JPH0675171B2 - Silver halide color photographic light-sensitive material having improved desilvering property - Google Patents

Description

The present invention relates to a silver halide color light-sensitive material having improved desilvering property and excellent sharpness.

BACKGROUND OF THE INVENTION In recent years, in color photographic light-sensitive materials, the screen size of photographic light-sensitive materials has become smaller due to advances in camera manufacturing technology and the like, and therefore the magnification of expansion to print light-sensitive materials tends to increase. Therefore, higher image quality is especially required for the photosensitive material for photographing, and various proposals have been made for this purpose.

As means for improving image quality, U.S. Pat.
It is known to use so-called DIR compounds described in 3,227,554, 3,615,506 or Japanese Patent Publication No. 55-34933.

Further, with the recent increase in image quality, a compound that releases a diffusible development-inhibiting compound or its precursor by a coupling reaction with an oxidant of a color developing agent for the purpose of obtaining a large edge effect (hereinafter referred to as a diffusible DIR compound) ) Tends to use a large amount.

However, if a large amount of the above-mentioned diffusible DIR compound is used to obtain a strong edge effect, it is necessary to add a large amount of the diffused DIR compound to the light-sensitive material. In comparison with the improvement effect expected from the case of adding a large amount of
When the compound was added, the improvement effect was small, and there was a strong tendency for the improvement effect to saturate with the amount added.

Furthermore, it is considered that the inclusion of a large amount of diffusible DIR as described above is caused by deterioration of desilvering property of silver halide in the photosensitive layer near the support or colloidal silver contained in the antihalation layer. Problems such as poor desilvering and clouding of color occur. If this is attempted to be solved by simply reducing the amount of colloidal silver or the amount of silver halide, the sharpness is deteriorated, the graininess is deteriorated, and the image quality is significantly deteriorated. Therefore, there has been a demand for an improved technique which maximizes the sharpness and has a very good desilvering property.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent desilvering property and excellent sharpness.

[Constitution of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material having a photographic constituent layer containing a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support, wherein Of silver halide emulsion layers containing a diffusible DIR compound in at least one emulsion layer and a bleach accelerator releasing coupler in at least one of the photographic constituent layers. It was

[Specific Structure of the Invention] Hereinafter, the present invention will be described in more detail.

Bleaching accelerator releasing coupler of the present invention (hereinafter referred to as Bleach Acc
elerator Releasing coupler = BAR coupler)
Is preferably represented by the following general formula [B].

General formula [B] In the formula, Cp represents a coupler residue capable of undergoing a coupling reaction with an oxidized product of a color developing agent, * represents a coupling position of the coupler, TIME represents a timing group, and m represents 0.
Or 1 and R ₁ is a divalent aliphatic group having 1 to 8 carbon atoms, or (Wherein L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), and R ₂ represents a water-soluble group or a precursor thereof.

Coupler residues represented by Cp include those that produce yellow, magenta, or cyan dyes and those that produce substantially colorless products.

In the coupler residue represented by Cp, a representative yellow coupler residue is represented by U.S. Pat.No. 2,298,443.
No. 2,407,210, 2,875,057, 3,048,19
No. 4, No. 3,265,506, No. 3,447,928, and "Farbukpraeine Literat Wolvergicht Agfamitting (Band II)" {Farbkupplere
ine Literaturuversiecht Agfa Mitteilung (Band I
I)} 112 to 126 (1961). Of these, acylacetanilides such as benzoylacetanilide and pivaloylacetanilide are preferable.

Typical as a magenta coupler residue, U.S. Patent Nos. 2,369,489, 2,343,703, 2,311,182,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3, No. 3,152,896, No. 3,519,429, No. 3,725,06
7, 4,540,654, JP-A-59-162548, and Agfa Mitteilung (Band II), pages 126-156 (1961).
Etc. Of these, pyrazolone or pyrazoloazole (eg, pyrazoloimidazole, pyrazolotriazole, etc.) is preferable.

A typical siccan coupler residue is described in US Pat.
2,367,531, No. 2,423,730, No. 2,474,293, No. 2,772,162, No. 2,395,826, No. 3,002,836,
Nos. 3,034,892, 3,041,236, 4,666,999 and Agfa Mitteilung (Band II) pp. 156-175 (1961). Of these, phenols or naphthols are preferable.

Typical coupler residues forming a substantially colorless product are, for example, British Patent No. 861,138, U.S. Pat.Nos. 3,632,345, 3,928,041, and 3,958,99.
No. 3 and No. 3,961,959, and the like.
Of these, cyclic carbonyl compounds are preferred.

The timing group represented by TIME is a bleaching accelerator group (-S
-R ₁ -R ₂ ) is a group that enables time-release from Cp, which is the reaction rate between Cp and the oxidant of the color developing agent, which is released from Cp- TIME-S-R ₁ -R ₂
Release rate of the diffusion rate, and -S-R ₁ -R ₂ may also include a group capable of control. Typical timing groups include intramolecular nucleophilic substitution reaction disclosed in U.S. Pat. No. 4,248,962 and JP-A-57-56837.
S-R ₁ -R ₂ and which emits, JP 56-114946 Patent, -S-R ₁ by an electron transfer reaction along a conjugated chain as disclosed in such as JP 57-154234 Pat - Examples thereof include those that release R ₂ . In addition, JP-A-57-188035 and 58-
98728, 59-206834, 60-7429, 60-214358
No. 50, No. 50-225844, No. 60-229030, No. 60-233649,
The timing groups disclosed in the specifications of No. 60-237446 and No. 60-237447 are also included.

Specific examples include the following.

Widen below -S-R ₁ -R ₂ is a -OCH ₂ CH ₂ NHCO- bleach accelerator group. R ₁ is a divalent aliphatic group having 1 to 8 carbon atoms, or (Wherein L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), and more preferably the following formula.

In the formula, R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 1 to 8. n
When is 2 or more, R ₃ and R ₄ may be the same or different. The alkyl group represented by R ₃ and R ₄ is
It may be linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, and n.
-Butyl group, ter-butyl group and the like. Preferred examples of R ₁ are shown below.

_{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -, −CH ₂ CH ₂ CH ₂ CH ₂ − −CH ₂ CH ₂ OCH ₂ CH ₂ −, Preferred examples of the water-solubilizing group represented by R ₂ or a precursor thereof are listed below.

_{-COOH, -COONa, -COOCH 3, -COOC} 2 H 5, -NHSO 2 CH 3, -
_{NHCOOCH 3, -NHCOOC 2 H 5,} -SO 3 H, -SO 3 K, -OH, _{-SO 2 NH 2, -NR 5 R} 6 [ wherein represents an alkyl group of R ₅ and R ₆ are each C1-4 hydrogen atom or a carbon atom. ] Particularly preferred as the bleaching accelerator group represented by -S-R ₁ -R ₂ is -S-CH ₂ CH ₂ COOH, -S-CH ₂ CH ₂ CH ₂ COOH, Is.

Specific examples of the BAR coupler used in the present invention are shown below, but the invention is not limited thereto.

The BAR coupler according to the present invention can be contained in any layer of a photographic material, for example, a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer, but is preferably used in the silver halide emulsion layer. Is good. Further, it is preferably used in the red-sensitive silver halide emulsion layer and / or the green-sensitive silver halide emulsion layer.

In order to include the BAR coupler of the present invention in the hydrophilic colloid layer of a color light-sensitive material, for example, a known high-boiling solvent such as dibutyl phthalate, tricresyl phosphate, and dinonylphenol, and a low boiling point solvent such as butyl acetate and propionic acid. Each of the BAR couplers according to the present invention is dissolved in a mixture with a boiling solvent, either alone or in combination, and then dissolved with a gelatin aqueous solution containing a surfactant, and then mixed with a high-speed rotary mixer or colloid mill or ultrasonic disperser. After emulsifying and dispersing using the above, it may be directly added to the emulsion, or after the above emulsified dispersion is set, it may be shredded and washed with water and then added to the emulsion.

The amount of the BAR coupler used according to the present invention is 1
The amount is preferably 0.0005 mol to 5.0 mol, and more preferably 0.005 mol to 1.0 mol per mol.

The BAR coupler according to the present invention may be used alone or in combination of two or more.

In the present invention, the diffusible DIR compound is a compound which is released by the reaction with an oxidized product of a color developing agent and has a diffusivity of a development inhibitor or a compound capable of releasing a development inhibitor, which is 0.40 or more in diffusivity according to the evaluation method described below. Is.

The diffusivity is evaluated by the following method.

Photosensitive material samples (I) and (II) having a layer having the following composition are prepared on a transparent support.

Sample (I): Sample having green-sensitive silver halide emulsion layer Silver iodobromide spectrally sensitized to green sensitivity (6 mol% silver iodide, average particle size 0.48 μm) and the following coupler per 1 mol of silver: 0.
A gelatin coating solution containing 07 moles was coated with a silver amount of 1.1 g / m ² ,
It was coated so that the amount of gelatin applied would be 3.0 g / m ² , and silver iodobromide (2 mol% silver iodide, average grain size 0.08 μm) that had not been chemically or spectrally sensitized as a protective layer thereon. ) Containing a gelatin coating solution with a silver amount of 0.1 g / m ² and a gelatin coating amount of
Apply so that it becomes 0.8 g / m ² .

Sample (II): Silver iodobromide removed from the protective layer of Sample (I).

In addition to the above, each layer contains a gelatin hardening agent and a surfactant.

Samples (I) and (II) were exposed to white light using a wedge,
It is processed according to the following processing method. A sample (I
What added the amount of various development inhibitors which suppresses the sensitivity of I) to 60% (-(DELTA) logE = 0.22 in a logarithmic display) and what did not add the development inhibitor are used.

Processing step (38 ℃) Color development 2 minutes 40 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Used in each processing step The composition of the treatment liquid is as follows.

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

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water and adjust to pH = 6.0 using ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH = 6.0 with acetic acid.

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

The sensitivity of the sample (I) when the development inhibitor is not added is S ₀ , the sensitivity of the sample (II) is So ′, the sensitivity of the sample (I) when the development inhibitor is added is S _I, and the sensitivity of the sample (II sensitivity) When S _II, expressed as reduced sensitivity ΔSo-So'-S _II diffusible = ΔS / ΔSo sample (reduced sensitivity ΔS-So-S _I sample I) (II).

However, all the sensitivities are the logarithm (-log E) of the reciprocal of the exposure amount at the density point of fog density + 0.3.

The diffusivity of several development inhibitors determined by this method is illustrated in the table below.

In the present invention, any diffusible DIR compound can be used regardless of its chemical structure as long as the diffusibility of the released group is within the above range.

Typical structural formulas are shown below.

General formula (D-1) A- (Y) m A represents a coupler residue, m represents 1 or 2, and
Y is a group which is bonded to the coupling position of the coupler residue A and is released by the reaction with the oxidant of the color developing agent and has a diffusibility of 0.40.
The above-mentioned development inhibitors or groups capable of releasing the development inhibitors are represented.

In the general formula (D-1), Y is typically represented by the following general formulas (D-2) to (D-19).

General formula (D-2) General formula (D-3) General formula (D-4) General formula (D-5) General formula (D-6) General formula (D-7) General formula (D-8) General formula (D-9) In formulas (D-2) to (D-7), Rd ₁ is a hydrogen atom, a halogen atom, or alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkyl. Carbamoyl, N, N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino,
It represents an alkylthio, arylthio, aryl, heterocycle, cyano, alkylsulfonyl or aryloxycarbonylamino group. n represents 0, 1 or 2, and when n is 2, each Rd ₁ may be the same or different. The total number of carbon atoms contained in n Rd ₁ is 0 to 10. The number of carbon atoms contained in Rd ₁ in the general formula (D-6) is 0 to 15.

X in the general formula (D-6) represents an oxygen atom or a sulfur atom.

In the general formula (D-8), Rd ₂ represents an alkyl group, an aryl group or a heterocyclic group.

In the general formula (D-9), Rd ₃ represents a hydrogen atom or an alkyl, cycloalkyl, aryl or heterocyclic group, and Rd ₄ represents a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, acylamino or alkoxycarbonyl. It represents an amino, aryloxycarbonylamino, alkanesulfonamide, cyano, heterocycle, alkylthio or amino group.

When Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ represents an alkyl group, the alkyl group includes those having a substituent and may be linear or branched.

When Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ represents an aryl group, the aryl group includes those having a substituent.

When Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ represents a heterocyclic group, this heterocyclic group includes those having a substituent, and at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom. A 5-membered or 6-membered single ring or fused ring containing one is preferable, and examples thereof include pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl,
It is selected from each group of imide and oxazine.

In the general formulas (D-6) and (D-8), the number of carbon atoms contained in Rd ₂ is 0 to 15.

In the general formula (D-9), the total number of carbon atoms contained in Rd ₃ and Rd ₄ is 0 to 15.

General formula (D-10) -TIME-INHIBIT In the formula, the TIME group is a group which is bonded to the coupling position of A and can be cleaved by the reaction with the oxidized product of the color developing agent. After cleavage from the coupler, the INHIBIT group is It is a group that can be appropriately controlled and released. The INHIBIT group is a group that becomes a development inhibitor by the above release (for example, a group represented by the general formulas (D-2) to (D-9)).

In the general formula (D-10), the -TIME-INHIBIT group is typically represented by the following general formulas (D-11) to (D-19).

General formula (D-11) General formula (D-12) General formula (D-13) General formula (D-14) General formula (D-15) General formula (D-16) General formula (D-17) General formula (D-18) General formula (D-19) In the general formulas (D-11) to (D-15) and (D-18), Rd ₅ is a hydrogen atom, a halogen atom or alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy,
Represents an alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, arboxy, sulfo, hydroxy or alkanesulfonyl group,
General formula (D-11)-(D-13), (D-15), (D-1
In 8), Rd _{5 s} may be bonded to each other to form a condensed ring, and in the general formulas (D-11), (D-14), (D-15) and (D-19), Rd ₅ Represents an alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle or aryl group, and in the general formulas (D-16) and (D-17), Rd ₇ represents a hydrogen atom or alkyl, alkenyl, aralkyl, cycloalkyl, Represents a heterocyclic group or an aryl group, Rd ₈ and Rd ₉ in the general formula (D-19) each represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms); 11),
K in (D-15) to (D-18) represents an integer of 0, 1 or 2, and k in the general formulas (D-11) to (D-13) and (D-
15), l in (D-18) represents an integer of 1 to 4,
M in the general formula (D-16) represents an integer of 1 or 2, and when m is 2, each Rd ₇ may be the same or different, and n in the general formula (D-19) is an integer of 2 to 4. Represent, n
Rd ₈ and Rd ₉ may be the same or different, and B in the general formulas (D-16) to (D-18) is an oxygen atom or (Rd ₆ has the same meaning as previously defined.) In the general formula (D-16) Represents a single bond or a double bond, m is 2 in the case of a single bond and m in the case of a double bond.
Is 1 and the INHIBIT group is represented by the general formula (D-2) to (D-
Except for the carbon number, it has the same meaning as the general formula defined in 9).

In the INHIBIT group, the total number of carbon atoms contained in R ₁ in one molecule in the general formulas (D-2) to (D-7) is 0 to 32.
And the number of carbon atoms contained in Rd ₂ in the general formula (D-8) is 1 to 32, and Rd ₂ and R in the general formula (D-9) are
The total number of carbon atoms contained in d ₄ is 0 to 32.

When Rd ₅ , Rd ₆ and Rd ₇ represent an alkyl group or a cycloalkyl group, those having a substituent are included.

When Rd ₅ , Rd ₆ and Rd ₇ represent an aryl group, the aryl group includes those having a substituent.

Among the diffusible DIR compounds, Y is preferably one represented by the general formula (D-2), (D-3) or (D-10), and in (D-10), INHIBIT Is the general formula (D
-2), (D-6) (particularly when X in the general formula (D-6) is an oxygen atom), or (D-8) (particularly the general formula (D-8)
Rd _{2 of} is hydroxyaryl or alkyl having 1 to 3 carbon atoms) is preferable.

Examples of the coupler component represented by A in formula (D-1) include a yellow color image forming coupler residue, a magenta color image forming coupler residue, a cyan color image forming coupler residue, and a non-colorless coupler residue.

The preferred diffusible DIR compounds used in the present invention include, but are not limited to, the following compounds.

Including these, specific examples of the diffusible DIR compound that can be used in the present invention are U.S. Patent Nos. 4,234,678 and 3,227,
No. 554, No. 3,617,291, No. 3,958,993, No. 4,149,886
No. 3,933,500, JP-A-57-56837, 51-13239,
U.S. Pat. Nos. 2,072,363 and 2,070,266, Research Disclosure, December 1981, No. 21228, and the like.

The amount of the diffusible DIR compound added to the silver halide photosensitive layer is preferably 0.1 mol% or more based on the silver halide in at least one of the photosensitive layers of the green-sensitive layer and the red-sensitive layer. , And more preferably both are 0.2 mol% or more. Particularly preferably, both are in the range of 0.35 mol% to 3.0 mol%.

In the present invention, by adding the diffusible DIR compound to both the green-sensitive layer and the red-sensitive layer, not only the edge effect becomes large but also the improvement effect becomes remarkable when evaluated as an actual image.

The layer to be added is a low-sensitivity layer when the color-sensitive layer according to the present invention has a so-called two-layer structure in which it is divided into a high-sensitivity layer and a low-sensitivity layer, and a middle and / or low-sensitivity layer when it is a 3-layer structure. Is preferable in terms of enhancing the edge effect of the image.

Further, the use of the following DIR compounds in combination with the diffusible DIR compound according to the present invention is not hindered, but in order to effectively bring out the present invention, it is desirable that the content thereof is within 0.2 mol% with respect to silver halide.

The diffusion DIR compound according to the present invention and the BAR coupler are preferably contained in the same layer.

Generally, the bleaching speed of black colloidal silver contained in the antihalation layer is very slow because the antihalation layer is located closer to the support than the photosensitive emulsion layer.

According to the constitution of the present invention, since the bleaching speed of the black colloidal silver is also high, it is preferable to apply 0.06 g / m ² or more from the viewpoint of improving the sharpness. More preferably 0.08 g / m ² to 0.5 g / m
It is in the range of ² .

The sharpness improving effect can be further increased by adding a dye which is substantially non-diffusible to the non-photosensitive layer. Preferably, a dye that absorbs red or green light is added to the protective layer in a concentration of 0.03 to 0.20.

The effect of the present invention is not impaired even when the amount of silver halide contained in the light-sensitive material is large. Converted to silver
Even if it is 100 mg / dm ² or more, the desilvering property is good.

The silver halide emulsion layer according to the present invention may have at least one red photosensitive layer, at least one green photosensitive layer and at least one blue photosensitive layer on the support, and the layer arrangement is from the support side. The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer may be arranged in this order, or may have another arrangement, but the former arrangement is preferable. Each photosensitive layer is composed of one or more layers, preferably two or three layers.

A part or all of the light-sensitive silver halide emulsion layers having different color sensitivities and between the light-sensitive silver halide emulsion layers having the same color sensitivities but different sensitivities are non-photosensitive hydrophilic. An intermediate layer of the organic colloid layer may be provided. Further, it is preferable that the uppermost layer is provided with a protective layer of a non-photosensitive hydrophilic colloid layer.

The silver halide emulsion used in the light-sensitive material of the present invention includes
Any of ordinary silver halide emulsions can be used.

The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and the hydrophilic colloid layer outside the emulsion layer can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Furthermore, by the coupling with colored couplers, competing couplers and oxidized products of developing agents, which have the effect of color correction, development accelerators, developers, silver halide solvents, toning agents, hardening agents, capry agents, capry Compounds that release photographically useful fragments such as inhibitors, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention 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.

A matting agent, a lubricant, an image stabilizer, a surfactant, an anti-color capping agent, a development accelerator, a development retarder and a bleaching accelerator can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like,
Polyethylene terephthalate film, baryta paper, cellulose triacetate and the like can be used.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Conventionally known color photographic processing can be performed.

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

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) A gelatin layer containing 0.31 g of black colloidal silver.

Second layer: intermediate layer (IL-1) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (Emulsion I) consisting of AgBrI containing 0.50 μm average grain size () and 5.5 mol% AgI ... Silver coating amount 1.8 g / m ² Sensitizing dye I …… 2 × 10 ^-4 mol per 1 mol of silver Sensitizing dye II …… 1.5 × 10 ^-4 mol per 1 mol of silver Siccan coupler (C-1) …… 1 silver 0.090 mol per mol Colored cyan coupler (CC-1) ... 0.0050 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver Fourth layer: high-sensitivity red-sensitive halogen Silver halide emulsion layer (RH-1) Average grain size () 1.05 μm, AgBrI containing 5.0 mol% AgI Monodisperse emulsion (Emulsion II) …… Silver coating amount 1.3 g / m ² Sensitizing dye I …… 2.5 × 10 ^-4 mol Sensitizing Dye II to 1 mol of silver 1.0 × 10 ^-4 mol Sensitizing Dye II to 1 mol of silver Cyan coupler (C-2) …… 0.007 mol to 1 mol of silver Cyan coupler ( C 3) ...... silver mole with respect to 0.021 mol colored cyan coupler (CC-1) ... 0.015 mol fifth layer per mol of silver; the intermediate layer (IL-2) same as the second layer, the gelatin layer.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-1 ... Coating amount of silver 1.5 g / m ² Sensitizing dye III: 2.0 × 10 ^-4 mol increase per 1 mol of silver Sensitizing dye IV: 0.8 × 10 ^-4 moles per 1 mole of silver Magenta coupler (M-1): 0.065 moles per 1 mole of silver Colored magenta coupler (CM-1): 1 mole of silver 0.0035 mol DIR compound (D-2) ... 0.0015 mol with respect to 1 mol of silver 7th layer; intermediate layer (IL-3) gelatin layer 8th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II: coating amount of silver 1.4 g / m ² Sensitizing dye III: 1.3 × 10 ^-4 mol for 1 mol of silver Sensitizing dye IV: 0.8 × 10 ^-4 mol for 1 mol of silver Magenta Coupler (M-1): 0.0018 mol per mol of silver Colored magenta coupler (CM-1): 0.002 mol per mol of silver Ninth layer: Yellow filter layer (YC-1) Gelatin layer containing emulsified dispersion of yellow colloidal silver 0.06g of 2,5-di -t- octylhydroquinone.

Layer 10: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion consisting of AgBrI with average grain size 0.7 μm and AgI 6 mol% (Emulsion III) ...... Silver coating amount increased 0.9 g / m ² Sensitizing dye V: 0.80 × 10 ^-4 mol per 1 mol of silver Yellow coupler (Y-1): 0.15 mol per 1 mol of silver 11th layer; high-sensitivity blue-sensitive emulsion layer (BH-1) average Monodisperse emulsion consisting of AgBrI with a grain size of 1.2 μm and containing 9 mol% of AgI (Emulsion IV) …… Silver coating amount 0.7 g / m ² Sensitizing dye V …… 4.0 × 10 ^-5 mol of yellow coupler to 1 mol of silver Yellow coupler (Y-1) ... 0.08 mol per mol of silver 12th layer; first protective layer (pro-1) Silver iodobromide (AgI 1 mol% average particle size 0.07 μm) Silver coating amount 0.1.
5g / m ² UV absorber UV-1, UV-2 and red transmission density 0.1
A gelatin layer containing the oil-soluble dye Dye-1 to be used.

Thirteenth layer; second protective layer (pro-2) Polymethylmethacrylate particles (gelatin layer containing 1.5 μm in diameter) Each layer contains a gelatin hardener (H-
1) and (H-2) and a surfactant were added.

Each color coupler, BAR coupler, DIR compound, ultraviolet absorber, and oil-soluble dye additive contained dibutyl phthalate as a high boiling point solvent in the same weight as each additive, and was added as a dispersion in each layer.

For each photosensitive silver halide, 1-phenyl-
5-mercaptotetrazole was used.

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-sulfo Propyl) 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' -Methoxythiacyanine anhydroxide Further, a total of 13 kinds of samples were prepared by changing only the additive of each layer of Sample 1 shown in Table 2 as shown in Sample Nos. 2 to 13 of Table 2.

Each of the sample Nos. 1 to 1 thus prepared was subjected to wedge exposure using white light and then subjected to the following development processing.

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 4.75g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

(Bleach) Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water and adjust to pH = 6.0 using ammonia water.

(Fixing solution) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metabisulfite 2.3 g Water is added to adjust to 1 and 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.

Next, each sample obtained by the development processing is irradiated with red light and green light.
The MTF (Modulation Transfer Function) was determined at a spatial frequency of 40 lines / mm, and the effect of improving sharpness was measured. The values in the table are relative values with Sample 1 as 100, and a high value indicates good sharpness.

The desilvering property was determined by measuring the amount of silver remaining in the light-sensitive material after the completion of processing by a thick absorption method.

The results obtained by the above method are shown in Table-3.

As can be seen from Samples 1 to 3 in which the amount of the diffusible DIR compound added was increased only in the red-sensitive layer and Sample 4 in which the diffusible DIR compound was added only to the green-sensitive layer in Table 3, the diffusible DIR compound was red-sensitized. Even if the amount is increased in the layer or green sensitivity, the sharpness improving effect tends to be saturated, a large improving effect cannot be obtained, and the desilvering property is extremely deteriorated. This tendency becomes remarkable in Sample 5 in which a large amount of diffusive DIR was used in both the green-sensitive layer and the red-sensitive layer.

On the other hand, Samples 2 and B using a diffusible DIR compound only for red sensitivity
Compared with the sample 6 to which the AR coupler was added, the desilvering property was certainly improved, but the sharpness was almost unchanged.

However, the desilvering property of Sample 7 of the present invention was improved by comparing Samples 7 and 5 of the present invention in which a diffusible DIR compound was contained in both the red-sensitive layer and the green-sensitive layer and the BAR coupler of the present invention was used. In addition to improving sharpness, this effect has a red-sensitive layer,
Both green-sensitive layers have a diffusivity of 0.3 mol% or more with respect to 1 mol of silver.
With the sample 8 of the present invention having an IR layer, sharpness is remarkably improved and desilvering property is improved. It can be seen from Samples 9 to 13 of the present invention that various embodiments are also effective.

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Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support, said green-sensitive and red-sensitive silver halide emulsion. A silver halide color photographic light-sensitive material characterized in that at least one emulsion layer of each layer contains a diffusible DIR compound and at least one of said photographic constituent layers contains a bleaching accelerator releasing coupler.