JPH04133056A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility, light resistance and yellowing resistance by using specific magnetic couplers and specific compd. CONSTITUTION:Polyethylene (PE) is laminated on one surface of a paper base. The PE contg. titanium oxide is then laminated on another surface. Further, a protective layer contg. gelatin, a UV absorbent layer, a red sensitive layer contg. a red sensitive silver chlorobromide emulsion and cyan coupler, etc., a UV absorbent layer, a green sensitive layer contg. a green sensitive silver chlorobromide emulsion and magenta coupler, etc., an intermediate layer, and a blue sensitive layer contg. a blue sensitive silver chlorobromide emulsion and magenta coupler, etc., are applied thereon. The photosensitive material is thereafter subjected to color developing, bleach fixing, stabilizing, and drying after exposing in accordance with the conventional method. The general formulas of the couplers incorporated into these photosensitive emulsion layers are expressed by formulas [M-I] or [C-I] and the compd. expressed by general formula [II] is incorporated into at least any one layer of the photosensitive emulsion layers or nonphotosensitive emulsion layers.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material.
The present invention relates to a silver halide photographic material that can improve color reproducibility and reduce fading and yellowing caused by light.

[Background of the invention]

The purpose of reducing undesirable side absorption near 430 nm of a dye formed from a conventionally used 5-pyrazolone magenta coupler in a silver halide photographic light-sensitive material (hereinafter sometimes simply referred to as a photographic material or a light-sensitive material). Many pyrazoloazole-type magenta couplers were developed (US Patent No. 3,725.067, British Patent No. 1).
, No. 252, 418, Research Disclos
ure 24220.24230.24531.246
26, JP-A-59-162548, etc.). The dyes formed from these pyrazoloazole type couplers have significantly smaller sub-absorption near 430 nm than the dyes formed from the 5-pyrazolones, are preferable for color reproduction, and are resistant to light, heat, and humidity. It has the advantage that yellowing (Y stain) of uncolored areas is less likely to occur. However, magenta dyes formed from these couplers have extremely low fastness to light and are easily discolored by light, which significantly impairs the performance of color photographic materials, particularly color photographic materials for direct observation. Although yellowing was also improved, it was not sufficient. JP-A-59-125732 discloses IH-pyrazolo [5
A technique has been proposed for improving the light resistance of magenta dye images obtained by using a phenol compound or a phenyl ether compound in combination with a ゜1-C)-1,2,4-) lyazole type magenta coupler. . However, even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light. Therefore, methods for improving light fastness using various anti-fading agents have been proposed. For example, JP-A-62-246053 describes the combination of an amine-based anti-fading agent and a phenol-based anti-fading agent. Further, JP-A-62-180366 discloses a method of using a hindered phenol anti-fading agent and a hydroquinone compound in combination. Although photofading can be prevented to some extent by methods using these antifading agents, it is insufficient. Various techniques have also been proposed for improving the light fastness of pyrazoloazole couplers themselves. For example, JP-A-61-120147, JP-A No. 61-1201
Examples include couplers having specific substituents, as described in No. 48 specification and the like. Although these compounds do improve the light resistance, the light resistance was not sufficient in the samples in which the light-sensitive materials were colored after being stored for a long time, and furthermore, the prevention of yellowing was insufficient. Also, JP-A-62-169160, JP-A-62-169
No. 159 and JP-A-63-18475 propose a method of improving light resistance by changing the type and amount of the hydroquinone color mixture inhibitor contained in the photosensitive material. It has been found that these methods are insufficiently effective, and that there is a problem in that the light resistance deteriorates especially in samples that are colored after the photosensitive material has been stored over time. On the other hand, regarding cyan couplers, a coupler in which a substituent is bonded to a phenol nucleus via a ureido bond and a chlorine atom is directly bonded to the phenol nucleus has been proposed as a coupler with good color reproducibility. However, like the magenta coupler described above, this cyan coupler still has problems in terms of light resistance and yellowing.

[Purpose of the invention]

Each invention of the present application aims to solve the above-mentioned problems. That is, the invention of claim 1 of the present application uses a magenta coupler with good color reproducibility to fully exhibit the effect of improving the color reproducibility, and also has good light fastness and yellowing resistance, so that it is resistant to light damage. An object of the present invention is to provide a silver halide photographic material that suppresses fading and yellowing. The invention of claim 2 of the present application uses a cyan coupler with good color reproducibility to fully exhibit the effect of improving color reproducibility, and also has good light fastness and yellowing resistance, thereby preventing color fading due to light. An object of the present invention is to provide a silver halide photographic material in which yellowing is suppressed. It is an object of the invention of claim 3 of the present application to provide a silver halide photographic material that solves all of the above requirements.

[Structure of the invention]

The invention of claim 1 of the present application provides a silver halide photographic material having at least one photosensitive emulsion layer and at least one non-photosensitive emulsion layer on a support, in which at least one layer of the photosensitive emulsion layer is provided. It is characterized by containing a coupler represented by CM-I) below, and containing a compound represented by general formula (n) below in at least one of the photosensitive emulsion layer or the non-photosensitive emulsion layer. This is a silver halide photographic light-sensitive material that achieves the above object. The invention according to claim 2 of the present invention provides a silver halide photographic material having at least one photosensitive emulsion layer and at least one non-photosensitive emulsion layer on a support, in which at least one layer of the photosensitive emulsion layer is provided. A compound represented by the general formula (II) according to claim 1, which contains a coupler represented by the below-mentioned - killing [C-1] and in at least one of the photosensitive emulsion layer or the non-photosensitive emulsion layer. A silver halide photographic light-sensitive material characterized by containing the following, thereby achieving the above object. The invention according to claim 3 of the present invention provides a silver halide photographic material having a light-sensitive emulsion layer and a non-light-sensitive emulsion layer each having a small number (one layer each) on a support, in which at least one of the light-sensitive emulsion layers One layer contains the general formula (M-I
), and at least one of the photosensitive emulsion layers contains a coupler represented by the general formula (C-1
A halogen compound containing a coupler represented by formula (3) and a compound represented by general formula (n) according to claim 1 in at least one of the photosensitive emulsion layer or the non-photosensitive emulsion layer IJii. A silver chemical photographic material,
This achieves the above objective. As a result of further consideration of the conventional technology and the findings of the present inventors, the present inventors have found that only when a specific coupler and a specific hydroquinone color mixture inhibitor are used in combination, color development occurs after the photosensitive material is stored over time. The inventions of the present application were completed by discovering that the light resistance of the sample was uniquely improved in a synergistic manner. Furthermore, it has been found that the above combination improves the level of yellowing caused by light to a level that cannot be achieved with conventional couplers, and has thus arrived at the inventions. The present invention will be explained in more detail below. In -Sakatsuki (M-1), Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing reagent. Also R9. R'' and R'' represent a substituent. Here, the term "substituent" includes various groups that can serve as a substituent in the above-mentioned structure, and substituent atoms, but excludes hydrogen atoms. The substituents represented by R9, R'' and R'' are not particularly limited, but typically include multiple groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. ,
In addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, Also included are polycarbonyl, heterocyclic thio, spiro compound residues, bridged hydrocarbon compound residues, and the like. The alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched. More preferably, R9 to R'' are multiple groups such as methyl and ethyl. The aryl group is preferably a phenyl group. The acylamino group includes an alkylcarbonylamino group, an arylcarbonylamino group, etc. Sulfonamide group Examples include an alkylsulfonylamino group, an arylsulfonylamino group, etc. Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the alkyl group and aryl group represented by R9, RID, and R'' above. The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched. The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred. Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and arylsulfonyl groups. , arylphosphonyl group, etc.; Acyl group includes alkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group includes, for example, alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes alkylsulfamoyl group, arylsulfamoyl group, etc. ;As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group ring;As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.;As an ureido group, an alkylureido group, an arylureido group, etc.;sulfamoylamino group Examples of the heterocyclic group include an alkylsulfamoylamino group and an arylsulfamoylamino group; examples of the heterocyclic group include 5- to 7-membered ones, and specific examples include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group,
2-hendithiazolyl group ring; 5 as a heterocyclic oxy group
Those having ~7-membered heterocycles are preferred, for example 3,4
, 5.6-tetrahydrobilanyl-2-oxy group, 1゛-phenyltetrazole-5-oxy group; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as a 2-pyridylthio group. , 2-benzothiazolylthio group, 2,4-diphenoxy1.3.5-)lyazole-6-thio group, etc.; As a siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; as an imide group is a succinimide group, a 3-heptadecylsuccinimide group, a fucurimide F group, a glutarimide group, etc.; as spiro-formed 11 residues, spiroC3,3]hebutane-
1-yl, etc.: As a bridged hydrocarbon compound residue, bicyclo[2゜2.1
]hebutan-1-yl, tricyclo[3°3.1.1'
"7] Decane-1-yl, 7,7-dimethyl-bicycloC2,2,1)hebutan-1yl, etc. are mentioned. As a group that leaves by reaction with the oxidized product of the color developing agent represented by For example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio , arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino, aryloxycarbonylamino,
carboxyl, (R1' has the same meaning as the above R, Z' has the same meaning as the above Z, R2r and R3' represent a hydrogen atom, an alkyl group, an alkyl group or a heterocyclic group), etc. Among these groups, a halogen atom, particularly a chlorine atom is preferable. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. More specifically, what is represented by the general formula (M-i) is represented by, for example, the following -Formation CM-II:l to general formula [M-■]. General formula (M-IN General formula [M-■] General formula (M-II[) Issatsu CM-■] General formula CM -V) R2 in the above-mentioned -Sassatsu CM-n) ~ -General formula M-■]
~R'l and X have the same meanings as R9, RIo, RI' and X above. In addition, the following -J1 formula [M-1] is preferable:
It is represented by the formula (M-■). -Massage CM-■] R11~ ~, 2 In the formula, R'', R'', R'', X and Zl are -formation 1:M
R9 in -1). Synonymous with R'', R'', X and Z. Among the magenta couplers represented by the above-mentioned -formation [M-11) to -general formula M-■], particularly preferred ones are -formation (
M-n) is a magenta coupler. In addition, substituents which the ring formed by Z in -formation CM-1) and the ring formed by Zl in -formation [M-■] may have, and -formation CM-II) ~ -
R2-R8 in general formula M-VI) is preferably represented by -formation CM-IX). General Section CM-IX) R'-3O□-R2 In the formula, R' represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group. The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether it is straight chain or branched. The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one. Typical specific examples of the coupler represented by the general formula CM-1) will be summarized below, but as a matter of course, the couplers that can be used in the present invention are not limited to these examples. As the coupler represented by CM-I), in addition to the typical examples listed below, compounds described on pages 66 to 122 of the specification of Japanese Patent Application No. 61-9791 are listed. be able to. The coupler is also described in the Journal of the Chemical Society.
chemical 5ociety) + Perkin (Per
kin) I (1977), 2047-2052
, U.S. Patent No. 3,725,067, JP-A-59-994
No. 37, No. 58-42045, No. 59-162548
No. 59-171956, No. 60-33552,
It can be synthesized by referring to No. 60-43659, No. 60-172982, No. 60-190779, etc. The above couplers are preferably 1/mol silver halide.
Xl0-” mol-1 mol, more preferably 1xio-2
It can be used in the range of -8x10-' moles. Next, the cyan coupler represented by the general formula ((, -1) will be described. Specific examples of the -formation (C-1) and the coupler represented by this formula will be summarized later, but the examples are limited to those shown below. - In formation (C-1), R1 represents a ballast group, R2 represents an alkyl group having 2 or more carbon atoms, and Zl is released by reaction with a hydrogen atom or an oxidized product of a color developing agent. In the cyan coupler represented by -formation (C-1) above, the alkyl group represented by R2 may be linear or branched, and includes those having a substituent. R2 is preferably It is an alkyl group having from 2 to 6 carbon atoms.The ballast group represented by R' imparts sufficient bulk to the coupler to make it substantially unable to diffuse from the layer to which it is applied to other layers. It is an organic group having the size and shape given to the molecule.The preferred ballast group is the following -formation% formula% General formula (C-1-A) CH-0-Ar R1l+ R11 has 1 to 1 carbon atoms. represents an alkyl group of 12, Ar
represents an aryl group such as a phenyl group, and this aryl group includes those having a substituent. Specific examples of the cyan coupler represented by the general formula (C-1) that can be used in the present invention, including the exemplified compounds shown below, are disclosed in Japanese Patent Publication No. 11572-1982 and Japanese Patent Application Laid-open No. 11572-1983.
No. 3142, No. 61-9652, No. 61-9653, No. 61-39045, No. 61-50136, No. 6
No. 1-99141, No. 61-105545, etc. - The cyan dye-forming coupler shown in (C-1) is usually preferably lXl0- per mole of silver halide.
'mol-1 mol, more preferably 1 x 10-2 mol-8
It can be used in the range of X10-' moles. Next, general formula (n) will be explained in detail. - Formation (II)
(described below), R12 and R'3 represent a secondary or tertiary alkyl group. However, RIZ and RIff
The total number of carbon atoms in the alkyl groups represented by is 20 or more. Examples of the alkyl group represented by RIZ RI3 include a 5ec-decyl group, a 5ec-dodecyl group, a t-dodecyl group, and the like. The compound represented by -formation (n) is a dialkyl/S idowaquinone, and typical examples thereof will be shown below, but the compounds that can be used in the present invention are not limited to these examples. The compound represented by the general formula [■] may be added to any layer of the light-sensitive material, but is preferably added to a layer other than the magenta coupler-containing layer, and more preferably adjacent to the magenta coupler- or cyan coupler-containing layer. It is a layer that
More preferably, it is a layer close to the support adjacent to the magenta coupler-containing layer. These compounds are usually used in an amount of 0.01 to 0.5 g/layer.
It is preferable that the amount of carbon dioxide is added.

【Effect of the invention】

According to each invention of the present invention, the effect of improving color reproducibility is fully exhibited by using a coupler with good color reproducibility, and the light fastness and yellowing resistance are also improved, thereby preventing discoloration due to light and yellowing. It is possible to provide a silver halide photographic light-sensitive material that suppresses .

【Example】

Examples of the present invention are shown below, but the present invention is not limited to the examples described below. Example 1 Each layer having the structure shown below was coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side, and each layer was coated with halogen. A silver oxide color photographic material sample 101 was prepared. The coating solution was prepared as follows. First layer coating liquid Yellow coupler (Y-6) 26.7g, dye image stabilizer (ST-1) 10.0g, (ST-2)
Add 60 d of ethyl acetate to 6.67 g of additive (HQ-1), 0.67 g of additive (HQ-1), and 6.67 g of high-boiling point organic solvent (D N P ), and dissolve this solution.
10% gelatin aqueous solution containing SU-1) 7d 220
d was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 9.23 g of silver) prepared under the following conditions to prepare a first layer coating solution. The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution. The composition of each layer is shown below (amounts are shown in g/rd). The structures of the compounds used are summarized below. 7th layer (protective layer): Gelatin 1.0 6th layer (ultraviolet absorption layer): Gelatin 0.4 ultraviolet absorber (UV-1) 0.10 ultraviolet absorber (U
V-2) 0.04 ultraviolet absorber (UV-3
) 0.16 Stain inhibitor (HQ-1>
0.01DNP
O, 2P V P
O,03 anti-irradiation dye (A, l-2) 0
．． 02 5th layer (red sensitive layer): Gelatin red malignant silver chlorobromide emulsion (EmC) Cyan coupler (C-2-1) in terms of silver Dye image stabilizer (ST-1) Stain inhibitor (HQ) -1) B5-1 OP 4th layer (ultraviolet absorption layer): Gelatin ultraviolet absorber (UV-1) ultraviolet absorber (UV-2) ultraviolet absorber (UV-3) stain inhibitor (HQ-2) 1 .30 0.21 0.4 0.20 0゜01 0.20 0.20 0.94 0.28 0.09 0゜38 0.03 D\P 3rd layer (green-sensitive layer): Gelatin green-sensitive layer Silver chlorobromide emulsion (EmB) Magenta coupler (M-23) in terms of silver IDP Ylang ion prevention dye (A1 0.40 1.40 0.17 0.35 0.50 0.01 Second layer ( Intermediate layer): Gelatin stain inhibitor (HQ-2) IDP 1st layer (blue-sensitive layer): Gelatin blue-sensitive silver chlorobromide emulsion (EmA) Yellow coupler (Y-6) in terms of silver Dye image stabilizer (ST-1) Dye image stabilizer (ST-2) 1.20 0.12 0.15 1.20 0.26 0.80 0.30 0.20 Anti-stain agent (HQ-1) 0.02 Anti-aging dye (AI-3) 0.01 DNP 0.20 Support: Polyethylene laminate paper H-1 was used as a hardener.Each emulsion used for sample preparation was: It was prepared by the following method. (Preparation method of blue-sensitive silver halide emulsion) The following (liquid A) and (liquid B) were added to a 2% aqueous gelatin solution at pAg=6.5. While controlling the pH to 3.0, they were simultaneously added over 30 minutes, and then the following (solution C) and (D
1 while controlling the liquid) at pAg=7.3 and pH-5.5.
They were added simultaneously over 80 minutes. 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) Sodium chloride 3.42g Potassium bromide 0.03g Add water 7
200d (B liquid) 6 xiao acid i 艮
10■ Add water
200ml (Liquid C) Sodium chloride 102.7g Potassium bromide 1.0g Add water
600d (Liquid D) Add 300g of silver nitrate water. After adding 600d, desalt using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mix with an aqueous gelatin solution. Average particle size 0.85 μm, coefficient of variation (σ/r
)-0.07, a monodisperse cubic emulsion E M Pl having a silver chloride content of 99.5 mol % was obtained. The following compound was added to the above emulsion EMP-1 at 50'(
Chemical ripening was carried out for 90 minutes at J2 to obtain a blue-sensitive silver halide emulsion (ShimA). (AgX represents silver halide. The same applies in the description of this specification). Sodium thiosulfate 0.8 ■ 1 mol AgX chloroauric acid 0.5 ■ 1 mol AgX stabilizer 5
B-5 6 x 10-4 mol 1 mol Agx Sensitizing dye D-1 5 x 10-' mol 1 mol AgX (Preparation method of green-sensitive silver halide emulsion) (A solution) and (B
The average particle size was 0.4 in the same manner as EMP-1 except that the addition time of liquid) and the addition time of liquid C and liquid D were changed.
Monodispersed cubic emulsion EMP-2 with 3 μm, coefficient of variation (σ/r) = 0.08, and silver chloride content of 99.5 mol%
I got it. 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 ■ 1 mole AgX chloroauric acid 1.0 ■ 1 mole AgX stabilizer
SB-5 6X10-' mol 1 mol AgX Sensitizing dye D-2 4X10-' mol 1 mol A g
The average particle size was 0.5 in the same manner as EMP-1 except for changing the addition time of liquid) and the addition time of (liquid C) and (liquid D).
A monodispersed cubic emulsion EMP-3 was obtained, with a coefficient of variation (σ/r) of 0.08 and a silver chloride content of 99.5 mol%. EMP-3 was heated to 90°C at 60'C using the following compound.
Red-sensitive silver halide emulsion (EmC) after separation chemical ripening
I got it. Sodium thiosulfate 1.8 ■ 1 mole AgX chloroauric acid 2.0 ■ 1 mole Agχ stabilizer
5B-5 6X10-' mol 1 mol AgX Sensitizing dye D-3 s, ox io-' mol 1 mol AgX The structures of the compounds used in the emulsion preparation are summarized below. The same sample was prepared in the same manner as Sample 101, except that the magenta coupler and HQ-2 in the first and fourth layers were changed to the combinations shown in Table 1 below. This sample was mixed with 40'C180R) at 1% according to a conventional method.
After heating and humidifying for days, heating was further carried out at 60° C. for 3 days, and after exposure to green light, processing was performed according to the following processing steps. (Processing process) Temperature Time 35.0±0.3°C 45 seconds 35.0±0.5"C 45 seconds 30-34°C 90 seconds 60-80°C 60 seconds Color development Bleach Fix Stabilization Dry Color developer > Pure water triethanolamine N, N-diethylhybromide Potassium chloride Potassium sulfite 00d N 10g Droxylamine 5g 0.02 g g 0.3g 1-Hydroxyethylidene-1,1 diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1 .0g Catechol-3
,5-disulfonic acid disodium salt 1.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g optical brightener (4,4'-diaminostilhendisulfone Acid derivative) 1.0g potassium carbonate 27g water was added to bring the total amount to 11, pH=10. Adjust to LO. <Bleach-fix solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100iyf Ammonium sulfite (40% solution> Add 2'7.5d water and bind the total amount by 1!) pH=5.7 with potassium carbonate or glacial acetic acid
Adjust to. <Stabilizing liquid> 5-chloro-2-methyl-4-isothiazolin-3-one 1. ．． 0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% solution) 3.0 g optical brightener (
4,4'-diaminostilhenesulfonic acid gN form) 1,5
g Add water to bring the total volume to 19V, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide. For each sample thus obtained, its concentration 1.
The light resistance (residual rate) at 0 was evaluated by irradiating sunlight for 14 days using an underglass outdoor exposure table. <Light yellow coloring> Increase in blue light reflection density (ΔD
Bmin) was measured. The obtained results are shown in Table 1 (see below). As is clear from Table 1, in the samples of the present invention, by using a specific magenta coupler in combination with a specific hydroquinone compound in the non-emulsion layer, light resistance (particularly when raw samples, i.e., samples before exposure and development, are stored over time) is improved. The light resistance of the sample that was subsequently colored was synergistically improved. The coupler of the present invention alone does not sufficiently improve the light resistance after storage, and the light resistance after storage does not improve until it is combined with the compound represented by the general formula (II) of the invention. This effect was completely unexpected. It can also be seen that the present invention was able to reduce pre-purchased coloring. Example-2 Regarding sample 5 of Example-1, 0.4 g/rrf of cyan coupler (C-2-1) contained in the fifth layer was
Cyan coupler CC-1-4) 0.4 g/n (changed to
It was set as 2. Further, Samples 13 to 19 were prepared by changing the cyan coupler of Sample 12 and the types of compounds added to the second layer and the fourth layer as shown in Table 2. For each sample, 60
After heating at °C for 3 days, a cyan colored image was obtained in the same manner as in Example-1. These samples were evaluated in the same manner as in Example 1 for light fastness and pre-coloring of cyan dye images. The results are shown in Table 2 (described later). In the sample of the present invention, the light fastness of the cyan image is good, and
A sample with less pre-existing coloring was obtained. -Formation (M-1) and Exemplary Compounds thereof-Formation CM-1) Exemplary compounds in the following margins: C5ti+t(t) CsH+t(t) Hs C8°CH. CJ+t(t) "sHlq(t) General formula [C 1] and its exemplary compound General formula [C 1] H Exemplary compound C1□Has -Formation (If) and exemplary compound general formula (n) H tI Exemplary compound: Lltl ■ Mixture CI □ ~ C, 4 Reaction product mixture of α-olefin and hydroquinone CI 2 '= CI II Reaction product mixture of α-olefin and hydroquinone CI 6 ~ C18 Reaction product between α-olefin and hydroquinone (in Examples) Compounds used) T-1 T-2 V-1 Kanashi sHz (t) UV-2 HBS-1 Q-1 H UV-3 0 Q-2 H OP Dioctyl phthalate NP Dinonyl phthalate U IDP Diisodecyl phthalate LH3no3 VP Polyvinylpyrrolidone I I

Claims (3)

[Claims] 1. A silver halide photographic material having at least one light-sensitive emulsion layer and one non-light-sensitive emulsion layer on a support, wherein at least one of the light-sensitive emulsion layers has the following general formula: A halogenated compound containing a coupler represented by M-I] and a compound represented by the following general formula [II] in at least one of the light-sensitive emulsion layer or the non-light-sensitive emulsion layer. Silver photosensitive material. General formula [M-I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [M-I], Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the The ring may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing reagent. R^9
, R^1^0 and R^1^1 represent a substituent. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [II], R^1^2 and R^1^3 represent a secondary or tertiary alkyl group. However, R^1^2 and R
The total number of carbon atoms in the alkyl group represented by ^1^3 is 20 or more. 2. A silver halide photographic material having at least one light-sensitive emulsion layer and one non-light-sensitive emulsion layer on a support, wherein at least one of the light-sensitive emulsion layers has the following general formula: C-1], and contains a compound represented by the general formula [II] according to claim 1 in at least one of the photosensitive emulsion layer or the non-photosensitive emulsion layer. Characteristic silver halide photographic materials. General formula [C-1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [C-1], R^1 represents a ballast group, and R^
2 represents an alkyl group having 2 or more carbon atoms. Z^1 represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of a color developing agent. 3. A silver halide photographic material having at least one light-sensitive emulsion layer and one non-light-sensitive emulsion layer on a support, wherein at least one of the light-sensitive emulsion layers comprises:
a coupler represented by the general formula [M-I] according to claim 2, and a coupler represented by the general formula [C-1] according to claim 2 in at least one of the photosensitive emulsion layers; A silver halide photographic material comprising a compound represented by the general formula [II] according to claim 1 in at least one of the photosensitive emulsion layer and the non-photosensitive emulsion layer.