JPS63106657A - Silver halide photographic sensitive material having superior color reproducibility - Google Patents

Abstract

PURPOSE:To make the maximum absorption wavelength of a cyan dye image longer in the red spectral region and to improve the color reproducibility by incorporating a specified cyan coupler and a specified compd. contg. fluorine into a silver halide emulsion layer. CONSTITUTION:At lest one kind of cyan coupler represented by formula I and at least one kind of compd. contg. >=20wt% fluorine are incorporated into at least one of silver halide emulsion layers. In the formula I, each of R1 and R2 is alkyl, cycloalkyl, alkenyl, aryl or a heterocyclic group, R3 is hydrogen, halogen atom, alkyl or alkoxy group, X is hydrogen atom or a group releasable by a reaction with the oxidized product of a color developing agent and m=0 or 1. The shelf stability and color reproducibility of a formed cyan dye image are improved.

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 a high maximum 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 color developing solutions. 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 there was no.

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. 5B-33251, No. 5B-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 that can improve color reproducibility by improving the color reproducibility1 and that 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-mentioned object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support. This is achieved by a silver halide photographic material containing at least one cyan coupler represented by formula [11] and at least one fluorine-containing compound having a fluorine content of 20% or more by weight.

General formula [I] × [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 hydrogen 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 that can be separated by reaction with an oxidized product of a color developing agent. Kaku 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.

Furthermore, 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 monomer of the color developing agent represented by X in general formula [I] include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, and sulfonylamino groups. group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group, but preferably a halogen atom, an aryloxy group,
It is an alkoxy group.

Among the cyan couplers of the present invention, those represented by the following general formula [IA] are particularly preferred.

General Formula [IA] 8^ In the formula, RAl 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. RAZ has the same meaning as R2 in the above general formula [I]. xA represents a halogen atom, an acyloxy 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.
No. 33 Akira! Book II, pages 26-35, JP-A-60-22
No. 5155, page 7, lower left column a1 to page 10, lower right column, JP-A-60-222853, page 6, upper-left column to page 8, lower-right column, and JP-A-59-185335, page 6 2,5-diacylamino cyan couplers and JP-A-13-13ctO3 described in the lower left column to the upper left column on page 9
Contains a phenolic cyan coupler having a ureido group at the 2-position described in the upper right column of page 8 of Publication No. 1 to the upper right column of page 11, and is synthesized according to the methods described in Mei 18 and the gazette. be able to.

The cyan coupler of the present invention is usually used in a silver halide emulsion layer, especially a red-sensitive emulsion layer, and the amount added is 2X'l0-3 to 8x10-1 mol, preferably lX10-2 per mol of silver halide. ~5X10'' moles.

Next, a fluorine-containing compound having a fluorine content of 20% or more (hereinafter referred to as the fluorine-containing compound of the present invention) used in combination with the cyan coupler of the present invention will be described.

In this specification, the fluorine content is the weight ratio of fluorine atoms in a molecule, and is defined as follows.

The fluorine-containing compound of the present invention has a fluorine content of 20
% or more, preferably 30% to 80%
It is a compound of

The fluorine atom contained in the fluorine-containing compound of the present invention is bonded to a carbon atom, and the fluorine-containing compound of the present invention may be an aliphatic compound or an aromatic compound.

Further, the fluorine-containing compound of the present invention may contain, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a chlorine atom, a bromine atom, an iodine atom, etc. in addition to a fluorine atom, a carbon atom, and a hydrogen atom. , and any functional groups and moieties of functional groups formed by these ° atoms (e.g. -
〇-1-CD-1-coo-1-0H1-COOH,-
C.N.

-.S-1-so-1-8O2-1-N' The fluorine-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 fluorine-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 fluorine-containing compound of the present invention is 8 to 5.
Preferably, it is 0.

Further, the molecule m of the fluorine-containing compound of the present invention is 150 to
15. Preferably it is Goo.

In addition, the fluorine-containing compound of the present invention is a compound capable of forming a pigment, that is, an active methylene compound, an active methine compound,
It is preferable that the compound is not a compound obtained from a cyan coupler residue in which the rose position of the phenol nucleus is active.

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

F''''6H(CF2CF2hCOO(CHI)tcH
.

F-8F(CF・)・COO(CH2)+ + CH2
”' H(CF2CF2)zcHio(CHt)*C
ooCH.

F-”H(CF2CF2)2COOCH,CFIC
F, H"" CH, C00CH, CF, CF, HCH
, C○OCH, CF, CF, H to F13 F-29) I CF * CF tCHzO(CHt)
aCNF-3' HO (CHI) 10CH, (CF
*CF, ), HF-328 (CF ICF *)sCH
zOCO(CH*)t-P-(OC*Hs)*F-3
3(.-04F, +r-N F-42F-43 F-48F-49 F-52Br(CHt)sCOOCH*(CF*)*
FF-54F-55 F-56F-57 (CF zc F C1-)n [Product name Nigeia 0
#1; Commercial product from Daikin Industries, Ltd.] (-CF ICF CI-)n [Product name Nigeia 0
Commercial product 1 (-CFi)n from Daikin Industries, Ltd. 4: Commercial product 1F-63 from Daikin Industries, Ltd. CF>S O2N 8 minutes C00CH, CF*CF2HF
” CF, C00CH, CH, CH, 0COCF.

″□ Among the fluorine-containing compounds used in the present invention, particularly preferable ones have a fluorine content of 20% or more and are represented by the following general formulas [I[] to [VI].

General formula [I[] R4-Co-Rs General formula [1 [[] % formula % General formula [rV] General formula [V] General formula [Vl] R14-8O2-R+5 In the formula, R ~ Rs * R11 , R+21 R1 and Rls each represent an alkyl group or an aryl group, and Rho and R13 each represent a hydrogen atom, an alkyl group, or an aryl group. However, the general formula [I[
], in at least one of R4 and R5, in general formula [1[], at least one of R6 and R7, and in general formula [IV], Ra, Rs, and Rt
o (both are rG; tR of general formula [v])
+1. A fluorine atom is contained in at least one of R12 and R13, and in at least one of R14 and R+s in the general formula [W].

The alkyl groups and aryl groups represented by R4 to R1s further include those having substituents other than fluorine atoms.

The fluorine-containing compound of the present invention is disclosed in JP-A-53-14662.
It includes the exemplified compounds listed in the columns from the upper right column of page 4 of Publication No. 2 to the lower left column of page 5, and can be synthesized by conventionally known methods such as the methods described.

The amount of the fluorine-containing compound of the present invention to be used is preferably 5 to 800 mol%, more preferably 20 to 500 mol%, based on the coupler represented by the general formula [I] of the present invention.

Some of the fluorine-containing compounds of the present invention are disclosed in JP-A-53-146
No. 622, Japanese Patent Application No. 61-48041, No. 61-507
It is also described in Meimii and publications such as No. 45 and No. 61-121476.

However, the above-mentioned documents do not suggest that the fluorine-containing compounds of the present invention improve color reproducibility by shifting the maximum absorption wavelength of the cyan dye to the longer wavelength side.

That is, as a result of intensive research, the present inventors have found that the fluorine-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, and as a result, color reproducibility is significantly improved. It has been found that this effect can be improved by the present invention for the first time.

The fluorine-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 layer, 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 fluorine-containing compound of the present invention are combined, if necessary, with a high boiling point organic solvent, and further with a low boiling point and/or water-soluble organic solvent, if necessary. It is preferable to simultaneously dissolve it, 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 fluorine-containing compound of the present invention itself may be used as the high-boiling organic solvent.

Examples of high-boiling organic solvents that may be used as necessary include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, trimesic esters, etc. An organic solvent having a boiling point of 150° C. or higher is preferable.

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 pyrazoloazole 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 I in the general formula [I] is 0, a preferred cyan coupler that can be used in combination is a cyan coupler represented by the following general formula [F]. An example of this is Kabuu.

General formula [F] ZIF In the formula, PIF represents a ballast group. R2F represents a hydrogen atom, a halogen atom, or an alkyl group.

R3F 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. 50-112038, No. 50-11742
No. 2, No. 5G-130441, U.S. Patent No. 2,369
, No. 929, No. 2,423,730, No. 2,434.
No. 272, No. 2,474,293, No. 2.698
．． No. 794, U.S. Pat.
No. 5-163537, U.S. Patent No. 3.772,002
No. 4,443,536, etc.

Further, in the case of the cyan coupler of the present invention in which m 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. .

The silver halide used in the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodide.

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, sulfur sensitizers, selenium sensitizers, reduction sensitizers, noble metal sensitizers, and the like.

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 material of the present invention includes a color antifoggant, an image 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, and surfactants can be used as desired.

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.

[Effects of the Invention] The silver halide photographic material of the present invention contains the cyan coupler of the present invention and the fluorine-containing compound of the present invention, so that the cyan dye image formed has good storage stability.
In addition, since the maximum absorption wavelength of the cyan dye was shifted to the longer wavelength side, color reproducibility was 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 a neutral method and a simultaneous mixing method.

Table-1 Ning 1 2++1 per mole of silver halide [1 addition*2
Addition of 5X10-5 mol per mol of silver halide 3 Addition of 0.9 mmol per mol of silver halide *4 Addition of 0.1 mmol per mol of silver halide 5 0.2 mmol per mol of silver halide Each added silver halide emulsion was treated with 5TB-1 shown below as an emulsion stabilizer after completion of chemical sensitization per mole of silver halide at 5X10.
'Mole added.

(SD-1) [S-ray 3] (Preparation of silver halide color photographic light-sensitive material sample) Next, the following layers 1 to 7 were sequentially coated (simultaneously coated) on a paper support whose both sides were coated with polyethylene. Silver halide color photographic materials 1 to 31 were produced. (In the following examples, the amount added is shown per 1f of photosensitive material.) Layer 1: Gelatin (1, 2a) and 0.29 (J
Blue-sensitive silver halide emulsion (E+-1) of (in terms of silver, same hereinafter) and TO, 750+7) l'Erocuff 7-(Y-1>, 0.39 light stabilizer 5T-1 and 0.
015 (l of 2,5-dioctylhydroquinone (HQ)
-1> dissolved in 0.3 g of dinonyl phthalate (DN
A layer containing P).

Layer 2...Gelatin (0.9o) and 0.04(
A layer containing 0.20 DOP (dioctyl phthalate) dissolved in 1 HQ-1.

H3...Gelatin (1,4CI') and 0.2
Green-sensitive silver halide emulsion (Elm-2) of g and o, s
og magenta coupler (M-1), 0.25! I+ light stabilizer 5T-2 and 0.01 g HQ-1 dissolved in 0.3 g DOP and 6 ip of the following filter dye Al
A layer containing -1.

Layer 4...Gelatin (1,2 (J) and the following 0
．． 6g of ultraviolet absorber UV-I and 0°05g of HQ-
A layer containing 0.3 g of DNP dissolved in 1.

Layer 5: Contains gelatin (1.4 g) and 0.200 g of red-sensitive silver halide emulsion (Elm-3), containing a cyan coupler, a fluorine-containing compound, and a high-boiling organic compound shown in Table 2. Solvent additionally 0.3 g of 5T-1 and o, o
A layer containing HQ-1 of ig.

Layer 6...Gelatin (1.1g) and 0.29L
0, 20 DOP and 5+no dissolved JV-1
A layer containing the following filter dye Al-2.

117... Gelatin (1,0!I+) and 0.
Layer containing sodium 2,4-dichloro o-6-hydroxytriazine of 05Q.

(S T -1) (S T -2) I-1 l-2 Na()38CH2NH00H (Y-1) ('J CsH+7('J 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 ( Dmax) was measured.

In addition, the maximum absorption wavelength λWaX when the degree of the cyan dye image is 1.0, and the density, DB, and Dq at 420 na+ and 550 nm 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 Development color development 34.7±0.3℃ 45 seconds Bleach fixing 34.7±0.5℃ 50 seconds stabilization
Dry at 30-34℃ for 90 seconds 60
~80℃ 60 seconds [Color developer] Pure water
aOO mosquito triethanolamine
89N,N-diethylhydroxyamine 5g Potassium chloride 2gN-ethyl-N
-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
30 potassium sulfite
0.2 (J optical brightener (4,4'-diaminostilbendisulfone 101 conductor) 1 (1
Add pure water to bring the total volume to 12, and adjust to p) 110.2.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100d Ammonium sulfite (40% solution) 27.5% Adjust to pH 5.7 with potassium carbonate or glacial acetic acid Adjust and add water to bring the total volume to 11.

[Stabilizing liquid] 5-chloro-2-methyl-4-inthiazolin-3-one 1g 1-hydroxyethylidene-1゜1-diphosphonic acid 2g was added to make 12, and the mixture was diluted with sulfuric acid or potassium hydroxide to p)I. 7.
Adjust to 0.

CG-1 CJ C-2 Comparative Compound I As can be seen from the results in Table 2, a conventionally used cyan coupler (CG-1) having a methyl group at the 5-position of the phenol nucleus was used. Sample No. 1 has the highest concentration (
Sample N containing the fluorine-containing compound of the present invention has a high Qmax), a long maximum absorption wavelength (λ-aX), and a small D(), but the dark fading property is very poor and it is not practical.
Although improvement in dark fading property was observed in samples o and 2, it was still insufficient. In addition, samples No. 11 and No. 12 both have large DB and poor blue reproducibility. Samples N053 and N014 using a cyan coupler (CG-2) having an ethyl group at the 5-position of the phenol nucleus have improved dark fading properties, but still have a large 9 and poor blue reproducibility. Sample No. 5 using only the cyan coupler of the present invention. No.

No. 7, No. 9, and No. 11 have very good dark fading properties, but in all of them, λll1ax is a short wave and D? Because the values of and are large, sufficient green color reproduction cannot be achieved. In addition, samples No. 13 and No. 15, in which the cyan coupler of the present invention and the cyan coupler outside the present invention were used in combination, also had a short wavelength λlaX, and although the DQ was slightly smaller, it was still insufficient. In contrast, sample No. of the present invention using the cyan coupler of the present invention and the fluorine-containing compound of the present invention,
6. No, 8. No. 10 and No. 12 are the corresponding sample No. 5 which does not contain a fluorine-containing compound, respectively. N
o, 7. Comparing with No. 9- and No. 11, [
) D(
is small, and a significant improvement in green reproducibility is observed. 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 DB. Samples No. 0.14 and No. 1 of the present invention in which a cyan coupler other than the present invention was used in combination with the cyan coupler of the present invention, and a fluorine-containing compound of the present invention was used.

16 has Q max when compared with the corresponding samples No. 13 and No. 15 that do not contain fluorine-containing compounds, respectively.
is high, λWaX has a longer wavelength, D6r is small, and a significant improvement in green reproducibility is recognized.

It can be seen that the dark fading property is also better than that of sample No. 013 and is satisfactory. Moreover, even when compared with sample No. 6 using the same fluorine-containing compound, 0 + nax
An increase in

Next, sample No. 5 using the same cyan coupler (C-2) of the present invention. No, 6. No, 17~No.

Comparing No. 24, Sample No. 17 using comparative compound crab (fluorine content 14.7%) is D■aX with respect to sample No. 015 which does not contain the fluorine-containing compound of the present invention.
However, as the wavelength of λWaX becomes longer and
The decrease was only slightly observed and was insufficient. On the other hand, sample No. 21 using the fluorine-containing compound (F-5) of the present invention with a fluorine content of 22.2% has a higher [ ) WaX and λlaX compared to sample No. 5. It can be seen that the wavelength is longer and the D x is smaller, and the effect of improving both color development and color reproducibility is large. Furthermore, Sample No. 6 using the fluorine-containing compound of the present invention having a fluorine content of 30% or more; No, 18. No, 22~N0
．． Further, it can be seen that in No. 24, λaiax is a long wavelength, the DCT is small, and the green reproducibility is significantly improved.

In addition, Sample No. 20, which used only the fluorine-containing compound of the present invention as a high-boiling organic solvent, and Sample No. 0.19, which had a different usage ratio with DOP, had similar effects of improving color development and green reproducibility. confirmed.

In addition, sample N was prepared using a cyan coupler of the present invention, a cyan coupler other than the present invention, and a fluorine-containing compound of the present invention.
0.25 to No. 31, the same sample N as described above was also used.
The same effect as 0.14 was observed.

As described above, only when the cyan coupler of the present invention and the fluorine-containing compound of the present invention are used, a high maximum density, which is the object of the present invention, can be obtained, and good dye image storage stability is obtained.
Moreover, it can be seen that a silver halide photographic material with excellent color reproducibility 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 Ell of Table 1.
-4, the green-sensitive silver halide emulsion of layer 3 was added to E of Table-1.
In lm-5, the red-sensitive silver halide emulsion of layer 5 is shown in Table-1.
Silver halide color photographic light-sensitive material sample No. 32 was prepared in the same manner as in Example 1 except that the cyan coupler shown in Table 3 and the non-color-forming compound of the present invention were used in layer 5 in place of El-6. ~54 were produced.

The obtained sample was passed through a photosensitive needle KS-7 type (manufactured by Konishi Rokushatsu Kogyo).
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 3 minutes 30 seconds Bleach fixing at 33℃
1 minute 30 seconds Temperature: 33℃ Water Washing 3 minutes Temperature: 33℃ Color developer formulation N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfur M salt 4.9g Hydroxylamine sulfate 2 .0g Potassium Carbonate 25.017 Sodium Bromide
0.69 anhydrous sodium sulfite
2.0g benzyl alcohol
131g polyethylene glycol (average degree of polymerization 400) 3-0. (
1 Add water to make 12, and add sodium hydroxide to DI-11.
Adjust to 0,0.

Bleach-fix solution formulation Ethylenediaminetetraacetic acid sodium salt 6.0 g Ammonium thiosulfate 100 g Sodium bisulfite io g Sodium metabisulfite 3 g Add water to make 12, adjust to p)l 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 is sufficiently high, and λ
WaX has a long wavelength, and both Dcr and DB have fine reproducibility of green and blue. Also, the chanting color has been 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 the cyan coupler shown in Table 4, the fluorine-containing compound of the present invention or tricresyl phosphate (TC
P) A mixed solution of 3Q, 3 g of dibutyl phthalate, and 18 g of ethyl acetate was heated to 60°C to dissolve it, and this was mixed with 10 G of a 5% aqueous gelatin solution containing alkanol root. The mixture was emulsified and dispersed using a sonic disperser to prepare a dispersion liquid.

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( 12m of vinylsulfonyl)ethane per gram of gelatin! After addition at a ratio of 7 to 1, the coated silver m was 1 8 1110/100c onto a subbed transparent cellulose triacetate film support.
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 1 5 Arrive at sand room 6 minutes 30 seconds wash
3 minutes 1 5 seconds stabilization
The composition of the treatment liquid used in the 1 minute 30 second treatment step is as follows.

[Color developer composition] 4-amino-3-methyl-N-ethyl-N-(β- and droxyethyl)-aniline VAm salt 4. 751J
Anhydrous sodium sulfite 4. 250 and droxyamine 1/2 sulfate 2.0g anhydrous 15H
l! Potassium 37.5 1; 1 Sodium Bromide 1.3g Nitrilotrivinegar! ! 3 Natrirum salt (monohydrate salt) 2.59 Potassium hydroxide 1.0 g Water was added to adjust to 11, and the pH was adjusted to 11 using potassium hydroxide. Adjust to o.

[Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10 Q ammonium bromide 150 Q glacial acetic acid
Add 1011 water to make it 11, and use ammonia water to adjust to 1))-1 6.0.

[Fixer composition] Ammonium thiosulfate (50% aqueous solution) 1 62. β
Anhydrous sodium sulfite 12.4 (] Add water to make 111 and adjust to pH 6.5 using acetic acid.

[Stabilizing liquid composition] Formalin (37% aqueous solution) 5. OiN
Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5te water to make 11.

The maximum absorption wavelength at the density (D) of the cyan dye image of the silver halide photographic material thus obtained is 1.0 (
λmax ) (nm) and the maximum density Q max 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. 55° which does not contain the fluorine-containing compound of the present invention 60.62.64 and 66, whereas samples No. 56 to 59.61.63.65 and 6 of the present invention containing fluorine-containing compounds of the present invention
No. 7 has a high maximum density (Dmax), a maximum absorption wavelength (λWaX) shifted to the long wavelength side, and has an absorption wavelength suitable for a negative photosensitive material for photography, and is a halogenated material with improved color reproducibility. It can be seen that it is a silver photographic material.

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 fluorine-containing compound having a fluorine content of 20% or more by weight. 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. ]