JPH0715562B2 - Silver halide color photosensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having significantly improved sharpness.

[Prior art]

In recent years, the image quality of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials) has been remarkably improved, but the sharpness is still insufficient. Particularly, in stretch printing from a small format of negative type color film (110 film, disc film, etc.), poor image sharpness as well as image roughness (granularity) significantly lowers the level of print image quality. This is because the sharpness of the negative type film has not reached the point where it can withstand high-magnification printing.

Conventionally, various techniques for improving the sharpness are known. One is a light scattering prevention technique, and the other is an edge effect improving technique.

The latter technique includes a method using a so-called DIR coupler and a method using an unsharp mask. In this
The method using the unsharp mask has a practical limit because it may cause deterioration of sensitivity and deterioration of graininess. There are many known methods using DIR couplers, and useful DIR
As a coupler, Japanese Examined Patent Publication No. 55-34933, JP-A-57-93344
U.S. Patents 3,227,554, 3,615,506, 3,617,29
There are compounds described in No. 1 and No. 3,701,783. However, when using the DIR coupler to enhance the edge effect, MTF (modulation transfer fun
ction = modulation transfer function) is improved, but MTF improvement in the high frequency region required for high magnification cannot be expected, and there are undesirable side effects such as reduced sensitivity and reduced concentration. By using a DIR coupler that exerts a so-called long-distance action effect such as diffusive DIR and timing DIR, the decrease in sensitivity and density can be reduced, but the MTF improvement area shifts further to the low frequency side and at high magnification ratios. We cannot expect much improvement in sharpness.

On the other hand, as a technique for preventing light scattering, a coloring substance addition method, reduction of silver halide amount, thinning, and the like are known.
A drastic reduction in the amount of coated silver leads to deterioration in graininess because the number of coloring points is reduced. In addition, although there are reductions in gelatin, couplers, coupler solvents, etc. in the coating liquid, all of them have limitations such as deterioration of coating property and reduction of color density.

Attempts to increase the sharpness by suppressing the light scattering by adding the former coloring substance have been made for a long time, and the following methods can be mentioned.

(A) Antihalation Layer This layer is always provided on the emulsion layer side away from the exposure source, between the emulsion and the film base or on the back side of the film base. The purpose of this layer is to allow light reflected at an optical interface, such as a gelatin-support or support-air, to penetrate downward through the emulsion layer to avoid blurring by so-called "reflection halation". Absorb completely. An example is in West German Patent Publication No. 2,711,220. Therefore, the ideal color for this layer is black. That is, this layer should have a strong uniform absorption over the entire visible spectral range as much as possible.

(B) Dyeing of Emulsion Layer A film dye is added directly to the emulsion in order to absorb the light scattered by the silver halide crystals and prevent the so-called "scattering halation" from occurring. The dyeing is commensurate with the sensitivity of the respective layers and causes a considerable loss of sensitivity and gradation.

(C) Filter intermediate layer This layer is useful for improving color reproduction as well as sharpness.

Seen from the exposure source, this layer is always below the layer whose sharpness is to be improved, so that it acts as a layer to prevent reflection halation in the sense of (a) and also the halogen of the emulsion layer below it. It acts as a protective layer against the light scattered back by the silver halide crystals, thereby contributing to halation reduction due to scattering. At the same time, this layer improves the color reproduction of the underlying emulsion layer by preventing unwanted exposure in the spectral regions outside the sensitive region provided for recording information. The filter interlayer therefore has to absorb as much light as possible in this region of disturbing side sensitivity, but--from the exposure source--the spectral region in which the highest sensitivity lies farther than the filter layer. Do not absorb the light of.

An important example is the yellow filter layer of a color light-sensitive material that corrects the unwanted blue sensitivity of emulsion layers sensitized for green or red light.

With the above-described technique of using dyes, the effect of improving sharpness is insufficient, and they are actually used only as an antihalation layer. In addition, it is the current situation that the above-mentioned MTF value in the high frequency region cannot be improved until it is practically used.

Therefore, it is required to develop a technique for improving the MTF value not only in the low frequency region but also in the high frequency region by appropriately using the dye and the developing effect.

[Object of the Invention]

An object of the present invention is to provide a color light-sensitive material having sharply improved sharpness, especially MT in a high frequency region so as to withstand stretching at a high magnification.
It is to provide a negative type color film in which F is improved.

[Structure of Invention]

In order to achieve the above object, the inventors of the present invention have earnestly studied the use of the edge effect in a multilayer color light-sensitive material and the technology of preventing light scattering by a dye, and as a result, released a leaving group by reacting with an oxidation product of a developing agent. And, the released different or the same leaving group contains a compound whose development inhibitory action, fogging action or development accelerating action can be changed by intermolecular reaction (hereinafter abbreviated as the compound of the present invention), and A silver halide color light-sensitive material characterized by containing a non-diffusible green or red light absorbing dye in the non-light-sensitive layer,
We have found that our goals are effectively achieved.

The effect of the present invention is clarified in the examples described below, but as the type of the compound of the present invention, the compound represented by the general formula (I
I) to (IV) are preferable, and (II) is particularly preferable. Further, the non-diffusible dye is preferably added to the non-photosensitive layer on the light source side of the silver halide emulsion layer having the same color sensitivity as the light mainly absorbed by the dye, from the viewpoint of the effect. Further, as the non-diffusible dye, an oil-soluble dye is preferable from the viewpoint of coating performance.

The compound of the present invention is preferably represented by the following general formula (I).

General formula (I) A- (TIME) _n -Y In the formula, A reacts with an oxidized product of a developing agent, and then (TIME) _n-
Represents a component capable of releasing Y, n is 0 or 1, and when n = 1, TIME is TIME-Y
And Y represents an organic residue having the property of reacting with each other after leaving to lose or produce a photographic effect.

In general formula (I), A is a coupler residue or a hydroquinone residue, preferably a coupler residue. Examples of coupler residues include, for example, yellow couplers, U.S. Pat.Nos. 2,298,443, 2,407,210, and 2,
875,057, 3,048,194, 3,265,506, and
No. 3,447,928 and {Farbkupplereine Literaturubersieht "Agfa Mitteilu
ng (BandII)} 112-126 pages (1961) and the like, benzoylacetanilide type yellow couplers, bivaloylacetanilide type yellow couplers, malonic acid diester type yellow couplers, malonic acid diamide type yellow couplers or malonic acid ester monoamides. Various yellow couplers such as type yellow couplers can be used. Further, regarding magenta couplers, U.S. Patent Nos. 2,369,489, 2,343,703, and 2,311,08
No. 2, No. 2,600,788, No. 2,908,573, No. 3,062,6
No. 53, No. 3,152,896, No. 3,519,429 and the above {Agfa Mitteungun (Band II)} Agfa Mitteilun
g (BandII)} 126 to 156 (1961), etc., pyrazolone-based magenta couplers, indazolone-based magenta couplers, pyrazolobenzimidazole-based magenta couplers, pyrazolotriazole-based magenta couplers, cyanoacetophenone-based magenta couplers, etc. Various magenta couplers can be used.

Further in the case of cyan couplers, U.S. Pat.No. 2,367,53
No. 1, No. 2,423,730, No. 2,474,293, No. 2,772,1
No. 62, No. 2,895,826, No. 3,002,836, No. 3,034,
No. 892, No. 3,041,236 and the above-mentioned Agfa Mitteilung (Band II) 156-
The naphthol-based or phenol-based couplers described on page 175 (1961) can be used.

In addition to these couplers, the black dye-forming coupler described in West German Patent Publication No. 2,644,914 can also be used.

On the other hand, a compound that reacts with an oxidized product of a color developing agent represented by a cyclic carbonyl compound but does not form a color developing dye can also be used as the coupling component according to the present invention. 3,
No. 632,354, No. 3,928,041, No. 3,958,993, No. 3
No. 3,961,959 and British Patent No. 861,138.

In the general formula (I), TIME is used for the purpose of controlling the coupling rate or controlling the diffusivity of Y, and is a molecule described in, for example, US Pat. No. 4,248,962 and JP-A-57-56837. Release of a development inhibitor by an internal nucleophilic substitution reaction, JP-A-56-114,946, 57-15
4,234, 57-188,035, 58-98,728, 58-160,9
54, 58-162,949, 58-209,736, 58-209,737
Issue 58-209,738, Issue 58-209,738, Issue 58-209,739
JP-A-57-111,536, JP-A-60-203,943, and JP-A-60-21, which release a group having a development inhibitory action by electron transfer along a conjugated chain as described in JP-A-58-209,740 and the like.
A coupling component capable of releasing a development inhibitor by a coupling reaction with an oxidized product of a developing agent as described in JP-A No. 3,944 and others
No., No. 53-29,717, No. 60-7,429, No. 60-185,950,
60-214,358, 60-218,645, 60-225,156,
60-225,844, 60-229,030, 60-230,139, 60
-249,148, 60-249,149, etc. can be mentioned.

In the general formula (I), Y is a photographically useful group, a precursor thereof, or a simple leaving group, which can react intermolecularly after leaving. As such a reaction, a nucleophilic substitution reaction, a nucleophilic addition reaction, a coupling reaction, a redox reaction and the like can be mainly mentioned.

The photographically useful group represented by Y and its precursor are preferably represented by the following general formulas (B-1), (B-II) and (B-II).
I), (B-IV), (B-V), (B-VI), (B-VI)
It is represented by I) and (B-VIII).

_{L 1 -G 3 -N = V 8} -G 9 (B-VII) In the formula, V ₁ , V ₂ and V ₃ each represent N or C-G ₃ , V ₄ represents N-G ₃ , S or O, and V ₅ represents O or N.
Represents -G _3, V ₆ represents O or N-G _12, V ₈ is N
Or C-G ₁₃ , G ₁ represents a substituent, G ₂ represents a hydroxy group or a substituted or unsubstituted amino group,
G ₃ represents a hydrogen atom, an aryl group or an aliphatic group, and G ₄
Represents an aryl group, G ₅ represents a hydrogen atom, or a component capable of coupling with an oxidized product of a developing agent after being released from L ₁ , and G ₆ represents an alkoxy group, an arylamino group, an acylamino group, an aryl group, an aliphatic group. Represents a group or a heterocyclic group, G ₇ represents an aryl group, an aliphatic group or a heterocyclic group, G ₈ represents a simple bond or an atomic group connecting L ₁ and a nitrogen atom (aryl group, aliphatic group, heterocyclic group Group), G ₉ represents an aliphatic group, an aryl group or a heterocyclic group when V ₈ is a nitrogen atom, an acyl group, a carbamoyl group when V ₈ is C-G ₁₃ , sulfamoyl group, a nitro group, a cyano group, an alkoxycarbonyl group, an sulfinyl group or a sulfonyl group, G ₁₀ and G ₁₁ are each a hydrogen atom, an aryl group, an aliphatic group, an acyl group, a carbamoyl group, a sulfo Group, a sulfamoyl group, an alkoxycarbonyl group or a sulfinyl group, G
₁₂ represents an aliphatic group, an aryl group, a heterocyclic group or an amino group, and when V ₆ is N-G ₁₂ , G ₁₂ can associate with G ₇ to form a ring. G ₁₃ represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a sulfamoyl group, a nitro group, a cyano group, an alkoxycarbonyl group, a sulfonyl group or a sulfinyl group, and G ₁₃ represents G ₉ Can form a ring in association with. R ₁ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon, an N-arylureido group, an acylamino group, —O—R ₂ or —S—R ₂ (wherein
R ₂ represents an aliphatic hydrocarbon group), l represents an integer of 1 to 4, f represents an integer of 0 to 4, and g and h represent integers of 1 to 3.

The simple leaving group represented by Y is preferably represented by the following general formulas (B-IX) and (BX).

L ₁ -V ₉ -Z ₂ (BX) In the formula, Z ₁ represents a group of non-metal atoms forming a hetero ring together with a nitrogen atom, and V ₉ represents an oxygen atom, a sulfur atom, a selenium atom or a hydrogen atom. Represents a substituted nitrogen atom, a substituted nitrogen atom, a methylene group, or a substituted methine group,
Z ₂ represents an organic residue.

The compound represented by the general formula (I) is more preferably the following general formulas (II-1), (II-2), (III) and (IV-
1), (IV-2), (V-1) and (V-2). However, the compound of the general formula (II-1) and the general formula (II-
2) the compound of the general formula (IV-1) and the general formula (IV
-2), and the compound of the general formula (V-1) and the compound of the general formula (V-2) are used in combination.

General formula (II-1) A- (TIME) _n -Z-E General formula (II-2) A-Nu In the formula, A reacts with an oxidized product of a developing agent and then (TI
ME) -Z-E or a component capable of leaving Nu, and n represents 0 or 1, and when n is 1, TIME is TIME-ZE
Represents a component capable of releasing ZE after leaving from A,
Z represents a basic bone nucleus for exhibiting a development inhibitory effect, and E represents
After leaving Nu, it represents a component that reacts with Nu to cause a nucleophilic substitution reaction and leaves from Z, and Nu is a group that generates a nucleophilic group after leaving from A. By reacting with ZE, a development inhibitory action is obtained. Represents a group capable of forming Z-Nu. A in general formula (II-1) and A in general formula (II-2) may be the same or different.

In the general formula (II-1) and the general formula (II-2), A,
The groups represented by and TIME are the same as those described in formula (I).

The group represented by E in the general formula (II-1) is preferably a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group or an alkoxy group.

The basic mother nucleus of the development inhibitor represented by Z in formula (II-1) is preferably a nitrogen-containing unsaturated heterocycle or a monocyclic or condensed ring heterocyclic thio group. The nitrogen-containing unsaturated heterocyclic group is bonded to A- (TIME) n- with a nitrogen atom, and the heterocyclic thio group is bonded to A- (TIME) n- with a sulfur atom. These nitrogen-containing unsaturated heterocyclic and heterocyclic thio groups have one or more substituents and are preferably linked to E via one of the substituents.

The group represented by Nu in the general formula (II-2) is preferably a group containing an oxygen atom, a nitrogen atom or a sulfur atom, and bonded to A through it, and examples thereof include an alkoxy group, an aryloxy group and a benzotriazolyl group. Group, benzimidazolyl group, triazolyl group, imidazolyl group, imidazolidinyl group, pyrazolyl group, alkylthio group, arylthio group or heterocyclic thio group.

A in the formula _{(III) A- (TIME) n} -Z in ₁ -E ₁ formula, A, n, TIME, Z 1 and E ₁ each general formulas (I) and (II), n, TIME , Z, and E, and Z ₁ -E ₁ undergoes a bimolecular nucleophilic substitution reaction to form Z ₁ -Z ₁ -E ₁ exhibiting a development inhibiting action.

General formula (IV-1) A- (TIME) _n -Z ₂ General formula (IV-2) A L _2- E _{2 In the} formula, A, n and TIME are the same as those described in the general formula (I). Z ₂ represents a development inhibitor, L ₂ -E ₂ represents Z ₂
When represents a component capable of two molecules nucleophilic substitution reaction, L ₂ -E ₂ by a nucleophilic group capable of generating a breakaway Z is E ₂ attacked generates L ₂ -Z ₂ disengaged from the L ₂ . L ₂ -Z ₂ is substantially no development inhibiting effect.

The group represented by L ₂ in the general formula (IV-2) is a group which is removed from A by reacting with an oxidized product of a developing agent, and is preferably
L ₂ is a group containing an oxygen atom, a nitrogen atom, and a sulfur atom and linked to A through it, and examples thereof include an alkoxy group, an aryloxy group, a benzotriazolyl group, a benzimidazolyl group, a triazolyl group, an imidazolyl group, and an imidazolidinyl group. Represents a group, a pyrazolyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. These leaving groups have one or more substituents and are preferably linked to E ₂ via one of the substituents.

Formula (V-1) A- (TIME ) n -ED formula (V-2) in A-L ₃ -E ₃ formula, A, n, TIME, L 3 and E ₃ respectively general formula (I) , A in general and general formula (IV-2), n, TIME,
L ₂ and E represent the same groups as described above, ED contains in the molecule a moiety serving as a fogging agent or a development accelerator, and A or TI
It represents a group of the nucleophilic attack on L ₃ -E ₃ resulting anion in the molecule after withdrawal from the ME. The resulting L ₃ -ED does not have a substantially photo action.

In the general formula (V-1), E is preferably one derived from thiourea, hydrazine, 3-pyrazolidone, rhodanine, thioamide and the like.

Next, typical examples of the compounds represented by formulas (II-1) and (III) are shown.

Next, typical examples of the compound represented by formula (II-2) are shown.

Next, typical examples of the compound represented by formula (IV-1) are shown.

Next, typical examples of the compounds represented by formulas (IV-2) and (V-2) are shown.

Next, typical examples of the compound represented by formula (V-1) are shown.

Any of the compounds of the present invention can be synthesized by a known method. Many of the compounds contained in the general formula (II-2), the general formula (IV-1) and the general formula (V-1) are known compounds, for example, British Patent Nos. 2,099,167 and 2,096,7.
No. 83, No. 2,072,363, No. 2,097,140, U.S. Pat.
It can be synthesized by the synthetic route described in 7,554, 3,639,417 or 4,063,950. General formula (II
The compounds included in -1), general formula (III), general formula (IV-2) and general formula (V-2) can be synthesized by a synthetic route in which the respective moieties are sequentially linked as follows. A → A-
TIME->A-TIME-Z-> A-TIME-Z-E A->AL-> AL-E The amount of these compounds used may be in accordance with the usual DIR coupler. Preferably, it is 0.00 per mol of silver halide.
01 to 0.1 mol, more preferably 0.001 to 0.2 mol.

The non-diffusible green absorbing dye and the non-diffusing red absorbing dye in the present invention are the above-mentioned dyes added at the time of preparation of the non-photosensitive hydrophilic colloid layer in the production process of the color photosensitive material, and other layers after the production is completed. Any substance can be used as long as it is present in the non-photosensitive hydrophilic colloid layer without being diffused into the non-photosensitive hydrophilic colloid layer.

As an example of the non-diffusible dye, for example, a non-diffusible acid dye is used by allowing a diffusible acid dye and a polymer mordant having a basic group to coexist in the same non-photosensitive hydrophilic colloid layer. You can

Examples of the polymer mordant having a basic group include polymers containing imidazole, pyridine, alkylaminoalkyl (meth) acrylate, quaternary salts thereof, aminoguanidine and the like. The base polymer mordant used preferably is described in detail in each of the US patent specifications indicated by the following patent numbers. I.e., 2,548,564
No. 2,675,316, No. 2,882,156 and No. 3,706,563, among them, particularly preferred basic polymer mordant in the present invention is Patent No. 2,882,156, and
It is a condensation product of polyvinyl alkyl ketone or poly-N-oxoalkyl (meth) acrylamide and aminoguanidine described in U.S. Pat. No. 3,706,563.

Next, typical examples of the basic polymer mordant used in the present invention will be given.

[Mordant-1] [Mordant-2] [Mordant-3] [Mordant-4] The dye used in combination with the basic polymer mordant may be any acidic dye, but is preferably an acidic dye having a sulfo group or a carboxy group, for example, azo type, triphenylmethane type, Acid dyes such as anthraquinone type, styryl type, benzylidene type, merocyanine type and oxonol type dyes can be used.

Next, typical examples of the acid dye used in the present invention will be given.

[Dye-1] [Dye-2] [Dye-3] [Dye-4] [Dye-5] [Dye-6] [Dye-7] [Dye-8] [Dye-9] The above-mentioned acid dye and basic polymer mordant can be synthesized by a known method and incorporated into the non-photosensitive hydrophilic colloid layer by a known method.

Examples of non-diffusible green absorbing dyes preferably used in the present invention include reaction products of known magenta couplers and known color developing agents, and examples of non-diffusing red absorbing dyes preferably used. Is a reaction product of a known cyan coupler and a known color developing agent.

Specific examples of the above magenta couplers include pyrazolone-based, pyrazolotriazole-based, pyrazoliinobenzimidazole-based, and indazolone-based couplers. Examples of such magenta couplers include U.S. Pat.Nos. 2,600,788, 2,983,608, and 3,602,653.
No. 3, No. 3,127,269, No. 3,311,476, No. 3,419,39
1, No. 3,519,429, No. 3,558,319, No. 3,582,3
No. 22, No. 3,615,506, No. 3,834,908, No. 3,891,
445, West German patent 1,810,464, West German patent application (OLS) 2,4
08,665, 2,417,945, 2,418,959, 2,424,
467, Japanese Examined Patent Publication No. 40-6031, JP-A-49-74027, 49-740
No. 28, No. 49-129538, No. 50-60233, No. 50-159336,
51-20826, 51-26541, 52-42121, 52-589
No. 22, No. 53-55122, Japanese Patent Application No. 55-110943, and the like.

Furthermore, examples of the cyan coupler include phenol or naphthol derivatives, and examples of such a cyan coupler include, for example, U.S. Patents 2,423,730 and 2,4.
74,293, 2,801,171, 2,895,826, 3,
No. 476,563, No. 3,737,326, No. 3,758,308, No. 3
3,893,044, JP-A-47-37425, 50-10135
No. 50, No. 50-25228, No. 50-112038, No. 50-117422,
Those described in Japanese Patent Publication No. 50-130441, etc.
The couplers described in JP 98731 are preferred.

As the known color developing agent to be reacted with the above-mentioned coupler, aromatic primary amine compounds, particularly p-phenylenediamine compounds are preferable, and N, N-diethyl-p-phenylenediamine hydrochloride and N-ethyl are used. -P-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N- (β-methane Sulfonamidoethyl) -3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline -P-toluenesulfonate, N, N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N- (β-hydroxyethyl) -3-methyl-4-ami It can be mentioned aniline.

Examples of other preferable non-diffusible green absorbing dyes include known color cyan dye couplers.

Known colored cyan couplers include, for example, U.S. Pat.Nos. 2,521,908, 3,034,892, and British Patent 1,255,
Examples thereof include compounds described in JP-A No. 111, JP-A-48-22028 and the like.

Further, U.S. Pat.No. 3,476,563, JP-A-50-10135, 50-
Colored cyan couplers of the type in which the dye flows out into the processing bath upon reaction with the oxidation product of the color developing agent as described in 123341 can also be used.

A particularly preferred colored coupler is represented by the following general formula [I] -a.
To [II] -b.

General formula [I] -a General formula [I] -b In the general formula [I] -a and the general formula [I] -b, R ₁
And R ₂ are each a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a mono- or bicycloalkyl group, (for example, a cyclohexyl group), a terpenyl group (for example, a nobornino group), an aryl group (for example, a phenyl group). , Naphthyl group, etc.), a heterocyclic group (for example, a benzimidazolyl group, a benzothiazoline group, etc.) or a nonmetal atom necessary for forming a heterocycle such as morpholine and pyridine. The above alkyl group, aryl group and heterocyclic group may be substituted, and examples of the substituent include the following groups. Halogen atom, nitro group, hydroxy group, carboxy group, (when the coupler has at least 12 carbon atoms or a corresponding ballast group at the uncoupling position), amino group, aryl group, substituted amino group, (alkylamino,
Dialkylamino, anilino, N-alkylanilino, etc.), carboxylic acid ester group (carboalkoxy, carboaryloxy, etc.), amide group (acetamide, butylamide, ethylsulfonamide, N-methylbenzamide, N-propylbenzamide, 4- t-butylbenzamide, etc.), carbamyl group (carbamyl, N-octadecylcarbamyl, N, N-dihexylcarbamyl, N-methyl-N-phenylcarbamyl, 3-pentadecylphenylcarbamyl, etc.), sulfamyl group (coupler) Has a ballast group having at least 12 carbon atoms or a corresponding ballast group in the non-coupling position, N-propylsulfamyl, N-tolylsulfamyl, etc.), an alkoxy group (ethoxy, octadecyloxy, etc.), a sulfo group (the coupler is At least carbon source in non-coupling position If with the number 12 or equivalent ballast group), a substituted sulfonyl group (methylsulfonyl,
Octadecylsulfonylethoxysulfonyl, decyloxysulfonyl, phenylsulfonyl, trisulfonyl, phenoxysulfonyl, etc.) and the like.

R ³ is represented by -COR ₅ and -COOR _5. (Wherein R ₅ represents an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group), and R ₄ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

General formula [II] -a General formula [II] -b In the general formulas [II] -a and [II] -b, R ₁ is a hydrocarbon residue, R ₂ is an amino group, an alkyl group, an acylamino group, a ureido group, an alkoxycarbonyl group and their substitution products, a carboxyl group, etc. Indicates. -L- has 1 carbon
~ 6 represents an alkyleneoxy group, and m represents 0 or 1.

[DD] represents a diffusible dye residue, and represents a diffusible dye residue having a known dye moiety such as azo, azomethine, indoaniline, indophenol, and anthraquinone.

A preferable [DD] is represented by the following formula.

Examples of preferred non-spreading powders used in the present invention include compounds represented by the following general formula [III].

General Formula [III] Ball (X) _n -Col where -Ball is an organic stabilizing group having a molecular size and configuration that renders the compound non-diffusible during development in an alkaline processing composition. Represent

Examples of the above organic stable groups include, for example, formulas (I) to (II
It is represented by I).

In the formula (I), Z represents a necessary nonmetallic atom group forming a saturated carbocycle (5-membered to 7-membered) bonded at the 5- and 6-positions to the benzene ring bonded to the OY group. Most preferably, Y is a hydrogen atom, but depending on the use and nature of the photographic element to be added, the hydroxide ion concentration is from 10 ^{-5 to} 2 mol.
It may be a group in which the bond with the oxygen atom is cleaved at / l. Among the latter groups, the more preferable effect is Is a group represented by. Here, R ⁽¹⁾ represents an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, a phenyl group or a substituted phenyl group.

B represents an organic group which renders the compound represented by the general formula [III] non-diffusible in a color light-sensitive material, and the organic group is a long-chain alkyl group; or an aromatic group such as a benzene group or a naphthalene group. Or a long-chain alkyl group bonded to one end of a suitable divalent group or a benzene-based or naphthalene-based aromatic group as a representative one. The long-chain alkyl group or aromatic group may be substituted here, and a suitable divalent group is -O-; -S-; -CR ⁽³⁾ R ⁽⁴⁾ ; -CR ⁽³⁾ = CR ⁽⁴⁾ -(wherein R ⁽²⁾ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁽³⁾ and R ⁽⁴⁾ Each represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group); and a substituted or unsubstituted aromatic divalent group, a non-aromatic carbocyclic group or a non-aromatic heterocyclic group. It is a divalent group consisting of one of these or a plurality of them arbitrarily combined in a linear form.

In the formula (II), W represents an organic group which renders the compound represented by the general formula [III] non-diffusible in the color light-sensitive material, and is generally an aliphatic group or aromatic group having 8 to 20 carbon atoms. Base,
Examples thereof include an alicyclic group and an organic stabilizing group having a heterocyclic group.
The compounds of the present invention is attached via the 5-position or 6-position to the nitrogen atom of these groups is an indole ring, a mode via such a nitrogen atom, -NHCO- group, -NHSO ₂ -
And a group via a group such as a group, a —NR ₃ — group (R ₃ represents a hydrogen atom or an alkyl group) and the like. The organic stabilizing group is bonded to the 5- or 6-position of the indole ring,
It is preferable to bind to the position.

In the general formula (II), R ₁ represents a monovalent organic group, and examples of the group include an alkyl group and an alkoxy group, and an alkyl group having 1 to 3 carbon atoms and an alkoxy group are preferable.

In the general formula (II), R ₂ represents a low-molecular group bonded through a carbon atom, and the group is preferably a substituent having 1 to 9 carbon atoms, for example, having 1 to 9 carbon atoms. Alkyl group, phenyl group and (R ₄ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₄ and R ₅ may simultaneously form a ring.)
Is mentioned.

More preferably as R ₂ , an unsubstituted or halogen atom,
Examples thereof include a phenyl group substituted with a group selected from the group consisting of an acetylamide group, a methylsulfonamide group, a nitro group, a carboxy group, a sulfo group, a methanesulfone group, an alkyl group and an alkoxy group.

In the formula, E is directly attached to the 6-membered aromatic ring or (R ′ is an alkyl group), an alkylene group (which may be branched) —O—, —S—, —SO ₂ —, a phenylene group (which may be substituted with an alkyl group, etc.) or these. A halogen atom, a sulfo group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, which is bonded through a group consisting of any combination of
It represents a heterocycle such as an amino group, a cyano group, an alkylamino group, an arylamino group, a cyano group, an alkylthio group and a pyridyl group, and may be the same or different.

n represents an integer of 0 to 4.

D represents a group represented by -OR ₁ or -NHR ₂ . Here, R ₁ is under the condition of hydrogen atom or hydroxide ion concentration of 10 ⁻⁵ to 2 mol / l.
Represents a group in which the bond between R ₃ and O is cleaved, preferably a hydrogen atom, Is a group represented by. Here, R ₃ is an alkyl group, particularly an alkyl group having 1 to 18 carbon atoms.

X in the general formula [III] represents a suitable divalent group, and as a suitable divalent group, -O-; -S-; -SO _2- ; -SO-; -NR ¹ CO-; -NR ¹ SO _2- ; CR ² R ^3- ;
-CR ³ = CR ⁴ -, and the like. (Where R ¹ is hydrogen atom,
It represents an alkyl group or an aryl group, and R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. -Col in the general formula [III] represents a diffusible magenta or cyan dye component or a precursor component of these dyes.

Such ingredients are well known to those of skill in the art and include azo,
Dyes such as azomethine, azopyrazolone, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, merocyanine, nitro, quinoline, cyanine, indigoid, phthalocyanine, metal complex forming dyes, as well as leuco dyes, pH value fluctuations,
"Shifted", which changes to a bathochromic or bathochromic color when different ambient environments such as reactions with complex-forming substances are applied
Contains dye precursors such as dyes and the like. Also, −Co
l is a coupler component such as phenol, naphthol,
It may be indazolone, pyrazolone, the compounds described in US Pat. No. 2,756,142 and the like. These components may optionally have a solubilizing group.

Examples of -Col include those represented by formulas (IV) to (IX).

In formulas (IV) to (VI), Q is at the 5-position or 8 with respect to G.
Position, the hydroxyl group or the formula --NHCOR ³ or --NHSO ₂ R
³ (wherein R ³ represents an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group or a substituted phenyl group having 6 to 9 carbon atoms) And G is a hydroxyl group or a salt thereof or a formula (Wherein R ⁴ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group or a substituted phenyl group having 6 to 18 carbon atoms) and represents a hydrolyzable acyloxy group, and r is 1 or 2 Represents an integer of Z, cyano group, trifluoromethyl group, fluorosulfonyl group, carboxy group, formula -COOR ⁴
(Wherein R ⁴ represents the above), a nitro group at the 2- or 8-position with respect to the azo bond, fluorine,
Chlorine or bromine atom, alkyl having 1 to 8 carbon atoms
Or a substituted alkylsulfonyl group, having 6 to 9 carbon atoms
A phenyl- or substituted phenylsulfonyl group, an alkylcarbonyl group having 2 to 5 carbon atoms, and a formula —SO ₂ NR ⁵ R
⁶ (wherein R ⁵ represents a hydrogen atom, an alkyl or substituted alkyl group having 1 to 8 carbon atoms, R ⁶ represents a hydrogen atom, 1 carbon atom)
~ 6 alkyl or substituted alkyl group, benzyl group,
Phenyl group, or substituted alkyl group, benzyl group, phenyl group or substituted phenyl group having 6 to 9 carbon atoms,
Alkyl- or substituted alkylcarbonyl group having 2 to 7 carbon atoms, phenyl- or substituted phenylcarbonyl group having 7 to 10 carbon atoms, alkylsulfonyl group or substituted alkylsulfonyl group having 1 to 6 carbon atoms, and 6 carbon atoms 9 represents a phenylsulfonyl group or a substituted phenylsulfonyl group, or R ⁵ and R ⁶ together with the nitrogen atom to which they are bonded represent a morpholine group or a piperidino group), a sulfamoyl group, or a formula -CO
N (R ⁵ ) ₂ (wherein R ⁵ is the same or different and represents the same as above), and Z ¹ is hydrogen or Z.
The stands, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, carbon atoms 1
~ 4 alkoxy group or halogen atom, D is a cyano group, a sulfo group, a fluorosulfonyl group, a halogen atom, -SO ₃ -phenyl group or a substituted -SO ₃ -phenyl group having 6 to 9 carbon atoms, carbon Alkylsulfonyl group or alkylsulfonyl group having 1 to 8 atoms, phenylsulfonyl group or substituted phenylsulfonyl group having 6 to 9 carbon atoms, alkyl- or substituted alkylsulfinyl group having 1 to 8 carbon atoms, and carbon atom number 6-9 phenyl - or substituted phenylsulfanyl Huy group, the formula -SO ₂ NR ⁵
A sulfamoyl group for R ⁶ or a formula —CON (R ⁵ ) ₂ (wherein R ⁵ and R ⁶ are the same as defined above for Z respectively)
Of the carbamoyl group of ## STR00003 ## wherein the compound has no more than one sulfo group and no more than one carboxy group.

In formulas (VII) to (IX), Y is a hydrogen atom, Represents Here, R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and R ₁₃ represents an acyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkyllenoxyalkyl group, a carboxyalkyl group, carboxyphenyl. The group represents a carboxyalkylphenyl group, a hydroxyalkylphenyl group, an alkoxyphenyl group, or a group having the same meaning as the group represented by R ₁₂ . W represents —CO— or —SO ₂ —, R ₇ represents an alkyl group having 1 to 6 carbon atoms, an aryl group, or Represents

(Wherein R ₁₄ and R ₁₅ represents a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms. However R ₁₄ and R ₁₅
Do not become hydrogen atoms at the same time. ) R ₈ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms
~ 10 represents an aryl group.

R ₉ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 1 to
8 represents a dialkylamino group having 8 carbon atoms, and R ₁₀ represents an alkyl group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an arylthio group, a halogen atom, or an acylamino group having 1 to 10 carbon atoms.

Here, n is 0, 1 or 2.

R ₁₁ represents an alkyl group having 1 to 6 carbon atoms or an aromatic group (eg, phenyl group).

Next, specific representative examples of the non-diffusing green absorbing dye and the non-diffusing red absorbing dye used in the present invention are shown, but the compounds used in the present invention are not limited to these.

The non-diffusible dye of the present invention is synthesized by a known method. For example, JP-A-48-33826, JP-A-50-115528, and JP-A-57-85
055, 54-54021, U.S. Pat.No. 4053312, JP-A-54-9
It can be synthesized by the method described in 9431, 53-50736 and the like.

Preferred non-diffusible green absorbing dyes and non-diffusible red dyes in the present invention are known high-boiling organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, carbon tetrachloride and chloroform. After dissolving in a low boiling point organic solvent represented by the following, it was mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a dispersing means such as a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic dispersing device, etc. Then, it is added to the non-photosensitive hydrophilic colloid layer coating composition for use.

Known high-boiling-point organic solvents used include organic acid amides, carbamates, esters, ketones, urea derivatives, etc., particularly dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, di-
n-octyl phthalate, diisooctyl phthalate,
Phthalates such as diamyl phthalate, dinonyl phthalate, diisodecyl phthalate, tricresyl phosphate, triphenyl phosphate, tri-
Phosphate esters such as (2-ethylhexyl) phosphate, trisononyl phosphate, dioctyl sebacate, sebacate esters such as di- (2-ethylhexyl) sebacate, diisodecyl sebacate, glycerol tripropionate, glycerol tributyrate, etc. Ester of glycerin, and other one or one of phenol derivatives such as adibic acid ester, glutaric acid ester, succinic acid ester, maleic acid ester, folic acid ester, citric acid ester, di-tert-amylphenol and n-octylphenol. They can be used in combination of two or more kinds.

The non-diffusible green absorbing dye and the non-diffusing red absorbing dye used in the present invention are preferably oil-soluble dyes as described above, which are dissolved in a known high-boiling point organic solvent and emulsified and dispersed, followed by non-photosensitive hydrophilicity. It is used by adding it to the colloid layer (filter layer).

The amount of the non-diffusible dye added to the filter layer is generally such that the transmission density of the filter layer is red and the absorption wavelength of the filter layer is light in the wavelength range corresponding to the red region (600 to 700 nm) of the red-sensitive emulsion layer. The green absorption filter layer emits light in a wavelength range corresponding to the color sensitivity of the green-sensitive emulsion layer in the green range (500 to 600 nm).
(0 to 600 nm) measured with light in the wavelength range suitable for color sensitivity,
It is 0.01 to 0.3, preferably 0.03 to 0.1. The filter layer preferably has a thickness of 0.1 to 3.0 μm, particularly 0.3 to 1.5.

A particularly preferable position of the red filter layer is a non-photosensitive hydrophilic colloid layer which is adjacent to the red-sensitive emulsion layer which is closest to the support and is distant from the support, and a particularly preferable position of the green absorption filter layer is closest to the support. It is a non-photosensitive layer adjacent to the green-sensitive colloid layer at a distance from the support.

The light absorption of the red filter layer other than the red region and the light absorption of the green absorption filter layer other than the green region are optional, but preferably, the performance of each photosensitive layer is changed independently and independently in the design of the color photosensitive material. From the viewpoint of light absorption, the former is that light absorption is outside the red region and the latter is outside the green region as little as possible.

In the present invention, the red absorption filter layer and the green absorption filter layer may be in the form of a filter layer that absorbs red and green, which performs these functions in one layer.

For the silver halide emulsion, any of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride and the like which are used in ordinary silver halide emulsions can be used. However, silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferable.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The conversion may be used at any step in the formation of AgX to change the halogen composition of the grains.

A known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of silver halide grains.

The silver halide grains are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming and / or growing the grain). Metal ions are added using at least one selected from the group consisting of complex salts)
Alternatively, these metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research Disclosure (hereinafter R)
It can be carried out based on the method described in Item 17643, Item II.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal form such as cubic, octahedral or tetradecahedron, or may have an irregular crystal form such as spherical or plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed. The size of the silver halide grain is 0.05 to 30μ, preferably
Those of 0.1 to 20 μm can be used.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown).
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
The noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye.

Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and / or after the completion of chemical ripening, before coating a silver halide emulsion, Compounds known in the art as antifoggants or stabilizers can be added.

As the binder (or protective colloid) of the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other macromolecules, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, a hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners which crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in such an amount that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent to the processing liquid.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives, (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3, 5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2.4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, muco) Phenoxycyclo acid, etc.) or the like can be used alone or in combination.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of enhancing flexibility. Preferred plasticizers are the compounds described in A of RD17643, section XII.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color development processing, the emulsion layer of the light-sensitive material forms a dye by a coupling reaction with an oxidant of an aromatic primary amine developer (eg, p-phenylenediamine derivative, aminophenol derivative). A coupler is used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ion even if they are 4 equivalence. Either of two equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidant of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR substance (collectively referred to as a DIR compound) which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used. The combined use of a DIR compound other than the present invention is an effective technique for improving color reproducibility and the like.

The DIR compound used has an inhibitor bound directly to the coupling position, and the inhibitor bound to the coupling position via a divalent group, and the intramolecular group within the group released by the coupling reaction. Included are compounds (referred to as timing DIR compounds) that are bound so that the inhibitor is released by a nucleophilic reaction or an intramolecular electron transfer reaction. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. A colorless coupler (also referred to as a competing coupler) that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with the dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and bivaloylacetanilide compounds are advantageous. Specific examples of yellow color forming couplers that can be used include, for example, U.S. Pat.
No. 7, No. 3,265,506, No. 3,408,194, No. 3,551,1
No. 55, No. 3,582,322, No. 3,725,072, No. 3,891,
445, West German patent 1,547,868, West German published application 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,425,
No. 020, Japanese Patent Publication No. 51-10783, JP-A Nos. 47-26133 and 48-73.
No. 147, No. 50-6341, No. 50-87650, No. 50-123342,
50-130442, 51-21827, 51-102636, 52-8
2424, 52-115219, and 58-95346.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used. Specific examples of magenta color couplers that can be used include, for example, U.S. Pat.Nos. 2,600,788 and 2,983,608.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,506, No. 3,834,
908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,41
8,959, 2,424,467, JP-B-40-6031, JP-A-49-
74027, 49-74028, 49-129538, 50-60233
No. 50, No. 50-159336, No. 51-20826, No. 51-26541, No. 5
2-42121, 52-58922, 53-55122, Japanese Patent Application No. 55-11
Examples include those described in 0943.

As the cyan dye forming coupler, a phenol or naphthol type coupler is generally used. Specific examples of cyan color forming couplers that can be used include, for example, U.S. Pat.
No. 0, No. 2,474,293, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,326, No. 3,758,
No. 308, No. 3,893,044, JP-A-47-37425,
50-10135, 50-25228, 50-112038, 50-1174
No. 22, No. 50-130441, etc.,
The couplers described in JP-A-58-98731 are preferred.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, optical brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solid. Various methods such as a dispersion method, a latex dispersion method and an oil-in-water type emulsion dispersion method can be used, which can be appropriately selected according to the chemical structure of the hydrophobic compound such as a coupler. The oil-in-water emulsification dispersion method can be a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point of about 150 ° C. or higher and a high boiling point organic solvent, and / or an aqueous solution. Using a dispersing means such as a stirrer, homogenizer, colloid mill, flowgit mixer, ultrasonic device, etc., using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After emulsifying and dispersing, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As a high boiling point solvent, organic compounds with a boiling point of 150 ° C or higher, such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, trimesic acid esters that do not react with the oxidized product of the developing agent. A solvent is used.

A low boiling or water soluble organic solvent can be used with or in place of the high boiling solvent. Examples of the organic solvent having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane and benzene.

When dye-forming couplers, colored couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, optical brighteners, etc. have acid groups such as carboxylic acids and sulfonic acids, they are hydrophilic colloids as alkaline aqueous solutions. It can also be introduced inside.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used.

Between the emulsion layers of the light-sensitive material (same color-sensitive layer and / or different color-sensitive layer), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity, deterioration of sharpness, and graininess. An antifoggant can be used to prevent the property from being conspicuous.

The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds that can be preferably used are those described in RD17643, item VII J.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction and the like and to prevent deterioration of the image by ultraviolet rays. Good.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. The compound which can be preferably used as the development accelerator is the compound described in Item XXI to D of RD17643, and the development retarder is 1
The compound is described in Item XXI, Item E of 7643. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The emulsion layer of the photographic light-sensitive material comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane derivative for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urea derivative, an imidazole derivative and the like.

In addition to the non-diffusible dye of the present invention, the light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes,
An azo dye etc. can be mentioned.

Reduction of gloss of the light-sensitive material, improvement of writing property on the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other. Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonate and styrene. And the copolymers thereof. The matting agent preferably has a particle size of 0.05 μ to 10 μ. The amount to be added is preferably 1 to 300 mg / m ² .

Lubricants may be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. May be used for. Antistatic agents preferably used are the compounds described in RD17643 XIII.

For the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property improvement, antistatic property, slipperiness improvement, emulsion dispersion,
Various surfactants can be used for the purpose of preventing adhesion, improving photographic characteristics (acceleration of development, hardening agent, sensitization, etc.).

The support used in the photosensitive material of the present invention, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate,
Films made of semi-synthetic or synthetic polymers such as polyamide are included.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness,
It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

At the time of applying the light-sensitive material, a thickener may be used to improve the coatability. For a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because it has a high reactivity, it is recommended to mix it with a static mixer or the like immediately before coating. preferable.

As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful, but packet coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, and examples thereof include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide-based, glycerin-based, glycidol-based, higher alkylamines, quaternary ammonium salts, pyridine and the like. Compounds such as compound rings, phosphonium or sulfonium, cationic surfactants, carboxylic acids, sulfonic acids,
Anionic surfactants containing an acidic group such as phosphoric acid, sulfuric acid ester and phosphoric acid ester, and amphoteric surface active agents such as amino acids, aminosulfonic acids and sulfuric acid or phosphoric acid esters of amino alcohol may be added.

Further, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilization processing step if necessary, but instead of a processing step using a bleaching solution and a processing step using a fixing solution. In addition, the bleach-fixing treatment step can be carried out using the 1-bath bleach-fixing solution, and the mono-bath processing step using the 1-bath development bleach-fixing solution capable of performing color development, bleaching and fixing in a single bath You can also do

In combination with these treatment steps, the pre-hardening treatment step, the neutralizing step thereof, the stop fixing treatment step, and the post-hardening treatment step may be performed. In these processes, instead of the color development processing step, a color developing agent, or a precursor thereof may be contained in the material, and an activator processing step in which the development processing is carried out with an activator solution may be performed, or an activator for the monobath processing. Treatments can be applied. Typical processing is shown below among these processings. (These steps include any one of a washing step, a washing step and a stabilizing step as the final step.) ・ Color development processing step-bleaching step-fixing step-Color development processing step-bleach-fixing step Process-Pre-hardening process-Color development process-Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplement Color development processing step-Stop processing step-Bleaching processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually 10 ° C. ~ 65 ℃, but 65 ℃
The temperature may be higher than that. It is preferably treated at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can.

These compounds are generally about 0.1 g per color developer 1.
It is used in a concentration of -30 g, more preferably in a concentration of about 1-15 g for Color Developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine-based color developing agents are N, N-dialkyl-p-phenylenediamine-based compounds, in which the alkyl and phenyl groups may or may not be substituted. Among them, particularly useful compound examples are NN-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5- (N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl N, N-diethylaniline, 4-
Amino-N- (2-methoxyethyl) -N-ethyl-3
-Methylaniline-p-toluene sulfonate etc. can be mentioned.

The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, the silver halide color photographic light-sensitive material can be processed with an alkaline solution (activator solution) instead of color development, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developer used in the light-sensitive material of the present invention contains an alkaline agent usually used in developers, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. Further, various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazinic acid, a preservative such as hydroxylamine or sulfite, and the like can be included. May be included. Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. may be appropriately contained.

The pH of the color developing solution used in the light-sensitive material of the present invention is usually 7 or more, preferably about 9-13.

In the color developer used in the present invention, if necessary, an antioxidant such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, secondary aromatic alcohol, hydroxamic acid, bentose or hexose is used. , Pyrogallol-1,3
-Dimethyl ether and the like may be contained.

In the color developing solution used for the light-sensitive material of the present invention, various chelating agents can be used in combination as sequestering agents. For example, as the chelating agent, an amine polycarboxylic acid such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid, an organic phosphonic acid such as 1-hydroxyethylidene-1,1′-diphosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, etc. Aminopolyphosphonic acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane 1,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, polyhydroxy compound, etc. Is mentioned.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper are coordinated are used. . Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, Examples include phenylenediamine tetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are used at 5-450 g / l, more preferably 20-250 g / l.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative is applied if necessary.
Further, it may be a bleaching solution having a composition containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and adding a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the light-sensitive material of the present invention is disclosed in JP-A-46-2
No. 80, Japanese Patent Publication No. 45-8506, No. 46-556, Belgium Patent No. 7
70,910, JP-B-45-8836, JP-A-53-9854, JP-A-54-7
Various bleaching accelerators described in 1634 and 49-42349 may be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0.

The fixer may have a commonly used composition. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixatives
5g / l or more, used in an amount that can be dissolved, but generally
Use at 70-250g / l. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethyl sulfamide or dimethyl sulfoxide can be appropriately contained.

The fixer is used at a pH of 3.0 or above, but generally 4.5-10
Is used, preferably 5 to 9.5, and most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the bleaching treatment step, and preferable compounds and concentrations in the processing solution are the same as in the bleaching treatment step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halide such as ammonium bromide A bleach-fix solution composed of a large amount of iron, and further ethylenediaminetetraacetate iron (II
I) A special bleach-fixing solution having a composition comprising a combination of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halide,
Hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used in addition to ammonium bromide.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the fixing processing step. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as those in the fixing processing step.

The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5, most preferably 6.8-8.5.

[Example-1] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-1 (Comparative) First layer: Antihalation layer (HC-1) Gelatin layer containing 0.18 g of black colloidal silver.

Second layer; intermediate layer (IL) Gelatin layer containing 2,4-di-t-octylhydroquinone 0.14 g.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (Emulsion I) consisting of AgBrI containing 0.30 μm average grain size () and 8 mol% AgI ... Silver coating amount 1.5 g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): relative to 1 mol of silver 0.08 mol Colored cyan coupler (CC-1) ... 0.005 mol per mol of silver DIR compound (D-1) ... 0.003 mol per mol of silver DIR compound (D-2) ... 1 mol of silver 0.004 moles 4th layer; high-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size () 0.65 μm, monodispersed emulsion consisting of AgBrI containing 6.0 mole% AgI (Emulsion II). Silver coating amount 1.3 g / m ² Sensitizing dye I …… 3 × 10 ^-5 mol for 1 mol of silver Sensitizing dye II …… 1.0 × 10 ^-5 mol for 1 mol of silver Cyan coupler (C-1 ) …… 1 mol silver On the other hand, 0.02 mol Colored cyan coupler (CC-1): 0.0015 mol per mol of silver DIR compound (D-2): 0.001 mol per mol of silver Fifth layer; Intermediate layer (IL) Second Same as layer, gelatin layer.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Coating amount of 1.2 g / m ² sensitizing dye III: 2.5 × 10 ^-5 mol increase per mol of silver Sensitizing dye IV: 1.2 × 10 ^-5 moles per 1 mole of silver Magenta coupler (M-1): 0.08 moles per 1 mole of silver Colored magenta coupler (CM-1): 1 mole of silver 0.015 mol DIR compound (D-3) …… 0.002 mol per 1 mol of silver 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II …… Coating silver amount 1.0 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol per 1 mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 mol per 1 mol of silver Magenta coupler (M-1): 1 mol of silver 0.025 mol Colored magenta coupler (CM-1) 0.002 mol per mol silver DIR compound (D-3) 0.0005 mol per mol silver 8th layer; yellow filter (YC-1) Gelatin layer containing yellow colloidal silver 0.09g of 2,5-di -t- octylhydroquinone 0.14 g.

Ninth layer: low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) made of AgBrI having an average grain size of 0.4 μm and AgI of 6 mol%.

Monodisperse emulsion (Emulsion III): Silver coating amount 0.7 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 moles per 1 mole of silver Yellow coupler (Y-1): 1 mole of silver 0.29 mol 10th layer; high-sensitivity blue-sensitive emulsion layer (BH-1) consisting of AgBrI containing 0.8 μm average grain size and 8 mol% AgI.

Monodisperse emulsion (Emulsion IV): Silver coating amount 0.5 g / m ² Sensitizing dye V: 1.0 × 10 ^-5 mol per 1 mol of silver Yellow coupler (Y-1): relative to 1 mol of silver 0.08 mol DIR compound (D-3): 0.0015 mol per mol of silver 11th layer: 1st protective layer (Pro-1) Silver iodobromide (AgI 1 mol% average particle size 0.07 μm) Silver coating amount 0.2 Serratin layer containing g / m ² UV absorbers UV-1 and UV-2 12th layer; 2nd protective layer (Pro-2) Polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) Gelatin layer In addition to the above composition, a gelatin hardening agent (H-
1) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl 3,
3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II: anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) 5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxythia Cyanine Similarly, the DIR compound D-3 of the sixth layer (GL-1) of Sample 1 was changed to the compound of Table 1, and Samples 2 to 9 were prepared by adding the dye as in Example 1. The samples 1 to 9 thus prepared were exposed to white light through a MTF measurement pattern for comparison of sharpness, and processed according to the following processing steps to prepare an MTF curve. The obtained values are shown in Table 1.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. Is the street.

[Color developer]

4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

[Bleaching solution]

Ethylenediaminetetraacetic acid ammonium ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water is added to adjust the pH to 1 using ammonia water.

[Fixer]

Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and the pH is adjusted to 6.0 using acetic acid.

[Stabilizer]

 Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

As is clear from MTF _G in Table 1, Samples 4 to 9 in which the DIR compound of the present invention and the dye were combined were all tested at 50 cycles / mm.
Significant improvement in MTF value. Especially, the effect is large in the samples 4 and 5 in which the compound of type (II) and the green light absorbing dye A-20 are added to the 8th and 12th layers.

Example-2 Samples shown in Table 2 were prepared in the same manner as in Example-1, and the same treatment as in Example-1 was performed to prepare MTF curves. The values obtained are shown in Table 2.

As is clear from the MTF _R in Table 2, all of the samples 11 to 14 in which the compound of the present invention and the dye are combined show a remarkable improvement in the MTF _R at 30 cycles / mm. In particular, red light absorbing dye A-17 was added to the 5th, 8th, 12th
The effect is large in Samples 11 to 13 added to the layers, respectively.

Claims (1)

[Claims] 1. A releasing group is reacted with an oxidation product of a developing agent to release a leaving group, and the released different type or the same type of leaving group changes its development inhibiting action, fogging action or development promoting action by intermolecular reaction. A silver halide color light-sensitive material containing a compound capable of absorbing light and a non-diffusible green and / or red light absorbing dye in the non-light-sensitive layer.