation layer is from 5 g to 5 g.
The addition amount is 0 g, and the preferable addition amount for the yellow filter layer is 50 g to 300 g. The preferred amount of the adjacent layers is 0.05 g / m ² from 0.005 g / m ^2.

The coating amount KG (g / m ² ) of the compound represented by the general formula (1) in the colloidal silver-containing hydrophilic layer of the present invention and the gelatin coating amount EG (g / m ² ) of the colloidal silver-containing hydrophilic layer.
The ratio of m ² ) is from 1: 3 to 1: 100. The ratio is preferably 1: 8 to 1:50, and when the ratio is 1: 100 or more, the effect of the present invention is small, and when the ratio is 1: 3 or less, coatability and performance with a film after coating are deteriorated.

The weight average molecular weight of the compound represented by the general formula (1) of the present invention is from 10,000 to 250,000, preferably from 10,000 to 200,000.

Next, the compound represented by formula (2) will be described in detail. In the general formula (2), R ¹¹ represents a hydrogen atom or a group which can be eliminated by a reaction with an oxidized form of an aromatic primary amine color developing agent. R ¹¹ is preferably a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent, and more preferably an arylthio group, from the viewpoint of saving silver and improving resistance to harmful gases.

R ¹² represents an aryl group, for example, a phenyl group, a pentachlorophenyl group, a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group, a 2,4-
Dichlorophenyl group, 2,6-dichloro-4-methylphenyl group, 2,6-dichloro-4-methanesulfonylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2,6-dichloro-4-morpholinosulfonylphenyl group, 2,4-dichloro-6-methoxyphenyl group, 2,
4-dichloro-6-methylphenyl group and the like.

When the compound of the present invention is used in a color negative film, R ¹² is a pentachlorophenyl group, and 2,6- is preferred in that the spectral absorption wavelength of the color dye obtained by reacting with the oxidized form of the color developing agent is preferable. Preferred are a dichloro-4-methanesulfonylphenyl group, a 2,6-dichloro-4-cyanophenyl group, and a 2,6-dichloro-4-morpholinosulfonylphenyl group.

R ¹³ represents a substituent, for example, chlorine, bromine,
Halogen atoms such as fluorine, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy groups, 2,6
-Dichlorobenzoylamino group, benzoylamino group such as 2,6-dimethoxybenzoylamino group, alkylsulfonyl group such as hexadecylsulfonyl, acylamino group such as acetylamino group, cyano group, nitro group, carboxyl group, amino group, Examples thereof include an alkoxycarbonyl group such as an ethoxycarbonyl group, and an alkyl group such as a methyl group, an ethyl group, and an isopropyl group. Of course, other monovalent substituents may be used.

It is preferable that at least one atom or group of R ¹³ is a halogen atom or an alkoxy group in terms of color development and spectral absorption wavelength.

Hereinafter, specific examples of the compound represented by the general formula [2] of the present invention are shown, but the present invention is not limited thereto.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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The compound represented by the general formula [2] according to the present invention (hereinafter also referred to as a magenta coupler represented by the general formula [2]) may be added to a photosensitive layer. It may be added to the layer. In order to introduce the magenta coupler represented by the general formula (2) according to the present invention into a silver halide color photographic light-sensitive material, it may be dispersed and added by various known dispersion methods described below. A mixture of a high-boiling solvent such as dibutyl phthalate and tricresyl phosphate and a low-boiling solvent such as butyl acetate and ethyl acetate, or a mixture of low-boiling solvents alone or in combination with the compound represented by the general formula (2). After dissolving by mixing with a gelatin aqueous solution containing a surfactant, then emulsifying and dispersing using a high-speed rotary mixer, colloid mill or ultrasonic disperser, then directly adding to the silver halide emulsion can do. Alternatively, the above emulsified dispersion may be set, shredded, washed with water, and then added to the silver halide emulsion.

In the present invention, more preferably, V
It is preferable that a compound capable of reacting with an oxidized form of a color developing agent represented by W-1, VW-2, or VW-3 is contained in the hydrophilic layer containing colloidal silver. The compound that reacts with the oxidized form of the color developing agent used in the present invention is a compound that can react with the oxidized form and capture it. Some of the compounds undergo an oxidation-reduction reaction with the oxidant, and others undergo a coupling reaction. Those that undergo an oxidation-reduction reaction are compounds that can be reduced with the oxidized form of the color developing agent.

[0040]

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With respect to the silver halide emulsion used in the present invention, a method for producing the silver halide emulsion and additives used in the production,
The physical ripening / chemical ripening / spectral sensitization and the additives used in these processes, various photographic additives / couplers, and their adding methods are described in, for example, RDNo. 17643, N
o. 18716 and the same No. 308119, and can be prepared with reference to them.

The above-mentioned RD can also be referred to for the auxiliary layer such as an intermediate layer, the layer structure such as a normal layer, a reverse layer and a unit structure, and the development processing which can be employed in the light-sensitive material of the present invention.

The light-sensitive material of the present invention can be applied to color light-sensitive materials such as color negative films for general use or movies, and color reversal films for slides or televisions.

The support used for the light-sensitive material of the present invention is not particularly limited, and those generally used in the art can be used. Preferable specific examples of the support include polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose. In addition, the support described in the RD can be used.

On the surface of the support on which the photographic constituent layer is formed,
If necessary, a surface activation treatment such as corona discharge and / or an undercoat layer can be applied prior to the formation of the constituent layer. The undercoat layer is disclosed in, for example, JP-A-59-199.
No. 41, 59-77439, 59-224841
And the undercoat layer described in JP-B-58-53029 can be mentioned as preferred examples.

[0046]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these embodiments. In the examples, “parts” represents “parts by weight”.

Example 1 Each layer having the following composition was provided on a 115 μm-thick triacetylcellulose transparent support provided with an undercoat layer to prepare Sample 101 as a multilayer color photosensitive material.

(Composition of photosensitive layer) For silver halide and colloidal silver, the coating amount is g / m ² in terms of metallic silver.
The amount expressed in units, and g for couplers and additives
/ M the amount expressed in ^two units, for Matazo sensitizing dye shown in mol per mol of silver halide in the same layer.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.002 Colored magenta coupler (CM-1) 003 High boiling solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 0.27 μm, silver iodide content: 2.0 mol%) 0.15 Silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content) 8.0 mol%) 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD-2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD-4) 0.7 × 10 ^-4 cyan coupler (C-1) 0.53 colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 high boiling point solvent (OIL-3) 0.48 gelatin 1.09.

Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 0.52 μm, silver iodide content 8.0 mol%) 0.89 Silver iodobromide emulsion (average particle size 0. 38 μm, silver iodide content 8.0 mol%) 0.22 sensitizing dye (SD-1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye ( SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C-1) 0.33 colored cyan coupler (CC-1) 0.013 DIR compound ( D-1) 0.02 High boiling solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: Highly sensitive red-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8) .0 mol%) 1.27 sensitizing dye (SD-1) 1.0 × 10 -4 sensitizing dye (SD-2) 1.0 × 10 -4 sensitizing dye (SD-3) 1 2 × 10 ^-5 cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 DIR compound (D-3) 0.001 High boiling solvent (OIL-1) 0.16 Gelatin 0. 79.

Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green-sensitive layer Silver iodobromide emulsion (average grain 0.38 μm diameter, silver iodide content 8.0 mol%) 0.64 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.21 sensitizing dye ( SD-4) 4.6 × 10 ^-5 sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (SD-4) CM-1) 0.06 DIR compound (D-1) 0.003 High boiling solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium sensitivity green sensitivity Layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.76 increase Sensitizing dye (SD-6) 1.2 × 10 ^-4 sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-3) ) 0.08 Colored magenta coupler (CM-2) 0.017 DIR compound (D-2) 0.025 High boiling solvent (OIL-4) 0.12 Gelatin 0.50.

Tenth layer: high-sensitivity green-sensitive layer Silver iodobromide emulsion (average particle size: 1.00 μm, silver iodide content: 8.0 mol%) 1.46 Sensitizing dye (SD-6) 7.1 × 10 ^-5 sensitizing dye (SD-7) 7.1 × 10 ^-5 sensitizing dye (SD-8) 7.1 × 10 ^-5 magenta coupler (M-3) 0.09 Colored magenta coupler (CM-) 2) 0.011 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0 .15 high boiling solvent (OIL-2) 0.19 gelatin 1.10 12th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.073 silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 3.0 mol% 0.16 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 sensitizing dye (SD-9) 6.3 × 10 ^-5 sensitizing dye ( SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40.

Thirteenth layer: high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average particle size: 1.00 μm, silver iodide content: 8.0 mol%) 0.95 Sensitizing dye (SD-9) 8.0 × 10 ^-5 sensitizing dye (SD-11) 3.1 × 10 ^-5 yellow coupler (Y-1) 0.12 DIR compound (D-6) 0.007 High boiling solvent (OIL-2) 0.05 Gelatin 0.79 Fourteenth layer: First protective layer Silver iodobromide emulsion (average particle size 0.08 μm, silver iodide content 1.0 mol%) 0.40 Ultraviolet absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size: 2 μm) 0.15 Polymethyl methacrylate (Average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1 and a dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggants AF-1, AF-2, and preservative D
I-1 was added.

The sample was simultaneously coated with a multi-slide hopper type coater on the first time from the first layer to the eighth layer, and on the second time on the ninth to fifteenth layers at the same time. The silver coating amount of Sample 101 was 6.25 g / m ² , the dry film thickness was 18 μm, and the specific photographic sensitivity was ISO420.

The compounds used are shown below.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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Sample No. Sample No. 101 was similarly prepared except that the first and eleventh layers of Sample No. 101 were changed as shown in Table 1 below. 1
Nos. 02 to 113 were produced.

[0068]

[Table 1]

For each sample, sensitometric measurement,
A test pattern for magenta image sharpness measurement was exposed, and a cine-type automatic developing machine for negative film (NCV-2) was used.
4, Noritsu Koki Co., Ltd.).

(Development processing) Processing details Processing time Processing temperature Replenishment rate (° C) (ml) Color development 3 minutes 15 seconds 38 ± 0.3 780 Bleaching 6 minutes 30 seconds 38 ± 2.0 150 Rinse water 3 minutes 15 Second 20 ± 10 200 Fixed 6 min 30 sec 38 ± 2.0 830 Washing 3 min 15 sec 20 ± 10 200 Stabilized 1 min 30 sec 38 ± 5.0 830 Drying 2 min 55 ± 5.0 − The replenishing amount is a value per 1 m ² of the photographic light-sensitive material.

The color developing solution, the bleaching solution, the fixing solution, the stabilizing solution, and the replenisher thereof were prepared as described below.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water was added to make 1 liter, and the pH was adjusted to 10.1.

<Bleaching solution> Ammonium iron (III) ethylenediaminetetraacetate 100 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150 g Glacial acetic acid 10 ml Add water to make 1 liter, and adjust to pH 6.0 using aqueous ammonia. It was adjusted.

<Fixing Solution> Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 with acetic acid.

<Stable liquid> Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konica Corporation) 7.5 ml Water was added to make 1 liter.

<Color developing replenisher> Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline sulfate 6.3 g potassium hydroxide 2 g diethylenetriaminepentaacetic acid 3.0 g water was added to make up to 1 liter, and the pH was adjusted to 10 using potassium hydroxide or 20% sulfuric acid. Adjusted to 18.

<Bleaching replenisher> Water 700 ml 1/3 ammonium ferric (III) diaminopropanetetraacetate 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjusted to pH 4.0 using aqueous ammonia or glacial acetic acid After that, water was added to make up 1 liter.

<Fixing replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, water was added to make 1 liter.

<Stable replenisher> Same as the stabilizer.

The sharpness of each of the developed samples was measured by the following method.

Sample No. After exposing 101 to 113 through a continuous wedge at a color temperature of 4700 K for 1/200 second, the above color development treatment was performed and the optical density was measured. Sample No. Samples in which 101 to 113 were stored for one week under the conditions of 55 ° C. and a relative humidity of 65% were similarly exposed and processed.
The photographic sensitivity is represented by the relative value of the reciprocal of the amount of exposure necessary to obtain an optical density of fog +0.1. The sensitivity of 101 was set to 100. The sensitivity and fog value after storage for one week
Sample No. immediately after application. The difference from the change value after storage was shown based on the sensitivity and fog of 101. The results are shown in Table 2 below.

[0082]

[Table 2]

From Table 2, it can be seen that the addition of an effective amount of the compound of the present invention immediately reduces the fog without the sensitivity and desensitization of the sample. Further, it can be seen that the sensitivity fluctuation and fog rise during storage are significantly suppressed. On the other hand, if added in an amount larger than the effective amount, the coating of the coating deteriorates, causing desensitization,
Raises fog on storage.

Example 2 As shown in Table 3 below, Sample No. Sample No. 101 was the same as Example 1 except that the second, tenth, and twelfth layers of Sample No. 101 were changed. Samples 201 to 214 were produced.

[0085]

[Table 3]

The results are shown in Table 4 below.

[0087]

[Table 4]

As can be seen from Table 4, when the compound of the present invention was added to the photosensitive layer or the non-photosensitive layer adjacent to the hydrophilic layer containing colloidal silver, the immediate sample was not accompanied by sensitivity and desensitization, and fog was not observed. Decrease. Further, it can be seen that sensitivity fluctuation and fog increase during storage are suppressed. On the other hand, those added in an amount larger than the effective amount significantly desensitize.

Example 3 The magenta couplers of the seventh, ninth, and tenth green-sensitive silver halide emulsion layers used in Example 1 were replaced with couplers shown in Table 5 below.

[0090]

[Table 5]

The sample No. of Example 1 was changed except that the couplers of the seventh, ninth and tenth layers were changed to A to F in Table 5 and the compounds of the tenth and eleventh layers were further changed. Sample No. 101 shown in Table 6 in the same manner as in Sample No. 101. Table 7 shows the results of preparing samples 301 to 320 and evaluating them in the same manner as described above.

[0092]

[Table 6]

[0093]

[Table 7]

According to Table 7, when the compound represented by the general formula (2) of the present invention was used, the compound represented by the general formula (1) of the present invention was converted to a hydrophilic layer containing colloidal silver and / or When added to the green photosensitive layer, its effect is further emphasized.
That is, the immediate sample reduces fog without sensitivity and desensitization. Further, it can be seen that sensitivity fluctuation and fog increase during storage are suppressed. On the other hand, those added in an amount larger than the effective amount significantly desensitize. In addition, VW-1 to 3
It can be seen that the addition of the compound further improves the stability.

[0095]

According to the present invention, it is possible to provide a silver halide color light-sensitive material which is high in sensitivity, has reduced slight fog accompanied by a decrease in sensitivity, and has reduced fog even during long-term storage.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 7/384 G03C 7/384

Claims (4)

[Claims] 1. A red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a hydrophilic layer containing colloidal silver each having at least one layer on a support.
In a silver halide color photographic light-sensitive material containing a layer,
The colloidal silver-containing hydrophilic layer is represented by the following general formula (1) and has a weight average molecular weight of 50,000 to 300,000.
A silver halide color photographic light-sensitive material containing from 5.00 to 500 g of a compound represented by formula (1) per mole of colloidal silver. Embedded image (In the formula, R ₀ represents a hydrogen atom or an alkyl group. Q represents a group of nonmetallic atoms necessary to form a 5- to 7-membered ring together with N and C。O. A and B are copolymerizable. Represents an ethylenically unsaturated compound, x, y, and z represent mol% and 10 ≦
x ≦ 100, 0 ≦ y ≦ 90, 0 ≦ z ≦ 90, and x +
y + z = 100. ) 2. The coating amount KG (g / m ² ) of the compound represented by the general formula (1) in the colloidal silver-containing hydrophilic layer and the gelatin coating amount EG (g / m ² ) of the colloidal silver-containing hydrophilic layer.
^{2. The} silver halide color photographic light-sensitive material according to claim 1, wherein the ratio of m ² ) is from 1: 3 to 1: 100. 3. A red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a hydrophilic layer containing colloidal silver each having at least one layer on a support.
In a silver halide color photographic light-sensitive material containing a layer,
0.001 g / m 2 of a compound represented by the general formula (1) and having a weight average molecular weight of 50,000 to 300,000 in a photosensitive layer or a non-photosensitive layer adjacent to the colloidal silver-containing hydrophilic layer. the silver halide color photographic light-sensitive material, characterized in that from ² containing 0.10 g / m ^2. 4. The photosensitive layer adjacent to the colloidal silver-containing hydrophilic layer is a green photosensitive layer, which contains a compound represented by the following general formula (2) and is represented by the general formula (1). the silver halide color photographic material, which comprises the compound 0.10 g / m ² containing from 0.001 g / m ² and being. Embedded image (Wherein, R ¹¹ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent. R ¹² represents an aryl group; R ¹³ represents a substituent; n ₁
Represents an integer of 1 to 5. When n ₁ is 2 or more, R ¹³ may be the same or different. )