JPH09203990A - Color negative silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color reproducibility by incorporating a green-sensitive sensitizing dye and a magenta coupler having a specified difference between the max. absorption wavelength of the spectral absorption spectrum of stain by the residual dye and that of a coloring dye by the coupler. SOLUTION: This sensitive material contains a green-sensitive sensitizing dye and a magenta coupler having 20-50nm, preferably 30-50nm difference between the max. absorption wavelength of the spectral absorption spectrum of stain by the residual dye and that of a coloring dye by the coupler. The deterioration of color reproducibility at the time of printing due to the overlapping of the spectral absorption spectrum of the stain and that of the coloring dye is avoided and a more significant effect is produced by using a compd. having a narrow half-width Δλ50, preferably <=110nm, especially preferably <=100nm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide light-sensitive material, and more particularly to a color negative silver halide light-sensitive material.

[0002]

2. Description of the Related Art The sensitizing dye contained in a silver halide light-sensitive material has been developed due to a rapid development process in recent years, a high aspect ratio of silver halide grains, and a large addition of a sensitizing dye accompanied with it. There is a problem in that coloring is left in the light-sensitive material without being completely dissolved during development processing. When the degree of the residual dye stain becomes severe, the linear correlation between the density of the negative film after development and the actual exposure amount is lost, so that the color reproducibility during printing is significantly impaired.
In addition, the density of residual dye stain generated tends to fluctuate depending on the storage condition of individual samples and the conditions during development.The larger the absolute value of the stain density, the larger the fluctuation range. Color reproducibility cannot be maintained.

Conventionally, in order to improve the residual dye stain, for example, JP-A-1-147451, JP-A-61-1
No. 294429, Japanese Patent Publication No. 45-32749,
Sensitizing dyes having a hydrophilic substituent such as a sulfamoyl group and a carbamoyl group described in 1-77843 and the like have been studied. However, if the sensitizing dye is increased in hydrophilicity, the adsorptivity generally decreases. In addition, not only the sensitivity is not sufficient, but also the residual degree of the residual dye stain has not reached a sufficiently satisfactory level. No. 3,282,933.
The sensitizing dyes described in the above publication also have an effect of improving the residual dye stain, but similarly, no sufficient effect has been obtained in terms of achieving both the residual dye stain and sensitivity.

As described above, the conventional method of reducing the level of the stain itself as a means for eliminating the influence of the residual dye stain on the color reproducibility has a serious problem that it adversely affects other photographic performances. It was happening.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is high sensitivity, excellent print level suitability, and color reproduction when printed out on photographic paper or the like. To provide a color negative silver halide light-sensitive material having improved properties.

[0006]

The object of the present invention has been achieved by the following constitutions.

(1) The difference between the maximum absorption wavelengths of the spectral absorption spectra of the residual dye stain and the coupler coloring dye is 2
A color negative silver halide photographic material comprising a green sensitizing dye having a wavelength of 0 to 50 nm and a magenta coupler.

That is, the present inventors have solved the above problems caused by residual dye stains that almost certainly occur when a sensitizing dye is used in a color negative silver halide light-sensitive material, by analyzing each of the residual dye stain and the coupler coloring dye. It is thought that this can be solved by setting the absorption spectrum ranges so that they do not overlap.Specifically, the difference in the maximum absorption wavelength of each spectral absorption spectrum is specified in a specific region, and the coupler coloring dye is set to a narrow wavelength region. If so, it is possible to control the influence on the sensitivity caused by the generation of the residual dye stain to a minimum, and therefore, it becomes easy to judge the negative, and
The inventors of the present invention have found that a color negative silver halide light-sensitive material having improved color reproducibility during printing, and further improved aging and processing dependence can be obtained.

Hereinafter, the present invention will be described in detail.

The color negative silver halide light-sensitive material of the present invention (hereinafter, simply referred to as light-sensitive material) has a difference in maximum absorption wavelength between the spectral absorption spectra of the residual dye stain and the coupler coloring dye of 20 to 50 nm. It is characterized by containing a dye and a magenta coupler.

The spectral absorption spectrum of residual dye stain in the present invention means the absorption waveform of each light-sensitive material was measured by a spectrophotometer after the total silver amount was removed by a fixing solution without treating the light-sensitive material with a developing solution. Show things.

Difference between the maximum absorption wavelength λd of the spectral absorption spectrum of the residual dye stain in the present invention and the maximum absorption wavelength λc of the spectral absorption spectrum of the coupler coloring dye | λd-λ
The range of c | is 20 to 50 nm, preferably 30 to
50 nm. This is to avoid the deterioration of color reproduction at the time of printing due to the overlap of the spectral absorption spectrum of the residual dye stain and the spectral absorption spectrum of the coloring dye, and by using a compound with a narrow half width, This is because a high effect can be obtained.

The maximum absorption wavelength and full width at half maximum of the spectral absorption spectrum of the coupler-coloring dye in the present invention are defined as the absorption waveform of the above residual dye stain spectrum as a baseline, and are subjected to ordinary exposure and development. The difference between the long-wave end and the short-wave end on the horizontal axis of the spectrum at the wavelength at the position showing the highest absorption in the absorption waveform obtained by measuring the material with a spectrophotometer and at half the height of the peak at that position. That is, the wavelength width is taken. In the present invention, the full width at half maximum Δλ50 is preferably 110 nm or less, more preferably 100 nm or less. Regarding the color reproducibility, for example, an object of neutral gray (object having a constant spectral reflectance or transmittance in the entire visible wavelength range) is photographed with a tungsten light source, and C.I.
I. E. FIG. Chromaticity diagram (Translated by Theory of Color Reproduction, Riki Uwatari and Tatsuro Kuniji.
The coordinates on page 6 and on pages 160 to 162) are obtained for the case where the tungsten light is used as the illumination light, and that point corresponds to C.I. I. E. FIG. It can be determined by whether or not the points on the chromaticity diagram match.

A method for obtaining the half-value width of the spectral absorption spectrum of the coupler coloring dye in the present invention will be described. A multi-layered light-sensitive material as described in Examples to be described later was prepared, and the light-sensitive material was used as Ratten No. 1 manufactured by Eastman Kodak Company.
Wedge exposure of green light is performed using a 99 filter, and ordinary development as described in the same embodiment is performed. The spectral transmission density of the light-sensitive material thus obtained at 450 to 650 nm is measured, and the wavelength difference between the long-wave end and the short-wave end at a transmission density of 50% of the transmission density a at the maximum absorption wavelength of the light-sensitive material is determined by half. Price range In the present invention, the value of the transmission density a is not particularly limited, but is preferably 0.5 to 2.5, more preferably 0.6 to 2.0.

In the present invention, the silver halide emulsion can be achieved by using the spectral sensitizing dye represented by the following general formula (1) alone or in combination, but it is not always limited to these spectral sensitizing dyes. Not something.

[0016]

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In the formula, R ₁ and R ₂ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group. It represents a substituent selected from a ring group. R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Z represents an atomic group necessary for forming a substituted or unsubstituted benzimidazole nucleus. X represents a charge balancing counter ion, and n represents a numerical value for controlling the charge of the whole molecule. Y represents a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, V ₁ , V ₂ , V ₃ and V ₄ are each a hydrogen atom or a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a cyano _{group, -OR 4, -COR 4, -COOR} 4, -CON
_{(R 4) R 5, -N} (R 4) COR 5, -N (R 4) R 5, -
_{SO 2 N (R 4) R} 5, -N (R 4) SO 2 R 5, -SO
₂ R ₄ represents a substituent selected from a heterocyclic group, and R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
V ₁ , V ₂ , V ₃ and V ₄ do not simultaneously become hydrogen atoms.

Examples of the alkyl group represented by R ₁ and R ₂ in the general formula (1) include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n- Examples thereof include a pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group and an n-dodecyl group. These alkyl groups further include alkenyl groups (eg vinyl group, allyl group etc.), alkynyl groups (eg propargyl group etc.), aryl groups (eg phenyl group, naphthyl group etc.), heterocyclic groups (eg pyridyl group). Group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, virazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc., halogen atom (for example, chlorine atom) , Bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, n-
Pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group, n-dodecyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (For example, methyloxycarbonyl group, ethyloxycarbonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxy) Carbonyl group, etc., sulfonamide group (for example, methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n-hexylsulfonylamino group, cyclohexylsulfonylamino group, n-octylsulfur group) Niruamino group, n- dodecylsulfonyl group, etc. phenylsulfonylamino group),
Sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group,
n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-
Octylaminosulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc., ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group) , N-octylureido group, n-dodecylureido group, phenylureido group, naphthylureido group, 2-
Pyridylaminoureido group, etc., acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, n-pentylcarbonyl group, cyclohexylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, Phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, n-octylaminocarbonyl group to 2-ethylhexylaminocarbamoyl group, n-dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2- Lysyl amino group etc.),
Amido group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, n-octylaminocarbonyl group , Dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, etc.),
Sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.) , Amino groups (for example, amino groups, ethylamino groups, dimethylamino groups, n-butylamino groups, cyclopentylamino groups, 2
-Ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group and the like.

Examples of the alkenyl group represented by R ₁ and R ₂ include a vinyl group and an allyl group. These groups can be substituted with an alkyl group represented by R ₁ or R ₂ and a group similar to the group shown as the substituent of the alkyl group.

Examples of the alkynyl group represented by R ₁ and R ₂ include a propargyl group and the like. These groups can be substituted with an alkyl group represented by R ₁ or R ₂ and a group similar to the group shown as the substituent of the alkyl group.

The aryl group represented by R ₁ and R ₂ is
Examples thereof include a phenyl group and a naphthyl group. These groups can be substituted with an alkyl group represented by R ₁ or R ₂ and a group similar to the group shown as the substituent of the alkyl group.

The heterocyclic group represented by R ₁ and R ₂ is a pyridyl group (eg, 2-pyridyl group, 3-pyridyl group,
4-pyridyl group, etc.) thiazolyl group, oxazolyl group, imidazolyl group, furyl group, thienyl group, pyrrolyl group, pyrazinyl group, imidazolyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyldinyl group, piperidinyl group, pyrazolyl group , A tetrazolyl group and the like. These groups can be substituted with an alkyl group represented by R ₁ or R ₂ and a group similar to the group shown as the substituent of the alkyl group.

R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Particularly, an ethyl group is preferable.

The benzimidazole nucleus represented by Z includes those having a substituent.

Specific examples of the substituent include the following.

Acyloxy groups (eg acetoxy, propionoxy etc.), alkoxycarnyl groups (eg
Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl, tolyloxycarbonyl,
β-naphthoxycarbonyl etc.), halogen atom (eg chloro atom, bromine atom, iodine atom, fluorine atom etc.), acyl group (eg acetyl, propionyl, benzoyl etc.), alkylsulfonyl group (eg methylsulfonyl, difluoro) Methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl (eg, phenylsulfonyl, p-tolylsulfonyl, etc.), carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, etc.), sulfamoyl group (eg, sulfamoyl, N -Methylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, etc.) and perfluorohydrocarbon group (eg, trifluoromethyl group, perfluorobutyl group, perfluorophenyl group, etc.) groups.

(X) n is included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye. Therefore n
Can take an appropriate value of 0 or more as required.
Typical cations are inorganic or organic ammonium ions, alkali metal ions, alkaline earth metal ions, while anions such as halogen anions,
Substituted aryl sulfonate ion, alkyl sulfate ion,
Examples thereof include thiocyanate ion, perchlorate ion, tetrafluoroborate ion and the like.

In the general formula (1), the alkyl group represented by R ₁ and R ₂ preferably has 1 carbon atom.
To 7 substituted or unsubstituted alkyl groups having 1 to 1 carbon atoms.
4 is particularly preferable. At least one of R _{1 and} R ₂ is preferably a substituent selected from a sulfoalkyl group or a carboxyalkyl group.

As the substituted alkyl group represented by R ₁ and R ₂ , alkyl groups containing a substituent which dissociates in an alkaline solution as described in JP-A-5-93978 and 6-82948 are also used in the present invention. It is preferably used.

In the general formula (1), V ₁ , V ₂ , V ₃ ,
V ₄ preferably used is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, an aryl group, or 4 carbon atoms.
The following alkoxy groups, aryloxy groups, acyl groups having 6 or less carbon atoms, alkoxycarbonyl groups having 8 or less carbon atoms,
A hydroxy group and a trifluoromethyl group are preferable, and a hydrogen atom, a halogen atom, an alkyl group having 3 or less carbon atoms, a phenyl group, an alkoxy group having 3 or less carbon atoms, and a trifluoromethyl group are more preferable. However, V ₁ , V ₂ , V ₃ , V ₄
But do not become hydrogen atoms at the same time.

In the general formula (1), the ring formed by V ₁ and V ₂ , V ₂ and V ₃ or V ₃ and V ₄ is, for example, benzene ring, thiophene ring, pyridine ring, furan ring, pyrimidine ring. , Cyclohexene ring, pyran ring, pyrrole ring, pyrazine ring, indole ring and the like. These rings can be substituted with an alkyl group represented by R ₁ or R ₂ and a group similar to the group shown as the substituent of the alkyl group.

Specific examples of the spectral sensitizing dye represented by the general formula (1) which are preferably used in the present invention are shown below, but the present invention is not limited thereto.

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[0037]

[Chemical 6]

To incorporate the spectral sensitizing dye into the silver halide emulsion, it may be added directly to the emulsion, or it may be added with water beforehand.
It may be added to the emulsion by dissolving it in a hydrophilic solvent such as methanol, ethanol, methyl cellosolve, N, N-dimethylformamide or the like alone or in a mixed solvent. or,
You may disperse | distribute in water or gelatin aqueous solution, without using these solvents.

The tabular silver halide grain-containing emulsion useful in the present invention is formed by first preparing a small size cubic (100) seed grain emulsion and ripening it.

The formation of small size cubic seed grain emulsions can be carried out by conventional techniques. A preferable seed grain emulsion is prepared by the double jet method. That is, an aqueous solution of silver salt such as silver nitrate and an aqueous solution of halide of sodium or potassium are simultaneously injected into one reaction vessel. The concentration of these aqueous solutions can be, for example, from about 0.2 mol to saturation, but it is preferable to carry out the stirring rapidly and uniformly, and a concentration of less than 4 mol, preferably 2 to 0.1 mol is used. It is preferable.

It is preferred to adjust the pAg in the reaction vessel during precipitation to form the preferred seed particles. To achieve this, pAg is preferably kept in the range of 2.5 to 8.5. When pAg is smaller or larger than this range, grains having twin planes are formed, which is not preferable. Further, in view of the stability of produced ions, pAg in which the equilibrium points, that is, the concentrations of silver and halide ions are stoichiometrically equal, are not preferable. To finally obtain a high aspect ratio silver halide emulsion, pAg
Is preferably 6.5 to 8.3, and more preferably 7.0 to 8.0.

The seed grain precipitation temperature affects the optimum value of pAg, but can be any temperature known to be useful for preparing emulsions of desired grain size. The preferred temperature is in the range of about 25-75 ° C, more preferably 45 ° C or lower.

The pH is preferably maintained in the range of about 2.0 to 5.0 in order to suppress ripening during the formation of seed particles. Nitric acid, sulfuric acid or acetic acid can be used to adjust the pH.

After precipitation, tabular silver halide grain-containing emulsions are prepared by Ostwald ripening the cubic seed grain emulsions. It is preferable to adjust pAg in the reaction vessel during aging. The aspect ratio can be adjusted by setting the pAg during ripening to be 5.2 to 6.2, and when the pAg is made smaller than this, the aspect ratio of the tabular silver halide grains obtained becomes too small. If it is too large, ripening is hindered. A more preferable pAg range for obtaining tabular silver halide grains having a high aspect ratio is 5.5 to 5.8.

Ripening temperature affects the optimum value of pAg, but can be any temperature known to be useful for preparing emulsions of desired grain size. The preferred temperature is in the range of about 50-80 ° C.

The pH is about 5.0 to accelerate aging.
It is preferable to maintain the range of -9.0. Sodium hydroxide and potassium hydroxide can be used to adjust the pH.

The silver halide emulsion prepared by the above method preferably has an aspect ratio of at least 2 and less than 20, and the grain size is 0.2 to 3.0 in terms of equivalent spherical diameter.
μm is preferred. The average aspect ratio in the present invention means the average value of the ratio of the diameter to the thickness of the silver halide grains. Here, the diameter means the diameter of a circle having an area equal to the projected area of the grain when the silver halide grain is observed with an electron microscope. As an example of the method of measuring the aspect ratio, there is a method of taking a transmission electron microscope photograph by the replica method and obtaining the circle equivalent system and the thickness of the projected area of each particle. In this case, the thickness is calculated from the length of the shadow of the replica. The spectral sensitizing dye may be added to the silver halide emulsion at any time, but it may be added to the photosensitive silver halide grains after the grain formation in combination with the chemical sensitizer until the end of the chemical sensitization. Is preferred. The addition amount of the spectral sensitizing dye is not uniform depending on the type of the dye, the shape and size of the silver halide grains or the purpose of the spectral sensitization, but the average coverage ratio θ when the silver halide grains in the above range are used. Is preferably 50 to 150% so that the effect of the present invention can be obtained with high sensitivity, and more preferably θ is 70 to 150%.
Here, the coverage θ means an area ratio of the sensitizing dye adsorbed to the surface area of the silver halide grain, and can be easily measured and calculated in the field.

The magenta coupler used in the present invention is not particularly limited, and conventionally known ones can be used, but the half width is preferably 100 nm or less, and its structure is not particularly limited. It may be a so-called 2-equivalent coupler or a 4-equivalent coupler, and may be a pyrazolone type or a pyrazolotriazole type. Also, a polymer type coupler may be used. The above couplers may be used alone or in combination. Examples of couplers that can be preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0049]

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[0059]

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[0060]

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[0063]

[Chemical 21]

[0064]

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[0065]

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[0067]

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[0068]

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[0069]

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[0070]

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To disperse the coupler according to the present invention in a gelatin solution, a solution of the coupler, a high boiling solvent, a surfactant, a low boiling solvent, and other additives is mixed with an aqueous solution of gelatin and a surfactant. Alternatively, a method of removing the low boiling point organic solvent by stirring, emulsifying and dispersing, and evaporating may be used, or a coupler, a high boiling point solvent, a surfactant, sodium hydroxide, n-propanol, and other additives may be uniformly added. A method of neutralizing and precipitating and dispersing the aqueous solution, or after making it into a fine powder by using high energy such as ultrasonic waves, adding it to a gelatin solution and dispersing it, wetting the coupler with water or a poor solvent,
The presence of a dispersion aid or hydrophilic colloid, or a dispersion method that does not substantially contain a high boiling point solvent, such as a method of dispersing fine particles at a high temperature in a mill using a medium having a narrow particle size distribution, results in a photosensitive material It is preferable because it leads to thinning.

A substance other than gelatin having adsorptivity to silver halide grains may be added to the silver halide emulsion at the time of preparation (including preparation of seed emulsion). Such adsorbents are useful, for example, compounds or heavy metal ions used in the art as spectral sensitizing dyes, antifoggants, or stabilizers. The above-mentioned adsorbent is disclosed in JP-A-62-704.
Specific examples are described in No. 0. It is preferable to add at least one of an antifoggant and a stabilizer among the adsorbents at the time of preparation of the seed emulsion from the viewpoint of reducing fog of the emulsion and improving stability over time. Among the antifoggants and stabilizers, a heterocyclic mercapto compound and / or an azaindene compound is particularly preferable. Specific examples of more preferable heterocyclic mercapto compounds and azaindene compounds are described in detail in JP-A-63-41848, and these can be used. The amount of the above heterocyclic mercapto compound and azaindene compound added is not limited, but is preferably 1 × 10 ⁻⁵ per mol of silver halide.
To 3 × 10 ⁻² mol, more preferably 5 × 10 ^{−5 to} 3 × 1
It is 0 ^-3 mol. This amount is appropriately selected depending on the production conditions of the silver halide grains, the average grain size, and the kind of the above compound.

In the present invention, the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are
Disclosure No. 17643, No. 1871
6 and No. 6 308119 (Respectively RD17
643, RD18716, RD308119). The places to be described are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E to J Items 23 to 24 648-9 Supersensitizer 996 IV-AE, Item 23-23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI Known photographic additives usable in the present invention are also the above Research Disclosures. It is described in. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII-C 25-26 649 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plastic Agent 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / coating aid 1005 XI 27 650 Matting agent 1007 XVI 26 to 27 650 Developer (contained in light-sensitive material) 1011 XXB Item The light-sensitive material of the present invention is RD17643 described above. 28-29
Page, RD18716, page 647 and RD308119
Development processing can be carried out by the usual method described in XVII.

[0076]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. In all the examples, the addition amount in the silver halide light-sensitive material is shown in grams per 1 m ² unless otherwise specified. or,
Silver halide and colloidal silver are shown in terms of silver. Further, the sensitizing dye is shown in mol / silver 1 mol.

Example 1 On a triacetyl cellulose film support, layers having the following compositions were sequentially formed from the support side to prepare a multilayer photosensitive material 101.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-4) 0.17 Gelatin 0.80 Third layer: low sensitivity red sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0. 35 Sensitizing dye (SD-1) 2.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.4 × 10 ⁻⁵ Sensitizing dye ( SD-4) 0.7 × 10 ^-4 Cyan coupler (C-2) 0.53 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 Fourth layer: Medium sensitivity red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye ( D-1) 1.7 × 10 ^-4 Sensitizing dye (SD-2) 0.86 × 10 -4 Sensitizing dye (SD-3) 1.15 × 10 -5 Sensitizing dye (SD-4) 0 .86 × 10 ⁻⁴ Cyan coupler (C-2) 0.33 DIR compound (D-1) 0.02 High boiling point solvent (OIL-3) 0.16 Gelatin 0.79 Fifth layer: High sensitivity red sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-1) 0.14 High boiling point solvent (OIL-1) 0.14 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-) 4) 0.11 gelatin 0.80 Seventh layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion E-1 0.50 Sensitizing dye (I-1) 3.2 × 10 ⁻⁴ Sensitizing dye ( I-2) 1.1 × 10 ⁻⁴ Sensitizing dye (I-3) 2.2 × 10 ⁻⁵ Magenta coupler (M-1) 0.33 High boiling point solvent (OIL-2) 0.16 Gelatin 70 Eighth Layer: Intermediate Layer Gelatin 0.41 Ninth Layer: Medium-Sensitivity Green Sensitive Layer Silver Iodobromide E-2 0.64 Sensitizing Dye (I-1) 2.8 × 10 ⁻⁴ Sensitizing Dye ( I-2) 0.97 × 10 ^-4 sensitizing dye (I-3) 1.8 × 10 ^-5 magenta coupler (M-1) 0.33 DIR compound (D-2) 0.025 DIR compound (D -3) 0.025 High boiling point solvent (OIL-2) 0.12 Gelatin 0.05 Tenth layer: High sensitivity green sensitive layer Silver iodobromide emulsion E-3 0.95 Sensitizing dye (I-1) 2 .8 × 10 ^-4 sensitizing dye (I-2) 0.96 × 10 -4 sensitizing dye (I-3) 1.8 × 10 -5 magenta coupler (M-1) 0.33 high boiling Solvent (OIL-2) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-4) 0.19 Gelatin 1.10 12th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-5) 6.3 × 10 ^{− 4} Sensitizing dye (SD-6) 0.86 × 10 ^-4 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D -5) 0.02 High boiling point solvent (OIL-4) 0.42 Gelatin 1.40 13th layer: High sensitivity blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitization Dye (SD-5) 8.0 × 10 ⁻⁵ Sensitizing Dye (SD-7) 3. 1 × 10 ⁻⁵ Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-4) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm , Silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0 .65 Fifteenth layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1, a dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggants AF-1, AF-2, AF-3, average molecular weight: 10,000 and average molecular weight: 1,100,
000 of two AF-4 and preservative DI-1 were added. The composition used for the above sample is as follows.

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The contents of the silver halide used are shown in Table 1.

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[Table 1]

Samples 102 to 108 were prepared by changing the silver halide emulsion, the sensitizing dye and the coupler of the green sensitive layer in the multilayer sample 101 prepared as described above as follows.

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[Table 2]

A color rendition chart manufactured by Macbeth was photographed using these samples 101 to 108, and the following color development processing was performed.

(Processing Step) 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Water washing 3 minutes and 15 seconds 24 to 41 ° C 4. 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Water washing 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ° C 7. Drying 50 ° C or less The composition of the processing solution used in each processing step is as follows.

(Color Developer) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2. 00 g anhydrous potassium carbonate 37.50 g sodium bromide 1.30 g nitrilotriacetic acid trisodium salt (monohydrate) 2.50 g potassium hydroxide 1.00 g Water is added to make 1 liter and pH is adjusted to 10.1.

(Bleach) Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and pH was adjusted to 6 with ammonia water. Adjust to 0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter. From the obtained film of each sample, color paper (Konica Color PC Paper) was printed so that the gray having an optical density of 0.7 in the above chart had the same density.

(Evaluation) The obtained prints were examined and evaluated according to the following criteria whether or not the original color tone of the chart was reproduced.

◎ The actual color tone is accurately reproduced. ○ The color tone matches the actual color. △ Some deviation from the actual color × Large deviation from the actual color.

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[Table 3]

As is clear from Table 3, according to the present invention, the samples 101 to 105 and the samples 101 to 105 in which the difference between the maximum absorption wavelengths of the spectral absorption spectra of the green-sensitive sensitizing dye and the magenta coupler is in the range of 20 to 50 nm. 108 has an excellent effect that the color reproducibility at the time of printing is remarkably improved. In addition, sample 10 of the present invention and sample 10 of comparison
The addition amount of the green sensitizing dye in each of the 9th layer of No. 6 was about twice as much as the above-mentioned addition amount (corresponding to 70% coverage) (coverage of 14%).
(Compared to 0%), the sample 101 of the present invention obtained higher sensitivity without impairing the color reproducibility, but the comparative sample 107 has the same sensitivity and the color difference due to the increase of the residual dye stain is caused. As a result, the reproducibility is significantly impaired, and it is understood that the present invention can provide a color negative silver halide light-sensitive material having high sensitivity and high color reproducibility.

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According to the present invention, there is an excellent effect that the color reproducibility during printing is remarkably improved.

Claims (2)

[Claims] 1. The difference between the maximum absorption wavelengths of the spectral absorption spectra of the residual dye stain and the coupler coloring dye is 20 to 20.
A color negative silver halide light-sensitive material comprising a green sensitizing dye having a wavelength of 50 nm and a magenta coupler. 2. The color negative silver halide photographic material according to claim 1, wherein the half-value width of the spectral absorption spectrum of the coupler coloring dye is 110 nm or less.