JPS63115165A - Silver halide photographic sensitive material superior in color reproduction performance - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance by incorporating one of cyan couplers and a compound having at least one of Br and I in the molecular structure in one of silver halide emulsion layers. CONSTITUTION:At least one of the silver halide emulsion layers of the photographic sensitive material contains at least one of the cyan couplers represented by formula I (each of R1 and R2 is alkyl, cycloalkyl, alkenyl, aryl, or a heterocyclic group, and R3 is H, halogen, alkyl, or alkoxy), and at least one of the brominated and/or iodinated compounds containing at least one of Br and I in an amount of >=40wt%, thus permitting the cyan color image to be formed to be improved in storage stability and to be enhanced in color reproducibility by the shift of the maximum absorption wavelength of the cyan dye toward the longer wavelength side, and further, the obtained photographic sensitive material to be enhanced in color developing performance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material which has excellent color reproducibility and image storage stability and which can provide high II^ density.

[Background of the Invention] As cyan couplers with excellent fading properties used for color photographic paper used for direct viewing, 2,5-diacylamino cyan couplers and alkyl groups having 2 or more carbon atoms at the 5-position are used. However, dyes formed from 2゜5-diacylamino cyan couplers can be formed from phenolic cyan couplers that do not have an acylamino group at the 5-position, which has been commonly used. Compared to the dye formed, the maximum absorption wavelength is on the short wavelength side, and therefore the magenta component due to the short wavelength side of the absorption spectrum is large, so it has the disadvantage that it is not possible to sufficiently reproduce a colorful green color. In addition, dyes formed from phenolic cyan couplers having an alkyl group with two or more carbon atoms at the 5th position have a large yellow component around 420 nm, and therefore have the disadvantage that they cannot adequately reproduce vivid blue colors. .

In addition, in recent years, due to environmental pollution and work problems, it has been desired not to include benzyl alcohol as a color development accelerator in the color development solution. When a silver halide photographic light-sensitive material using a phenolic cyan coupler having an alkyl group having two or more carbon atoms is color-developed with a color developer that does not contain benzyl alcohol, the color density is low and a sufficient maximum density is obtained. The problem was that I couldn't get it.

On the other hand, as a cyan coupler used in high-sensitivity silver halide color photographic materials, for example,
No. 6-65134, No. 57-204543, No. 57-
No. 204544, No. 57-204545, No. 58-
No. 33249, No. 58-33251, No. 58-332
A phenolic cyan coupler having a ureido group at the 2-position described in Japanese Patent No. 52 is known. This phenolic cyan coupler, which has a ureido group at the 2-position of the phenol mother nucleus, is superior to conventionally used naphthol-based cyan couplers in that it does not cause reductive fading of the cyan dye during the bleaching or bleach-fixing process. However, this cyan coupler has the drawback that the maximum absorption wavelength of the dye is on the shorter wavelength side than that of the naphthol-based cyan coupler used conventionally.

Therefore, conventionally, in silver halide photographic materials using the above-mentioned cyan couplers, which have excellent storage stability of cyan dye images, that is, dark fading resistance and reduction fading resistance of cyan dye images, the spectral absorption characteristics of cyan dyes have been improved. It has been desired to develop a silver halide photographic material which can improve color reproducibility by improving the color reproducibility and can obtain sufficient color density through color development processing without using benzyl alcohol as a color development accelerator.

[Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and a first object of the present invention is that the maximum absorption wavelength of a cyan dye image is on the sufficiently long wavelength side of the red spectral region, and the color An object of the present invention is to provide a silver halide photographic material with excellent reproducibility.

A second object of the present invention is to provide a silver halide photographic material with excellent cyan dye image storage stability.

A third object of the present invention is to provide a silver halide photographic material that has high color density and can provide a sufficient maximum density.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula [I] A compound containing at least one cyan coupler represented by This can be achieved by using a silver halide photographic material containing at least one kind of a certain halogen-containing compound.

General formula [I] λ [wherein R1 and R2 each represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

However, R2 and R3 may jointly form a ring. X
represents a hydrogen atom or a group capable of eliminating thIl by reaction with an oxidized product of a color developing agent. m represents 0 or 1. ] [Specific structure of the invention] Next, the present invention will be specifically explained.

In the cyan coupler represented by the general formula [I] according to the present invention (hereinafter referred to as the cyan coupler of the present invention), the alkyl group represented by R1 or R2 is:
Those with 1 to 32 carbon atoms, and 2 carbon atoms as alkenyl groups
-32, cycloalkyl group has 3 to 1 carbon atoms
These alkyl groups, alkenyl groups, and cycloalkyl groups include those having substituents.

The aryl group represented by R1 or R2 is preferably a phenyl group, including those having substituents.

The heterocyclic group represented by R1 or R2 is preferably 5- to 7-membered, and may be substituted or fused.

R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom.

Mata, the ring formed jointly by R2 and R3 is 5 to 6
Preferably, a 5- to 6-membered ring is formed.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X in general formula [I] include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamimu L sulfonylamino group, Alkoxy groups include carbonyloxy, aryloxycarbonyloxy, halogen atoms, aryloxy groups, and alkoxy groups.

Particularly preferred among the cyan couplers of the present invention are those represented by the following general formula [IA].

General formula [I-A1 In the formula, R^1 represents a phenyl group substituted with at least one halogen atom, and these phenyl groups may further have a substituent other than the halogen atom. RA2 has the same meaning as R2 in the above general formula [I]. X^ represents a halogen atom, an aryloxy group or an alkoxy group.

Typical specific examples of the cyan coupler represented by the general formula [I] are shown below.

The cyan coupler of the present invention is disclosed in Japanese Patent Application No. 61-218, for example.
Specification No. 43, pages 26 to 35, JP-A-60-2251
Publication No. 55, page 7, lower left m - page 10, lower right page, JP-A No. 6
0-222853 Publication, page 6, top left a to page 8, bottom right column and JP-A-59-185335, page 6, bottom left column to
2,5-diacylamino cyan couplers described in the upper left column of page 9 and ureido group at the 2-position described in the upper right column of pages 8 to 11 of JP-A-59-139031. Contains a phenolic cyan coupler with
It can be synthesized according to the methods described in these specifications and publications.

The cyan coupler of the present invention is usually used in silver halide emulsion layers, especially red-sensitive emulsion layers, and its addition m is from 2.times.10@-3 to 8.times.10@-1 mol per mole of silver halide, preferably 1.times.10. -2 to 5 x 10'' moles.

Next, the halogen-containing compound (hereinafter referred to as the halogen-containing compound of the present invention) used in combination with the cyan coupler of the present invention will be explained.

The halogen-containing compound of the present invention is a compound containing a bromine atom and/or an iodine atom, and the combined content of bromine atoms and iodine atoms in the compound is 40% or more by weight.

That is, the halogen-containing compound of the present invention is a bromine-containing compound having a bromine content of 40% or more in terms of ff1ffi ratio,
Iodine-containing compounds with an iodine content of 40% or more by weight, and bromine/iodine containing both bromine atoms and iodine atoms, where the combined content of bromine and iodine atoms is 40% or more by weight This includes the compounds contained therein.

In this specification, the bromine content is the fiffl ratio occupied by bromine atoms in a molecule, and the iodine content is the weight ratio occupied by iodine atoms in a molecule, and each is defined as follows.

Further, the combined content of bromine atoms and iodine atoms in the bromine/iodine containing compound can be calculated as the sum of the bromine content and the iodine content.

Preferred among the halogen-containing compounds of the present invention are bromine-containing compounds and iodine-containing compounds, each preferably having the above bromine content or iodine content of 50% to 9.
0% compound.

The bromine atom contained in the bromine-containing compound of the present invention and the iodine atom contained in the iodine-containing compound of the present invention are bonded to carbon atoms, and the halogen-containing compound of the present invention may be an aliphatic compound. It may also be an aromatic compound.

Further, the halogen-containing compound of the present invention may contain, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a fluorine atom, a chlorine atom, etc. in place of a bromine atom, an iodine atom, a carbon atom, or a hydrogen atom. , and any functional groups and moieties of functional groups formed by these atoms (e.g. -
〇-1-CO-1-COO-1-0H1-COOH.

-〇N, -8-1-8O-1-502-1-N 1-
NH2, -NO2, -CON, -302N-1OP
-, etc.) may be included.

The halogen-containing compound of the present invention is added to the light-sensitive material in order to improve the hue of the cyan coloring dye after development. Therefore, the halogen-containing compound of the present invention is preferably one that does not flow out or undergo changes (eg, hydrolysis) during the development process. Therefore, the total number of carbon atoms in the halogen-containing compound of the present invention is preferably 3 or more, more preferably 8 to 50.

Further, the molecule m of the halogen-containing compound of the present invention is 200
~i, soo is preferred.

Further, the halogen-containing compound of the present invention is preferably not a compound capable of forming a dye, such as an active methylene compound, an active methine compound, or a compound containing an active cyan coupler residue at the rose position of the phenol nucleus.

Among the halogen-containing compounds of the present invention, particularly preferred are brominated paraffins with a bromine content of 40% or more, iodinated paraffins with an iodine content of 40% or more, and brominated paraffins with a bromine content or iodine content of 40% or more. Therefore, the following general formula [
II] to [■].

General formula [I[] R4-Go-Rs General formula [1 [[] % formula % General formula [rV] General formula [V] General formula [VI] R1 Do-8O2-R+s General formula [■1 R16 0= P -OR17 0R+a where R4~Rs, R1+* R12 and R14~
R+a each represents an alkyl group or an aryl group, and Rho and R+3 each represent a hydrogen atom, an alkyl group, or an aryl group. However, in the general formula [I[], at least one of R4 and R5 is substituted with the general formula [I[].
1[[], at least one of R6 and R7, and in the general formula [rV], Ra, Rs and Rho
at least one of the general formula [VIE is R11
, R12 and R13, the general formula [V
In I), at least one of R special and Rho,
In general formula [VI], R+6. R17 and Rho
At least one of them contains a bromine atom or an iodine atom.

Further, the alkyl groups and aryl groups represented by R4 to R+a include those having substituents other than bromine atoms and iodine atoms.

Typical specific examples of the halogen-containing compound of the present invention are shown below.

A-I A-2CH*
Br*CHs(CH-)
-BrA-3A-4 CHs(CHz)sCHBrCH3Br(CHJ4Br
A-5A-6 (CHa)*CBrCBr(CHi)*Br(
CHJeBrA-7A-8 Br(CHHsBr BrCHsCHBrC
H Gizu A-9A-10 Br Snow CHCHBrt CH*BrCHBr
CHBrCH*BrA-11A-12 p.

5r CHs (CHz) 1-Co OCHtc HBr
CHz BrA-2OA-21 CH*Br A-83A-24 Br Br r A-32 A-33A-34 A-37A-38 BrCHzCHBrCHtOCH*CHBrCHsBr
C4kl @ (L) A-49A-50 A-51A-52 CH3 (CHI)? I CH*I*
A-53A-54 I (CHI)t I I (C
H,)4 IA-55A-56 ICHtCHtCOO(CHt)ycHsA -58A
-59 A -8OA -61 A-62A-68 A-66A-67 ■ A-73A-74 p.

Some of the halogen-containing compounds of the present invention are commercially available products, and other compounds can be very easily synthesized from such commercially available products by generally known methods.

Use a of the halogen-containing compound of the present invention is 5 to 800% relative to the coupler represented by the general formula [I] of the present invention.
The amount is preferably mol, more preferably 20 to 500 mol%.

The halogen-containing compound of the present invention is a conventionally known compound or can be produced very easily from these compounds.

However, it was completely unknown that these halogen-containing compounds of the present invention improve color reproducibility by shifting the maximum absorption wavelength of cyan dye to the longer wavelength side.

That is, as a result of intensive research, the present inventors have found that the halogen-containing compound of the present invention shifts the maximum absorption wavelength of the cyan dye obtained from the cyan coupler of the present invention to the longer wavelength side,
As a result, it was found that color reproducibility was significantly improved, and such an effect was obtained for the first time by the present invention.

The halogen-containing compounds of the present invention may be used alone or in combination of two or more.

The cyan coupler of the present invention and the fluorine-containing compound of the present invention are preferably used in the same space, most preferably in the same hydrophobic organic phase (eg, oil phase) in the same layer. Specifically, the cyan coupler of the present invention and the halogen-containing compound of the present invention are combined, if necessary, with a high boiling point organic solvent, and optionally with a low boiling point and/or water-soluble organic solvent. It is preferable to dissolve the colloid at the same time, emulsify and disperse it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then add it to the desired hydrophilic colloid layer.

In this case, the halogen-containing compound of the present invention itself may be used as the high-boiling organic solvent.

High boiling point organic solvents that can be used as necessary include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, phosphoric esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters. Organic solvents having a boiling point of 150° C. or higher are preferred.

Examples of low boiling point organic solvents that may be used as necessary include:
Examples include ethyl acetate, cyclohexanol, methyl ethyl ketone, and the like.

In the present invention, as the yellow coupler, acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

In the present invention, as the magenta coupler, the well-known 5
-Pyrazolone couplers, pyrazolotriazole couplers, other birazoloazole couplers, etc. can be preferably used.

The cyan coupler of the present invention can be used in combination with conventionally known cyan couplers as long as it does not contradict the purpose of the present invention. In the case of the cyan coupler of the present invention in which m in the general formula [I] is O, that is, a 2゜5-diacylamino cyan coupler, a preferable cyan coupler that can be used in combination is represented by the following general formula [F]. An example is a coupler.

General formula [F] In the formula, R+F represents a balas 1- group. R2F represents a hydrogen atom, a halogen atom, or an alkyl group.

R3r represents an alkyl group having 1 to 6 carbon atoms.

ZIF represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

Examples of these cyan couplers are disclosed in Japanese Patent Application Laid-open No. 47-3, for example.
No. 7425, No. 50-10135, No. 50-2522
No. 8, No. 5G-112038, No. 50-117422
No. 50-130441, U.S. Patent No. 2,369,
No. 929, No. 2,423,730, No. 2,434.2
No. 72, No. 2,474,293, No. 2,698,
No. 794, U.S. Pat.
No. 2, No. 4,443,536, etc.

In addition, in the case of the cyan coupler of the present invention in which l in the general formula [I] is 1, that is, a phenolic cyan coupler having a ureido group at the 2-position, examples of the cyan coupler preferably used in combination include naphthol cyan couplers. .

Silver halides used in the present invention include silver chloride,
Any silver halide such as silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, etc. is included.

However, in silver halide photographic materials such as color photographic paper which require particularly fast developability, silver halide grains having a silver chloride content of 90 mol % or more are preferred.

In this case, the silver halide grains have a silver chloride content of 90 mol% or more, a silver bromide content of 10 mol% or less, and a silver iodide content of 0.5 mol% or less. is preferred. More preferably, silver chlorobromide has a silver bromide content of 0.1 to 5 mol%.

The silver halide used in the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred.

These silver halide emulsions may be chemically sensitized with active gelatin, a sulfur sensitizer, a selenium sensitizer, a reduction sensitizer, or a noble metal sensitizer.

The silver halide used in the present invention may be optically sensitized by adding a suitable sensitizing dye to impart photosensitivity to a desired wavelength range.

The silver halide photographic light-sensitive material of the present invention includes a color antifoggant, a stabilizer, a hardening agent, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger-1 mordant,
Development accelerators, development retarders, optical brighteners, matting agents, lubricants, antistatic agents, surfactants, and the like can be optionally used.

Various color development processes can be applied to the development process of the silver halide photographic light-sensitive material of the present invention.

The silver halide photographic material of the present invention can be applied to, for example, color negative and positive films, and color photographic papers of negative-positive and positive-positive systems.

[Effect of the Invention 1] The silver halide photographic light-sensitive material of the present invention contains the cyan coupler of the present invention and the halogen-containing compound of the present invention, so that the cyan dye image formed has good storage stability and Since the maximum absorption wavelength of the dye is shifted to the longer wavelength side, color reproducibility is also improved. Moreover, the silver halide photographic material of the present invention has excellent color development properties.

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

Example 1 (Preparation of silver halide emulsions) Six types of silver halide emulsions shown in Table 1 were prepared by the neutral method and simultaneous mixing method.

Table-1 Rate 1 Addition of 2ma per mole of silver halide *2 Addition of 5X10-5 mole per mole of silver halide *3 Addition of 0.9 mmol per mole of silver halide $4 0.7 per mole of silver halide Millimole addition: $5 0.2 millimole added per mole of silver halide Each silver halide emulsion contains the following 5TB emulsion stabilizer after chemical sensitization.
-1 was added in an amount of 5.times.10@-3 moles per mole of silver halide.

[5D-31 (Preparation of silver halide color photographic light-sensitive material sample) Next, the following FM1 to FM7 were sequentially coated (simultaneously coated) on a paper support coated with polyethylene on both sides to prepare a silver halide color photographic light-sensitive material. 1 to 22 were produced. (In the following examples, the addition m is expressed as m per 1f of light-sensitive material.) Layer 1: Gelatin (1,2+I+) and 0.29
g (in terms of silver, the same applies hereinafter) of blue-sensitive silver halide emulsion (Ei-1) and 0.75 g of yellow coupler (Y
-1>, 0.3 g of light stabilizer 5T-1 and 0.0151
A layer containing 0.3 g of dinonyl phthalate (DNP) in which 2,5-dioctylhydroquinone (HQ-1) of ) was dissolved.

Layer 2... Gelatin (0,90> and 0.04 (l
A layer containing 0.2 g of DOP (dioctyl phthalate) dissolved in HQ-1.

Layer 3: Gelatin (1,4(+) and 0,2g
green-sensitive silver halide emulsion (ErA-2) and 0.50
! 1117)? Zenta Kabler (M-1), 0.259
of light stabilizer 5T-2 and 0.3 g of DOP dissolved in 0.01 (l) of HQ-1 and 6 mg of filter dye Al-1 below.

Layer 4... Gelatin (1,2!II) and 0.6g of the following ultraviolet absorbers UV-1 and 0.05o (7)
A sample containing 0.3 g of DNP in which HQ-1 was dissolved.

l! ! 5...Gelatin (1,4(+) and 0.
Contains 20 g of a red-sensitive silver halide emulsion (Elm-3), a cyan coupler, a halogen-containing compound, and a high boiling point solvent shown in Table 2, and 0.3 (J of 5T-
1 and 0.0117 HQ-1.

Layer 6--gelatin (1,10),! :, 0.2g
(7) A layer containing 0.29 DOP and 1 g of 5II filter dye Al-2 with dissolved UV-1.

Layer 7... Gelatin (1,0(+) and 0.05
(layer containing 1 of sodium 2,4-dichloro-6-hydroxytriazine.

(S T -t) (S T -2) I-1 l-2 N &Sus'6CH*NH00H (y-j) I CaH+t(tl After wedge exposure using a photosensitive emulsion (manufactured by Konishi Rokusha Co., Ltd.) and processing according to the following color development processing steps, the highest density of the red-sensitive emulsion layer ( Qmax) was measured.

Further, the maximum absorption wavelength λWaX when the density of the cyan dye image was 1.0, and the density, D, and Dc of 42OnI11 and 550nl at that time were measured.

In addition, the obtained sample was kept at 85°C and 60% relative humidity for 20 days.
After storage for several days, the residual rate of the dye image at the initial density of 1.0 (
%) to evaluate the dark fading property.

The results are shown in Table-2.

[Processing process] Temperature Time Developed color development 34.7±0.3℃ Bleach for 45 seconds Stabilization for 34.7±0.5℃ 50 seconds 3
Dry at 0-34℃ for 90 seconds 60-80℃ for 60 seconds [
Color developer] Pure water
8001 (1 triethanolamine
89N,N-diethylhydroxyamine 5g
Potassium chloride 2ON-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
3 (l Q potassium sulfite
0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add pure water to bring the total volume to 12, and adjust the pH to 10.2.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 60 (1 liter ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100d ammonium sulfite (40% solution) 27.5.Q pH 5 with potassium carbonate or glacial acetic acid , adjust to 7 and add water to bring the total volume to 12
shall be.

[Stabilizing solution] 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-human Oxyethylidene-1゜1-diphosphonic acid 2g Add water to make it 111, and adjust the pH with sulfuric acid or potassium hydroxide. 7.0
Adjust to.

CC-1 CI G-2 (Bromine content: 21.6% by weight) Comparative compound (Iodine content: 32.1% by weight) As can be seen from the results in Table 2, the conventionally used phenol nuclei Sample N011 using a cyan coupler (CC-1) having a methyl group at the 5-position of
Qmax) is high, the maximum absorption wavelength (λWaX) is a long wavelength, and Dcr is small, but the dark fading property is very poor and it is not of practical use. Sample No. 12 containing the halogen-containing compound of the present invention showed a slight improvement in dark fading resistance, but it was still insufficient.

In addition, samples N011 and NO12 both have large DB and poor blue reproducibility. Sample No. 1 using a cyan coupler (CC-2) having an ethyl group at the 5-position of the phenol nucleus
3 and N014 have improved dark fading properties, but they still have large DB and poor blue reproducibility.

Sample No. 5°N using only the cyan coupler of the present invention
o, 10. No. 12 and No. 14 have very good fading properties, but in all cases, λIaX is a short wave and D
(Because the value of is large, sufficient green color reproduction cannot be achieved.

Further, samples No. 16, No. 21, in which the cyan coupler of the present invention and the cyan coupler outside the present invention were used in combination, also had short waves in λlaX, and although the DcT was slightly smaller, it was still insufficient. In addition, sample N006 using the cyan coupler of the present invention and a halogen-containing compound other than the present invention
and No. 7, D l1aX is high, but
λWaX is still a short wave, and DCr has become only slightly smaller.

In contrast, sample No. 8 of the present invention using the cyan coupler of the present invention and the halogen-containing compound of the present invention. No
,9. No. 11, No. 13 and No.

Sample No. 15 does not contain the corresponding fluorine-containing compound, and Sample No. 5. No, 10. No. 12 and No.

Compared to No. 14, DIlax is higher, λlaX has a longer wavelength, DI:T is smaller, and a significant improvement in green reproducibility is recognized. It can be seen that it is an excellent silver halide photographic light-sensitive material with excellent blue reproducibility and extremely good dark fading resistance due to its relatively small oe.

Samples Nos. 17 to 20 and No. 22 of the present invention, in which the cyan coupler of the present invention is used together with a cyan coupler other than the present invention, and the halogen-containing compounds of the present invention are used, respectively. Sample N that does not contain
Comparing with o, 16 and No, 21, [) WaX is high, λll1ax has a long wavelength, DQ is small,
Significant improvement in green color reproducibility is observed. It can be seen that the dark fading property is also better than that of sample No. 013 and is satisfactory.

Samples No. 18 and No. 17 and Samples No. 19 and No.

Comparing samples No. 22 and 22, among the samples of the present invention, sample No. 17 and No.
, 22, [) 1IlaX increase and Qc,
It can be seen that the reduction effect is greater.

As described above, only when the cyan coupler of the present invention and the halogen-containing compound of the present invention are used, a high maximum density, which is the object of the present invention, can be obtained, good dye image storage stability, and color reproducibility are achieved. It can be seen that a silver halide photographic material with excellent properties can be obtained.

Example 2 The blue-sensitive silver halide emulsion of layer 1 of the silver halide color photographic light-sensitive material prepared in Example 1 was used as El-4 in Table 1.
The green-sensitive silver halide emulsion of Layer 3 was added to Em- in Table 1.
5, the red-sensitive silver halide emulsion of [15] was added to E of Table 1.
Silver halide color photographic light-sensitive material sample No. 1 was prepared in the same manner as in Example 1, except that the cyan coupler shown in Table 3, the halogen-containing compound of the present invention, and the high-boiling organic solvent were used in place of 115 and e-6 respectively. , 23-44 were prepared.

The obtained sample was passed through a photosensitive needle KS-7 type (manufactured by Konishiroku Photo Industry).
After wedge exposure using the following color development process, the same measurements as in Example 1 were carried out.

The results are shown in Table-3.

[Processing process] Color development ring f113 minutes 30 seconds Temperature 33℃ bleach fixing
1 minute 30 seconds Temperature: 33°C Water washing 3 minutes Temperature: 33°C Color developer formulation N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7 Minoaniline sulfur Jll salt 4,9Q hydroxylamine sulfate 2 .0g Potassium carbonate 25.0g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Benzyl alcohol
131g polyethylene glycol (average degree of polymerization 400) 3.01
Add J water to bring the pH to 11, and adjust the pH to 10 with sodium hydroxide.
Adjust to 0.

Bleach-fix solution formulation Ethylenediaminetetraacetic acid sodium salt 6.0g Ammonium thiosulfate 1009 Sodium bisulfite 10 Q Sodium metabisulfite 3g Add water to make 11, and adjust to pH 7.0 with aqueous ammonia.

As is clear from the results in Table 3, in this example as well, in the samples of the present invention, □ wax was sufficient^, and λ1
IlaX has a long wavelength, and both DCT and DB are small, and the reproducibility of green and blue colors is excellent. Furthermore, the dark fading resistance is greatly improved.

By the way, in this example, a developer containing benzyl alcohol as a color development accelerator, which is commonly used in the past, was used as a color developer.

From the results of this example, it can be seen that the present invention has sufficient effects even in such a system.

Example 3 To 6 g of cyan coupler shown in Table 4, a halogen-containing compound of the present invention or tricresyl phosphate (T
CP) 3 (l) was added, dibdelphthalate (3q) was added to the colander, and ethyl acetate (18) was added to the colander.
After heating and dissolving at ℃, this was mixed with 10 G 11 of a 5% aqueous gelatin solution containing alkanol sulfonate d, and emulsified and dispersed using an ultrasonic dispersion machine to prepare a ml dispersion.

Next, the above dispersion was added to a silver iodobromide emulsion (containing 6 mol% silver iodide) so that the cyan coupler was 10 mol% based on silver, and 1,2-bis( After adding vinylsulfonyl)ethane at a rate of 12 mg/g of gelatin, a coated silver weight of 1 8 II! II/100c
It was applied so that it became f. Each of the silver halide photographic materials thus obtained was subjected to wedge exposure in a conventional manner and then subjected to the following development treatment.

[Processing process] Processing process (38℃) Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds fixed
Arrive 6 minutes 30
Second wash
3 minutes 1 5 seconds stabilization 1 minute 30
The composition of the treatment liquid used in the second treatment step is as follows.

[Color developer composition] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 475g Anhydrous sodium sulfite 4.251) Hydroxyamine 1/2 sulfate 2.0 ( J Anhydrous Potassium Carbonate 37.59 Sodium Bromide
1.3g nitrilotriacetic acid trisodium ram salt (monohydrate) 2.5 (potassium monohydroxide 1.O Q Add water to make 1ffi, use potassium hydroxide to make 1) Hlo.
Adjust to O.

[Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10 1J ammonium bromide 150g Glacial acetic acid
Add 10112 water to make 12 and adjust to pal 6.0 using ammonia water.

[Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162i1
2 Anhydrous sodium sulfite 12.4 0 Add water to make 12, and adjust to pH 6.5 using acetic acid.

[Stabilizing liquid composition] Formalin (37% aqueous solution> 5.OmQ
Conidax (Konishi Roku Photo Industry Co., Ltd. MA>) Add 7.5d water to make 1i.

The maximum absorption wavelength at the density (D) of the cyan dye image of the silver halide photographic material thus obtained is 1.0 (
λwax ) (ni), and the maximum density Dllax of the cyan dye image were measured.

The results are shown in Table 4.

As is clear from the results in Table 4, even when a phenolic cyan coupler having a ureido group is used as the cyan coupler of the present invention, comparative sample NO. .54 and 56, samples Nos. 46-49, 51, 53.55 and 57 of the present invention containing the halogen-containing compound of the present invention all have a high maximum concentration (Qa+ax) and a maximum absorption wavelength (λWaX) is shifted to the longer wavelength side, indicating that the silver halide photographic material has an absorption wavelength suitable for use as a negative photographic material and has improved color reproducibility.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a cyan coupler represented by the following general formula [I]. and at least one halogen-containing compound, which is a compound containing a bromine atom and/or an iodine atom, and the combined content of bromine atoms and iodine atoms in the compound is 40% or more by weight. A silver halide photographic material comprising: General Formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 each represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R_3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. However, R_2 and R_3 may jointly form a ring. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. m represents 0 or 1. ]