JPH0339950A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the shelf stability of a dyestuff image and to obtain suitability to rapid processing without deteriorating other photographic performance by forming at least one silver halide emulsion layer contg. silver halide particles having >=90mol% silver chloride content and a specified compd. CONSTITUTION:At least one silver halide emulsion layer contg. silver halide particles having >=90mol% silver chloride content and a compd. represented by formula I is formed on a support. In the formula I, each of R1 and R2 is H or alkyl, each of R3 and R4 is H, alkyl, aryl or a heterocyclic group, each of R5 and R6 is H, alkyl, aryl, acyl or alkoxycarbonyl, X is a divalent group contg. C as a constituent atom of the 6-membered ring and n is 0, 1 or 2. High color development is attained, gradation, light fastness and shelf stability can be improved and suitability to rapid processing can be obtd.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, it has high color development, high gradation, and rapid processability, The present invention also relates to a light-sensitive material having a dye image having good light fastness.

[Background of the invention]

Aromatic primary
Dye images of light-sensitive materials formed using grade amine developing agents have insufficient light fastness.

In order to improve this drawback, Japanese Patent Application Laid-open No. 54-48535,
No. 60-222853 contains compounds having sterically hindered phenol groups, Nos. 59-119351 and 60-22.
No. 2854, No. 61-6652, No. 62-23914
Although amine compounds have been proposed in No. 9, they are still insufficient.

On the other hand, there has recently been a strong desire for light-sensitive materials that are suitable for rapid processing.

Using silver halide grains with a high silver chloride content can achieve a high development speed, but there are problems in terms of maximum density (hereinafter referred to as color development) and gradation, and furthermore, rapid processing reduces image storage stability. There were times when I tried to influence him. It has been found that when the above-mentioned compound having a sterically hindered phenol group is used in this system, the storage stability is improved to some extent, but it is not sufficient, and the color development and gradation are further deteriorated.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material which has good dye image storage stability and is suitable for rapid processing without deteriorating other photographic properties.

[Structure of the invention]

The above object is achieved by a silver halide color photographic light-sensitive material having the following structure.

A halogen compound characterized by having at least one silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol % or more and a compound represented by the following general formula 1:T = 1 on a support. Silver chemical color photographic material.

General formula (T) In the formula, R8 and R2 are hydrogen atoms or alkyl groups, R3
, R4 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R,, R is a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, and X is a constituent atom of the above 6-membered ring. A divalent group having carbon atoms of
n represents O, 1 or 2.

The compound represented by the general formula [T] (hereinafter referred to as the compound of the present invention) will be described in detail below.

The alkyl group represented by R1 or R2 is preferably a methyl group.

The alkyl group represented by R1-R6 has 1 to 4 carbon atoms.
The aryl group is preferably a phenyl group.

The heterocyclic group represented by R3 or R1 is preferably a thienyl group.

The alkoxycarbonyl group represented by R, , R, is preferably one having 2 to 19 carbon atoms, and the acyl group is preferably an acetyl group or a benzoyl group.

The interaction represented by R1-R1 includes those having a substituent, and when R,, R, is phenyl, preferred substituents include a halogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a cyclohexyl group. group, an alkoxy group having 1 to 18 carbon atoms, a feralkyl group having 7 to 9 carbon atoms, and a hydroxyl group. When R6゜R5 is an alkyl group, preferable substituents include a hydroxyl group, a phenyl group, a
-12 alkoxy group, benzoyloxy group, carbon number 2
-18 alkylcarbonyloxy groups.

Preferred divalent groups represented by X are >C=FJ
NII-acyl is punched, here R7 is a hydrogen atom,
alkyl having 1 to 4 carbon atoms, R is a hydrogen atom, a methyl group,
phenyl group, -P (OXO alkyl)2 (alkyl has 1 to 4 carbon atoms), allyloxy group, benzyloxy group, alkoxy group having 1 to 12 carbon atoms, R9 is a hydrogen atom,
Oll, allyloxy group, benzyloxy group, carbon number 1
~12 alkoxy groups, acyloxy groups, acylamino groups, R,. is a hydrogen atom, an acyl group, R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -CH20RI,
R, □ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R8
represents a hydrogen atom or an acyl group.

Acyloxy group represented by R3, acyl group S in the acylamino group, acyl group represented by R+o+R++, and C=NNi (-acyl group) in the acyl group represented by In addition to 18 alkylcarbonyl groups, preferable ones include 4 as shown below.

Here, R,=R,,n has the same meaning as above, and α1
m is O or l, m≧Q, and Ro is a simple bond or a divalent bonding group (for example, alkylene-carbon number 1-14).
(p is 0 or 1) group, R1 is a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), an acyl group,
an alkoxyoxalyl group, a sulfonyl group, a carbamoyl group, RIa+R17 represents a hydrogen atom, an alkyl group, an aryl group, R3, represents water R17 is the same as the above, and R1 represents an atom of 〇-21, an alkyl group] . ) represents.

Specific examples of the compound represented by the general formula (T) are shown below.

f13 T-13 T-14 T-30 The compound represented by the general formula (T) can be made into synthetic leather by a known method. For example, a method of acylating a 4-hydroxytetrahydrothiopyran compound with an acid chloride, a method of reacting a 4-ketotetrahydrothiopyran compound with a diol, and 1,5-dioxa-9-thia-spiro[5,5]-undecane. A method for obtaining a l,4-dioxa-8-thia-spiro[4,5]-decane type compound, etc. can be used.

The compound of the present invention is preferably added in a silver halide emulsion layer containing a coupler and silver halide grains having a silver chloride content of 90 mol% or more, particularly in a silver halide emulsion layer containing a yellow coupler and a cyan coupler. It is preferable to add it to at least one of the silver halide emulsion layers. It is also most preferred to use the coupler in a dispersion using a high boiling organic solvent.

At this time, if necessary, there is no problem in using a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading preventive agent. Examples include compounds described in the following numbers. At this time, there is no problem even if two or more kinds of compounds of the present invention are mixed.

The amount of the compound of the present invention added is preferably 1.5 g or less per 112 silver halide emulsion layers, particularly 0.5 g or less. 1 to 0.6 g of O is preferable.

The silver halide grains of the present invention have a silver chloride content of 90 mol% or more, a silver bromide content of 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of 10 mol % or less.

In addition, in the silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol % or more according to the present invention, The proportion of silver halide grains having a silver chloride content of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grains of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

The grain size of the silver halide grains of the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.42 to 1.6 μm, more preferably 0.05 μm to 1.6 μm.
It is in the range of 25 to 1.2 μm.

Note that the particle size can be measured by various methods commonly used in the technical field. A typical method is Loveland's "Particle Size Analysis Method J.
(A, S, T, M, Symposium on Light Microscopy 1955, pp. 94-122) or "The Theory of the Photographic Process" (by Mies and James, 3rd edition, published by Macmillan, 1966). Chapter 2).

The particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodispersed silver halide grains having a particle size distribution of 15 and a coefficient of variation of 0.22 or less, more preferably 0.15 or less. The coefficient of variation here is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri represents the particle diameter of each particle, and nl represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the circumferential area in the case of grains with shapes other than cubic or spherical. represent.

The silver halogenide grains used in the emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating and growing the seed particles may be the same or different.

Further, the method for reacting the soluble silver salt or soluble halogen salt may be a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but it is preferable to use a method obtained by a simultaneous mixing method. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the method described in No. 48521 and the like for the pAg-control doder. .

If further necessary, chlorine fB such as thioether, etc.
A solvent may also be used. Also, mercap I-group-containing compound,
A compound such as a nitrogen-containing heterocyclic compound or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

Any shape of the silver halogenide grains according to the present invention can be used. One preferred example is (1001
It is a cube with planes as crystal surfaces.

Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, Japanese Patent Publication No. 55-26589, Special Publication No. 55-4
No. 2737, The Journal Office (J, Photogr, Sci,
), 21.39 (1973), etc., a ladle for forming particles having shapes such as octahedron, tetradecahedron, dodecahedron, etc. can also be used. Furthermore, particles with twin planes may be used. The silver fluoride grains according to the present invention may have a single shape or may be a mixture of grains of various shapes.

The silver halogenide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, IJ dium salts or complex salts, rhodium salts or Metal ions can be added using complex salts, iron salts, or complex salts to be included inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, it is possible to Reduction-sensitizing nuclei can be added to the particle surface.

The emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention) is prepared by removing unnecessary soluble salts after the growth of the silver halide grains is completed.1. You can leave it as is, or you can leave it as it is. When removing the salt m, Research Disclosure! , No. 7643.

The silver halide grains used in the present invention may be grains in which the latent image is mainly formed on the surface, or grains in which the latent image is mainly formed inside the grain. Preferably, the latent image is formed primarily on the surface of the particles.

The emulsion of the present invention is chemically sensitized by conventional methods.

The high boiling point organic solvent used for dispersing couplers etc. has a boiling point of 15
It refers to an organic solvent at 0°C, preferably one with a dielectric constant of 6.0 or less. The types are not particularly limited, and examples include esters such as phthalate esters, phosphate esters, and benzoate esters with a dielectric constant of 6.0 or less, organic acid amides,
Examples include ketones and hydrocarbons themselves. More preferably, it is a high boiling point organic solvent having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mmHg or less at 100°C.

Further, more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent may be a mixture of two or more.

Note that the above-mentioned dielectric constant refers to a dielectric constant at 30°C.

Phthalic acid esters advantageously used in the present invention include those represented by the following general formula (S-1).

General Formula 1:5-1] In the formula, R1 and R2 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by R1 and R2 is 12 to 32. More preferably, the total number of carbon atoms is I6 to 24, and even more preferably 18 to 24.

In the present invention, R1 and R2 of the general formula C8-1]
The alkyl group represented by may be linear or branched, and examples include butyl group, pentyl group, hexyl group, 2-ethylhexyl group, 3,5.5-trimethylhexyl group, octyl group, and nonyl group. , decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc. R
The aryl group represented by 1 and R2 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group, etc.

These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents, and examples of substituents for alkyl and alkenyl groups include halogen atoms, alkokino groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. Examples of substituents for the aryl group include halogen atoms,
Examples include an alkyl group, an alkokene group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group.

In the above, R1 and R2 are preferably alkyl groups, such as 2-ethylhexyl group, 3,5.5-trimethylhexyl group, n-octyl group, n-nonyl group, etc.

Phosphoric esters advantageously used in the present invention include those represented by the following general formula (S-2).

General Formula 1:5-1] In the formula, R3, R4 and R5 each represent an alkyl group, an alkenyl group or an aryl group. However, R3R4 and R
The total number of carbon atoms in the group represented by 6 is 24 to 54, preferably 27 to 36.

The alkyl group represented by R''R' and R5 in general formula (S-2) is, for example, a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, a nonyl group, a decyl group, a dodecyl group, Tetradecyl group, hexadecyl group,
octadecyl group, nonadecyl group, etc., and aryl groups include phenyl group, naphthyl group, etc.
Examples of the alkenyl group include hexenyl group, heptenyl group, and octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents. Preferably R3R' and R5 are alkyl groups, for example 2-
Ethylhexyl group, n-octyl group, 3,5.5-trimethylhexyl group, n-nonyl group, n-decyl group, 5
Examples include ec-decyl group, 5ec-dodecyl group, t-octyl group, and the like.

Typical specific examples of high boiling point organic solvents preferably used in the present invention are shown below, but the present invention is not limited thereto.

-1 C2) 1° CH.

-8 -10 1 0”P 0CHzCHC*Hs C,H.

CHzCIIC4Hs 2H5 -13 -14 -15 -16 -17 -18 -21 2 The amount of high boiling point organic solvent used is preferably 0.1 to 10 m12, particularly 0.1 to 10 m12 per 1 g of coupler.
5+a (2 is preferred.

Examples of high-boiling organic solvents that may be used in combination with the above-mentioned high-boiling organic solvents include phenol derivatives that do not react with oxidized developing agents, phthalic esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, An organic solvent having a boiling point of 150° C. or higher, such as trimesic acid ester, is used.

Various types of couplers can be used in the light-sensitive material of the present invention. Examples of yellow couplers include those based on benzoylacetanilide and pivaloylacetanilide, and examples of magenta couplers include those based on 5-pyrazolone. Examples of cyan couplers include phenolic couplers.

In the light-sensitive material of the present invention, the silver halide emulsion layers are arranged on the support in the following order: a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. It is preferable.

After exposure, the light-sensitive material of the present invention can be subjected to a process including at least a color development process and a desilvering process to give a dye image, but preferably, after exposure, a color development process is performed, and then a bleach-fixing process is performed. This treatment method involves washing with water or stabilizing.

In the color development process, a color developing agent is usually contained in a color developing solution, but some or all of the color developing agent is incorporated into a color photographic light-sensitive material, and color development with or without a color developing agent is used. It also includes processing with liquid.

The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and is an aminophenol-based and p-7 color developing agent.
Although p-phenylenediamine derivatives are included, p-phenylenediamine derivatives are particularly preferred. These color developing agents can be used as salts of organic and inorganic acids;
For example, hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used.

Ru.

These compounds generally have a color developer IQ of about 0.
1 to about 30 g, more preferably color developer II
2 is used at a concentration of about 1 g to about 15 g.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phinidine diamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,N-diethyl-p-7unicine diamine salt am, N-methyl-p-phunidine diamine salt u
Salt, N-,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dotecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl -4-aminoaniline sulfate, N-ethyl-N-β ~ hydroxyethylaminoalinine, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N-(2-methquinethyl) -N Examples include ethyl-3-methylaniline-p-toluenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. The color developer may also contain commonly used alkaline agents such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metaborate, borax, etc., and may also contain various additives. , for example, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citradinic acid, preservatives such as hydroxylamine, polyethyleneimine, glucose or sulfites such as sodium salts, potassium salts, etc. May be contained. Furthermore, various antifoaming agents and surfactants, such as methanol, N,N-dinotylformamide, ethylene glycol, diethylene glycol or dimethyl sulfoxide, benzyl alcohol, etc. can be contained, but in the present invention, benzyl alcohol is substantially used. It is preferable to process with a color developing solution that does not contain sulfite and contains 2 x 10-" mol/Q or less of sulfite. The sulfite concentration is between 1 x 10-' and 1.7 x 10-" mol/Q.
is more preferable, especially 5 X 10-3 to I X 10
-'mol/(l is preferred. Also, "substantially free of benzyl alcohol" means that the concentration is less than 0.5a+ff/12, and it is preferable that it does not contain it at all.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

Further, the temperature of the processing solution in the color developing tank is preferably 10°C to 6°C.
The temperature is preferably 25°C to 45°C.

The developing time is preferably within 2 minutes and 30 seconds, more preferably within 2 minutes.

After color development, silver halide color photosensitive materials are usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment, or may be carried out separately (bleaching and fixing), but it is preferable to use a bleach-fixing bath that processes bleaching and fixing in one bath. The pH of the bleach-fix solution is preferably 4.5 to 6.8,
Particularly preferred is 4.5 to 6.0.

The bleaching agent that can be used in the bleach-fix solution is preferably a metal complex salt of an organic acid, particularly a complex salt of an organic acid such as aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt or copper. Preferably.

Additives added to the bleach-fix solution include, in particular, alkali halides or ammonium halides, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, metal salts, chelating agents, etc. can be mentioned.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the bleach-fix solution contains sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite, as well as boric acid, borax, and hydroxide. Contains one or more pH buffers consisting of various salts such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. I can do it.

〔Example〕

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

Example 1 Each layer having 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, and a multilayer silver halide layer was formed. A color photographic material sample 1 was prepared.

Preparation of photosensitive silver halide emulsion layer coating solution Dissolve the coupler shown in Table-1 in a mixed solvent of a high boiling point organic solvent and ethyl acetate, and add this solution to a 5% aqueous gelatin solution containing sodium dodenlebenzene sulfonate. After that, the mixture was fractionated using an ultrasonic homogenizer to obtain a coupler dispersion.

This dispersion contains a photosensitive silver chlorobromide emulsion (silver bromide 80 mol%).
was added to prepare a blue-sensitive silver halide emulsion layer coating solution.

The silver chlorobromide emulsion was chemically ripened using sodium thiosulfate, chloroauric acid, a stabilizer, and a sensitizing dye.

Table (1) Table (2) -t PVP (Polyvinylpyrrolidone) B (Dibutyl phthalate) ■ 1 ■ In addition, 10% 2.4dihydroxy-6-chloro-5-1 riazine sodium is used as a hardening agent during coating. An aqueous salt solution was used.

Next, as shown in Table 2, samples were prepared in which the silver chloride content of the silver halide emulsion in each light-sensitive emulsion layer and the additives and high-boiling point organic solvent in the blue-sensitive layer were changed. The additive was added together with the coupler after being dissolved in a high boiling point organic solvent.

Preparation of high silver chloride content silver chlorobromide emulsion [Preparation method of blue-sensitive silver halide emulsion] The following (A
liquid) and (liquid B) with pAg=6.5, p[]-3,0
They were simultaneously added over a period of 30 minutes while controlling the pAg to be 7.3 and the pH was 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) N a CQ 3.42
gK B r O,0
Add 3gH and O to 200+n
12 (B liquid) A g N 03 10g
Add H2O to 200 m (2
(Liquid C) N a CQ 102.7
gK B r 1.0
Add gH2O to 600mQ (
Solution D) Add 3300 g of A g N O and 600 m (! After the addition, desalt using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magunium sulfate, and then add a gelatin aqueous solution and Mix to obtain an average particle size of 0.85μm
A monodisperse cubic emulsion EMP-1 with a coefficient of variation (S/r) = 0.07 and a silver chloride content of 99.5 mol % was obtained.

The following compound was used for the above emulsion EMP-1, and the temperature was 50°C.
A blue-sensitive silver halide emulsion (
EmA) was obtained.

Sodium thiosulfate 0.8 mg 1 mol 1 mol A Auric acid 0.5 mg 1 mol 1 mol A fixer 5B-5exto-' mol 1 mol AgX sensitizing dye D-15X10-◆ mol 1 mol AgX [Green-sensitive silver halide emulsion Preparation method 1 Same as EMP-1 except for changing the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D), average particle size 0.43 μm 1 coefficient of variation (S/r) -0.08, silver chloride content 99
．． A 5 mol % monodisperse cubic emulsion EMP-2 was obtained.

For EMP-2, the following compound was used at 55 °C for 12
After chemical ripening for 0 minutes, a green-sensitive silver halide emulsion (EmB
) was obtained.

Sodium thiosulfate 1.5 mg 1 mol 1 mol A Auric acid 1.0 mg 1 mol 1 mol A fixer 5B-56XIO-' mol 1 mol AgX sensitizing dye D -24,OX 10-' mol 1 mol AgX [red-sensitive halogen Preparation method of silver oxide emulsion 1 (liquid A) and (liquid B)
The average particle size was 0650μ in the same manner as EMP-1 except for changing the addition time of , and the addition time of (Liquid C) and (Liquid D).
A monodisperse cubic emulsion EMP-3 was obtained, having a coefficient of variation (S/r) of 0.08 and a silver chloride content of 99.5 mol%.

90°C at 60°C using the following compound for EMP-3.
After separation chemical ripening, red-sensitive silver halide emulsion (EmC)
I got it.

Sodium thiosulfate 1.8 mg 1 mol 1 mol A Auric acid 2.0 mg 1 mol 1 mol A fixative S B -56X 10-' mol 1 mol AgX
-1 -3 g-5 A O-1 Oji, H37 This sample was treated according to the conventional method according to the treatment steps described in the blue paper.

[Processing process 1 Temperature Development color development 3
5.0±0.3℃ 45 seconds bleach fixing 35.0±
Stabilized at 0.5°C for 45 seconds 30-34°0 Dry for 90 seconds 60-80°C 60
Second [Color developer 1 Pure water TRIETA] - Luamine N,N-diethylhydroxylamine Potassium chloride Potassium sulfite 1-Hydroxyethylidene-1,l-Diphosphonic acid Ethylenediamitetraacetic acid Catechol-3, 5-disulfonic acid disodium salt N-ethyl-N-β-methanesulfonate 800m after exposure 0g g 0.02g go, 3g 1.0g 1.0g 1.0g Amidoethyl-3-methyl-4 Aminoaniline 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 = 10.10.

[Bleach-fix solution/bleach-fix solution la contains 60 g of ferric ammonium ethylenediaminetetraacetic acid dihydrate, 3 g of ammonium thiosulfate (70% aqueous solution), 100 mf2 ammonium sulfite (40% aqueous solution), and 27.5+I2.

Adjust to pH=5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid 1 In stabilizing liquid 112, 5-chloro-2-methyl-4-isothiazolin 3-one 10 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 diphosphonic acid 2, Og ethylenediaminetetraacetic acid], Og water Ammonium oxide (20% aqueous solution) 3.0g Ammonium sulfite 3.0g Optical brightener (4,4'
-diaminostilbendisulfonic acid derivative)
Contains 1.5g. pH- with sulfuric acid or potassium hydroxide
Adjust to 7.0.

For each sample obtained, a PDA-65 densitometer (Konica) was used.
Co., Ltd.), the reflection density was measured using blue light, and the following characteristics were determined.

Color development: Shown as the maximum density achieved.

Gradation: The slope of the line connecting the points of density 0.25 and 0.75 on the characteristic curve. Light fastness: Attach an ultraviolet cut filter to the sample.
The residual rate (DsX
loo:D, . . . density after fading test) was determined.

In addition, in order to check suitability for rapid processing, the maximum density achieved when the color development time was changed to 90 seconds was determined.

The results are shown in Table-2.

As is clear from Table 2, Sample 1.2 has no suitability for rapid processing at all, and is also considerably inferior in color development, gradation, and light fastness, and the effect of AO-1 on light fastness. is also insufficient.

On the other hand, Sample 3 using an emulsion with a high silver chloride content has little variation due to changes in processing time and is suitable for rapid processing, but color development, gradation, and light fastness are further deteriorated. A
The effect of O-1 is not only insufficient, but also affects color development and gradation.

In contrast, in the sample of the present invention, all of these problems have been improved. This was not expected based on conventional knowledge, and the present invention makes it possible to provide a silver halide color photographic material that has high color development, high gradation, excellent light fastness, and is suitable for rapid processing. did it.

Furthermore, it can be seen that the effects of the present invention were further improved when a high boiling point organic solvent having a low dielectric constant was used as in samples 10 to 16.

In addition, each sample used T-1, T-14° and T-17 instead of T-2 of sample 5, and T-20, T-29, 7-31 instead of T-24 of sample 6. and silver chloride content of 93 instead of the silver chlorobromide emulsion of sample IO.
The effect of the present invention was also observed in a sample using a silver chlorobromide emulsion of mol %.

Example 2 A sample was prepared by changing the silver chloride content of the silver halide emulsion of each light-sensitive emulsion layer in Sample 1 of Example 1, and the additives and high-boiling point organic solvent of the red-sensitive layer as shown in Table 3. was prepared, and its color development, gradation, and light fastness were evaluated in the same manner as in Example I using red light.

The results are shown in Table-3.

From Table 3, it contains cyan coupler. It can be seen that the effect of the present invention is great even when added at the same time.

Furthermore, the effects of the present invention were also observed in samples in which T-7 and T16 were used instead of T-9 in sample 28, and in samples in which the support in sample 23 was replaced with titanium oxide-containing polyethylene terephthalate 1 to support. was recognized.

Claims (1)

[Scope of Claims] A support having at least one silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more and a compound represented by the following general formula [T-1] Characteristic silver halide color photographic material. General formula [T] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms or alkyl groups, R_3 and R_4 are hydrogen atoms, alkyl groups, aryl groups or heterocyclic groups, R_6 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, X represents a divalent group having a carbon atom as a constituent atom of the 6-membered ring, and n represents 0, 1 or 2. ]