JP3030587B2 - Silver halide photographic light-sensitive material and processing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material (hereinafter also simply referred to as "photosensitive material") and a processing method thereof.
The present invention also relates to a photosensitive material having excellent storage stability before exposure and performance stability during continuous processing, and a method for processing a photosensitive material capable of reducing the replenishment of a color developing solution.

[0002]

BACKGROUND OF THE INVENTION Recently developed 1H-pyrazolo- [1,5-b] -1,
Unlike the conventionally used 5-pyrazolone magenta coupler, the 2,4-triazole magenta coupler has the characteristic that the coloring dye has excellent color reproducibility because the coloring dye does not have side absorption around 430 nm. It is known that the obtained magenta dye has poor light fastness.

On the other hand, for example, Japanese Patent Application Laid-Open No. 60-262159 discloses that the use of a phenol or phenyl ether compound is used to improve the light fastness, but the effect is still unsatisfactory. Instead, further improvements are desired.

Attempts to improve the light fastness have also been made from the viewpoint of the coupler structure. For example, JP-A-63-307453 and JP-A-64-66.
No. 646, JP-A-2-161430, JP-A-2-96241, JP-A-2-111943
The 1H-pyrazolo- [1,5-b] -1,2,4-triazole-based magenta couplers having a bulky substituent at the 6-position described in Known as an excellent coupler. However, with these couplers,
It has been revealed that fluctuations in photographic performance when raw materials are stored unexposed (raw storability) and fluctuations in photographic performance when running continuously in a process involving a color developer increase. There is a need for improvements.

On the other hand, in the method of continuously running a photosensitive material, the running process is performed while replenishing each processing solution with a replenisher in order to prevent a change in the characteristics of a finished print due to a change in the concentration of the processing solution. This is commonly done. However, in this case, a large amount of overflow liquid is generated with the replenishment of the replenisher concentration, which is a serious problem in terms of pollution and cost. Accordingly, it has been strongly desired in recent years to reduce the amount of replenisher of the color developing solution (reduce the amount of replenisher) to reduce the amount of overflow solution, and to further reduce the amount of replenisher until no overflow solution is generated.

However, the light-sensitive material containing the 1H-pyrazolo- [1,5-b] -1,2,4-triazole-based magenta coupler having a bulky substituent at the 6-position is prepared by reducing the replenishment of color. When the developer is continuously processed with a developer, the above-described problem that the photographic performance fluctuates significantly becomes apparent, and improvement thereof is desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide excellent color reproducibility and fastness of a dye image, and a change or continuous change in photographic performance during unexposed storage. An object of the present invention is to provide a silver halide photographic light-sensitive material in which fluctuations in photographic performance during dynamic running processing are reduced, and a processing method for the light-sensitive material capable of reducing the replenishment of a color developing solution.

[0008]

The object of the present invention is to provide a silver halide photographic light-sensitive material having a photographic component layer comprising at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is provided. Contains a magenta coupler represented by the following general formula [MI], and the total amount of gelatin contained in the silver halide photographic material is 7.0.
g / m ² , and the iron content of gelatin contained in the silver halide photographic material is less than 5 ppm.

[0009]

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In the formula, J represents —O—, —S— or —N (R ₃ ) —, R ₃ represents a hydrogen atom or a substituent, and n represents 0 or 1.
Represents When n = 0, R ₁ represents an alkyl group or an aryl group having 2 or more carbon atoms, and when n = 1, R ₁ represents an alkyl group or an aryl group.

R ₂ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent.

The replenishing amount of the above photosensitive material is 1
A continuous processing with a color developing solution of 20 to 60 ml per m ² is a preferable processing method because the effects of the present invention are effectively exhibited.

[0013]

DETAILED DESCRIPTION OF THE INVENTION First, the magenta coupler represented by the general formula [MI] will be described in detail.

As the alkyl group represented by R ₁ , n =
When it is 0, it preferably has 2 to 32 carbon atoms, and may be linear or branched, but is preferably a branched alkyl group. n = 1
In this case, those having 1 to 32 carbon atoms are preferable, and they may be linear or branched. The aryl group represented by R ₁ is preferably a phenyl group.

The alkyl group and aryl group represented by R ₁ may further have a substituent.

The substituents represented by R ₂ and R ₃ are not particularly limited, but typically include groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Is, in addition, a halogen atom and cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino , Imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbons Compound residue and the like are also mentioned.

The alkyl group represented by R ₂ and R ₃ preferably has 1 to 32 carbon atoms, and may be linear or branched.
The aryl group represented by R ₂ and R ₃ is preferably a phenyl group.

The acylamino groups represented by R ₂ and R ₃ include an alkylcarbonylamino group, an arylcarbonylamino group and the like. Examples of the sulfonamide group represented by R ₂ and R ₃ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkylthio group represented by R _2, R _3, alkyl moieties in the arylthio group, the aryl component, an alkyl group represented by R _2, R _3, and an aryl group.

The alkenyl group represented by R ₂ and R ₃ is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. It may be a branch. The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

Examples of the sulfonyl group represented by R ₂ and R ₃ include an alkylsulfonyl group and an arylsulfonyl group;
As a sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, etc .; As a phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an arylphosphonyl group, an aryloxyphosphonyl group, etc .; As an acyl group, an alkylcarbonyl group, Arylcarboxy group, arylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc. A carbamoyloxy group such as an alkylcarbamoyloxy group or an arylcarbamoyloxy group; a ureido group such as an alkylureido group or an arylureido group; The alkyl sulfamoylamino group, an aryl sulfamoylamino group group; preferably has 5 to 7 membered the heterocyclic group, specifically 2-
A furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6-tetrahydropyranyl Ru-2-oxy group, 1-phenyltetrazole-
5-oxy group and the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4-diphenoxy-1,3,5 -Triazole-6-thio group, etc .; siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide groups include succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutar Imido group, etc .; spiro compound residue as spiro [3.3]
Heptane-1-yl and the like. Examples of the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^37] decane-1-yl, 7,7-dimethyl-bicyclo [2.2 .1] heptane-1-yl and the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include, for example, a halogen atom (chlorine, bromine, fluorine, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, alkyloxalyloxy,
Alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, N
Each group such as a 6π- or 10π-electron-containing nitrogen-containing heterocyclic ring bonded by an atom is exemplified.

Of the magenta couplers represented by the general formula [MI], particularly preferred are those represented by the following general formulas [M-II] and [M-III].

[0024]

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In the formula, R ₄ represents an i-propyl or t-butyl group, R ₅ represents a substituent, and R ₆ represents an alkyl group or an aryl group. X ₁ represents a group capable of leaving by reaction with an oxidized form of the color developing agent.

The alkyl group represented by R ₆ preferably has 1 to 32 carbon atoms, and may be linear or branched.
The aryl group represented by R ₆ is preferably a phenyl group. These alkyl groups and aryl groups may further have a substituent.

Examples of the substituent represented by R ₅ include the substituents represented by R ₂ in the above formula [MI], preferably an alkyl group or an aryl group, and particularly preferably General formula [M-IV] or General formula [MV]
Is a group represented by

[0028]

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In the formula, Z represents a carbon atom or a sulfur atom;
m represents 1 when Z is a carbon atom, and represents 2 when Z is a sulfur atom. R ₇ represents an alkyl group or an aryl group.

The alkyl group represented by R ₇ preferably has 1 to 32 carbon atoms, and may be linear or branched. The aryl group represented by R ₇ is preferably a phenyl group. These alkyl groups and aryl groups may further have a substituent.

[0031]

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In the formula, R ₈ represents a substituent, and 1 represents an integer of 0 to 5.

As the substituent represented by R ₈ , the substituent represented by R ₂ in the general formula [MI] can be mentioned.

The group capable of leaving by reaction with the oxidized form of the color developing agent represented by X ₁ includes the group represented by the aforementioned general formula [M-
And a group represented by X in formula (I), preferably a fluorine atom, a chlorine atom or the following general formulas (M-VI) to (M
-VIII].

[0035]

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In the formula, R ₉ represents a substituent, and p represents an integer of 0 to 5.

[0037]

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In the formula, R ₁₀ and R ₁₁ represent a substituent, and q is 0
Represents an integer of from 4 to 4.

[0039]

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In the formula, Y represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring together with a nitrogen atom.

Examples of the substituents represented by R ₉ , R ₁₀ and R ₁₁ include the substituents represented by R ₂ in the above formula [MI], wherein R ₁₀ is an oxygen atom or a nitrogen atom. Is preferable, and an alkoxy group or an acylamino group is particularly preferable.

The general formula [M-
Representative specific examples of the magenta coupler represented by I] (referred to as the magenta coupler of the present invention) are shown below, but it should not be construed that the invention is limited thereto.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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In addition to the specific examples described above, examples of the magenta coupler of the present invention include exemplified compounds (1) to (15) described on pages 6 to 7 of JP-A-63-307453 and JP-A 64-7047. Exemplified compounds (1) to (31), (46) to (50), (52) to (60), and
Exemplified compounds I-1 to I-2 described on pages 3 to 5 of 64-66646
4, exemplified compounds described on pages 5 to 6 of JP-A-1-277236
(6)-(8), (10), (12)-(15), (18)-(20), 2-160233
Compounds M-4 to M-35, M-3 described on pages 11 to 18 of
7, M-50 to M-53, exemplified compounds M-1 to M-89 described on pages 5 to 9 of JP-A No. 2-14430, and exemplified compounds M- described on pages 5 to 8 of JP-A No. 2-296241. 1 to M-6, M-8 to M-12, M-14
Compounds M-2 to M-29, m-2 to m-28 and 3-200143 described on pages 5 to 7 and page 35 of JP-A-3-13845.
Compounds M-3 to M-5, M-
Exemplary compounds M-1 to M-38 described on pages 6 to 10 of Nos. 7 to M-12, M-14, M-16 to M-30 and 3-138644 can be exemplified. Further, the magenta coupler of the present invention can be synthesized according to the method described in the above patent.

The magenta coupler of the present invention is generally used in an amount of 1 × 10 ^-3 to 1, preferably 1 × 10 ^-2 per mol of silver halide.
It is used in the range of ７7 × 10 ⁻¹ mol.

Next, the gelatin used in the present invention will be described.

Gelatin contains various heavy metals such as iron, copper, zinc, and manganese as impurities.
Contains 20ppm iron ions.

The iron content of gelatin contained in the light-sensitive material of the present invention is less than 5 ppm, more preferably less than 3 ppm. In the present invention, the iron content of gelatin is the content of iron and iron ions contained in gelatin, and is determined by the Pagii method (published by the Joint Council for the Test of Gelatin for Photography, 6th edition,
It is measured based on the method (atomic absorption method) described in October 1987).

When the light-sensitive material of the present invention contains a plurality of different gelatins, the average value of the iron content of all the gelatins contained in the light-sensitive material, that is, the light-sensitive material with respect to the total gelatin contained in the light-sensitive materials Is defined by the weight ratio of iron in the total gelatin contained in the gelatin.

As a method for reducing metal ions in gelatin, ion exchange treatment using an ion exchange resin is generally performed. However, it is not always effective for removing a trace amount of iron ions contained in gelatin. Further, methods such as the use of a chelate resin, solvent extraction, and foam separation are also used.
Producing gelatin using a raw material having a low iron content is effective in reducing the iron content in gelatin, and further preventing the mixing of iron from a production apparatus in a gelatin production process, Removal of the mixed iron powder by a magnet or the like is also effective in reducing the iron content in gelatin.

The gelatin used in the present invention has a jelly strength (based on the Pagui's method) of preferably at least 250 g, particularly preferably at least 270 g.

The calcium content of the gelatin used in the present invention (according to the Pagui's method) is preferably at most 1,000 ppm, particularly preferably at most 500 ppm. In order to reduce the calcium content in gelatin, generally, treatment with an ion exchange resin column is preferably used.

The molecular weight of the gelatin of the present invention is not particularly limited, but is preferably 10,000 to 200,000 in average molecular weight.

The total amount of gelatin contained in the light-sensitive material of the present invention is less than 7.0 g / m ² . Although the lower limit is not particularly limited, it is generally preferably at least 3.0 g / m ² from the viewpoint of physical properties or photographic performance. The amount of gelatin was determined to be 11.0 by the moisture measurement method described in the Pagii method.
% Of water-containing gelatin.

The gelatin contained in the light-sensitive material of the present invention is hardened by a hardener.

The hardening system that can be used is not particularly limited, and hardening agents known in the photographic industry, for example, aldehyde-based, active vinyl-based, active halogen-based, epoxy-based, ethyleneimine-based, and methanesulfonic acid ester-based hardening agents. ,
Examples thereof include carboxyl-activated hardeners such as carbodiimide-based, isoxazole-based, and carbamoylpyridinium salts, and polymer hardeners. Particularly preferred hardeners are vinyl sulfone hardeners (for example, compounds H-1 to H-1 described in JP-A-2-1888753, pp. 13-14).
-24, etc.) and / or chlorotriazine hardeners (for example, compound II-1 described in JP-A-1-216340, pp. 20-21).
To II-13, III-1 to III-10, etc.) or JP-A-2-82.
No. 237, No. 1-129245 and the like.

The swelling ratio of the light-sensitive material of the present invention (the thickness of the hydrophilic colloid layer in the processing solution / the thickness of the hydrophilic colloid layer in a dry state) is preferably from 1.5 to 4.0, more preferably from 2.0 to 3.0. It is.

The silver halide used in the silver halide emulsion layer of the present invention includes silver halide, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like. Silver halide.

The silver halide grains preferably used in the present invention have a silver chloride content of 95 mol% or more, a silver bromide content of 5 mol% or less, and a silver iodide content of 0.5 mol%.
The following is preferred. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or as a mixture with other silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of 95 mol% or less. Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 95 mol% or more, a silver chloride content of 95 mol% of all silver halide grains contained in the emulsion layer is contained. The proportion of the silver halide grains is at least 60% by weight, preferably at least 80% by weight. The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.2 to 1.6 μm, and more preferably 0.25 to 1.2 in consideration of other photographic properties such as rapid processing and sensitivity.
It is in the range of μm.

The size distribution of the silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a variation coefficient of preferably 0.22 or less, more preferably 0.15 or less, in the grain size distribution of the silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = standard deviation of particle size distribution / average particle size The silver halide grains used in the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method.
The particles may be grown at one time, or may be grown after seed particles are formed. The method of producing the seed particles and the method of growing them may be the same or different. The form of reacting a soluble silver salt with a soluble halide salt includes a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like.
Either one may be used, but one obtained by the simultaneous mixing method is preferable. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

If necessary, a silver halide solvent such as thioether or imidazole may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. U.S. Pat.Nos. 4,183,756 and 4,225,666;
No. 55-26589, Japanese Patent Publication No. 55-42737, etc.
Photographic Science (J.Photgr.Sc
i.), 21 , 39 (1973), etc., particles having a shape such as an octahedron, a tetrahedron, or a dodecahedron can be produced and used. Further, particles having a twin plane may be used. The silver halide grains used in the present invention may be grains having a single shape or a mixture of grains having various shapes.

In the present invention, in the process of forming and / or growing silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt) and rhodium salt (including complex salt) are used. ), An iron salt (including a complex salt) to add a metal ion to be contained inside the particle and / or on the surface of the particle. Alternatively, a reduction sensitizing nucleus can be provided on the surface of the grain.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or they may be kept contained.

In the present invention, the silver halide grains used in the emulsion may be grains whose latent image is mainly formed on the surface, or grains mainly formed inside the grain. Preferably, the latent image is a particle mainly formed on the surface.

In the present invention, the emulsion is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization using gold or another noble metal compound. Sensing methods or the like can be used alone or in combination.

The emulsion can be optically sensitized to a desired wavelength region by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, a hemioxanol dye, and the like can be used. Specific examples thereof include, for example, the exemplified compound BS- described in Japanese Patent Application No. 2-76278, pp. 76-82.
1 to BS-9, GS-1 to GS-5, RS-1 to RS-
8 and IRS-1 to IRS-10. Examples of supersensitizers that can be used in combination with these include, for example, the exemplified compounds SS-1 to SS-9 described in Japanese Patent Application No. 2-76278, pp. 84-85.

The dye-forming coupler used in the light-sensitive material of the present invention is usually selected so that a dye absorbing the light in the photosensitive spectrum of the emulsion layer is formed for each emulsion layer. The emulsion layer contains a yellow dye-forming coupler, the green-sensitive emulsion layer contains a magenta dye-forming coupler,
A cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a color light-sensitive material may be produced in a manner different from the above-mentioned combination depending on the purpose.

In the present invention, an acylacetanilide coupler can be preferably used as a yellow dye-forming coupler. Among them, benzoylacetoanilide compounds and pivaloylacetoanilide compounds are advantageous.

Hereinafter, specific examples of the yellow coupler preferably used in the present invention will be described.

[0079]

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[0080]

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[0081]

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Further, in addition to the above compounds, JP-A-63-856
Exemplified compounds Y-1 to Y-146 and 6 described in No. 31, pages 7 to 16
Exemplified compounds Y-1 to Y-9 described in 3-97951, pp. 6-10.
8, Exemplified compound Y- described in JP-A-1-156748, pages 18-20.
Illustrative compounds I-1 to I-50 described on pages 4 to 7 of JP-A-2-298943 and Illustrative compounds Y-1 to Y- described on pages 114 to 120 of JP-A-62-215272. 48.

In the present invention, naphthol-based couplers and phenol-based couplers can be preferably used as the cyan dye-forming coupler.

In addition to naphthol-based and phenol-based cyan couplers, JP-A-1-156748, JP-A-3-174153,
3-196039 and the like, imidazole cyan couplers and JP-A-2-136854, pyrazoloazole-based cyan couplers disclosed in JP-A-3-96039 and the like, pyrazoloazine-based cyan couplers, and further, 3-103848, same
No. 3-103849, a hydroxypyridine cyan coupler, a hydroxydiazine cyan coupler, an aminopyridine cyan coupler disclosed in JP-A-3-206450, etc. have color reproducibility, image preservability, and recoloring. It is excellent in properties and is advantageously used.

Hereinafter, specific examples of the cyan coupler used in the present invention will be shown.

[0086]

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[0087]

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[0088]

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A hydrophobic compound such as a dye-forming coupler is usually dissolved in a high-boiling organic solvent having a boiling point of about 150 ° C. or higher, if necessary, in combination with a low-boiling and / or water-soluble organic solvent. After emulsifying and dispersing using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic device using a surfactant in a hydrophilic binder, and then adding it to the intended hydrophilic colloid layer, Good.

Examples of the high boiling organic solvent used in the present invention include esters such as phthalic acid esters and phosphoric acid esters.
Examples thereof include organic acid amides, ketones, and hydrocarbon compounds. Specific examples of these include, for example,
Compounds A-1 to A-120, 8 to 8 described on pages 4 to 7
Exemplified compounds II-1 to II-29 described on page 9, Exemplified compounds H-1 to H-22 described on pages 14 to 15, and JP-A-1-209446.
Exemplified compounds S-1 to S-69 described on page 7, JP-A-63-253
Exemplary compounds I-1 to I-95 described in No. 943, pp. 10-12 can be exemplified.

The light-sensitive material of the present invention includes a color fogging inhibitor,
Image stabilizer, hardener, plasticizer, anti-irradiation dye, polymer latex, ultraviolet absorber, formalin scavenger, development accelerator, development retarder, fluorescent brightener, matting agent, lubricant, antistatic agent, interface Activators and the like can be optionally used. These compounds are described in, for example, JP-A Nos. 62-215272 and 63-46436.

As the color developing agent used in the color developing solution in the development processing of the light-sensitive material according to the present invention, aminophenol and p-phenylenediamine compounds widely used in various color photographic processes are used. In particular, an aromatic primary amine color developing agent is preferably used.

The following are examples of the aromatic primary amine developing agent.

(1) N, N-dimethyl-p-phenylenediamine hydrochloride (2) N-methyl-p-phenylenediamine hydrochloride (3) 2-amino-5- (N-ethyl-N-dodecylamino) Toluene (4) N-ethyl-N- (β-methanesulfonamidoethyl) -3
-Methyl-4-aminoaniline sulfate (5) N-ethyl-N- (β-hydroxyethyl) -3-methyl-4-
Aminoaniline sulfate (6) 4-Amino-3-methyl-N, N, -diethylaniline (7) 4-Amino-N- (β-methoxyethyl) -N-ethyl-3-
Methylaniline / p-toluenesulfonate (8) 4-amino-N-ethyl-N- (γ-hydroxypropyl)
3-Methylaniline / p-toluenesulfonate These color developing agents are used in an amount of 0.00
Preferably used in the range of 1 to 0.2 mol, 0.005 to
More preferably, it is used in the range of 0.2 mol.

To the color developing solution, a known developer component compound can be added in addition to the above color developing agent. Usually, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazoles, a preservative, a chelating agent and the like are used.

As the alkaline agent used in the color developing solution, potassium carbonate, potassium borate, trisodium phosphate and the like are used, and sodium hydroxide, potassium hydroxide and the like are mainly used for pH adjustment and the like. PH of color developer
Is generally 9 to 12, and 9.5 to 11 is preferably used.

For the purpose of suppressing development, halide ions are often used, but in order to speed up the development processing, chloride ions are mainly used, and potassium chloride, sodium chloride and the like are used. The amount of chloride ion is about 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol per liter of the color developing solution. Bromide ion has a large effect of suppressing development, and it is desired that the amount is approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ or less per liter of the color developing solution.

As preservatives, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids,
Particularly effective organic compounds are hydrazines, hydrazide amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused amines. It is a preservative. Particularly, dialkyl-substituted hydroxylamines such as diethylhydroalkylamine and alkanolamines such as triethanolamine are preferably used.

As the chelating agent used in the color developing solution according to the present invention, compounds such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are used. In particular, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid is preferably used.

The color development temperature is usually 15 ° C. or higher, generally in the range of 20 to 50 ° C. 30 ° C for rapid processing
It is preferable to perform the above.

The color development processing time is generally from 10 seconds to 4 minutes, but in the case of speeding up, it is preferably performed in the range of 10 seconds to 1 minute. Is preferably performed in the range of 10 to 30 seconds.

In the present invention, when the running process is performed while continuously replenishing the color developing solution, in order to eliminate the overflow solution of the color developing solution and to reduce the pollution problem due to the waste solution, it is necessary to use the color developing solution. Replenishment amount is 1m ² of photosensitive material
The amount is preferably 20 to 60 ml, and the effect of the present invention is more effectively exhibited when such low replenishment running is performed.

The light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as an alternative to the washing process, a stabilizing process may be performed. The developing apparatus used for developing the photosensitive material of the present invention is a roller transport type in which the photosensitive material is sandwiched between rollers arranged in a processing tank and transported, and the photosensitive material is transported while being fixed to a belt. An endless belt system may be used. In particular, a system in which a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank, and a photosensitive material is conveyed may be used.

[0104]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto.

REFERENCE EXAMPLE 1 Each layer having the constitution shown in Tables 1 and 2 was laminated on a paper support on which polyethylene was laminated on one side and polyethylene containing titanium oxide was laminated on the other side (emulsion layer coated side). Was simultaneously coated in multiple layers using a slide hopper to prepare a multilayer color photosensitive material sample 101. The coating solution was adjusted as follows.

First layer coating solution 26.7 g of yellow coupler (YC-8), 10.0 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), 0.67 g of stain inhibitor (HQ-1) and High boiling organic solvent (DNP) 6.
Add 60 ml of ethyl acetate to 67 g and dissolve.
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% aqueous gelatin solution containing 7 ml of a surfactant (SU-2) using an ultrasonic homogenizer. This dispersion was prepared under the following conditions using a blue-sensitive silver halide emulsion (silver 8.67).
g) and mixed with an anti-irradiation dye (A
I-3) was added to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, (H) was added to the second and fourth layers.
H-1) and (HH-2) were added to the seventh layer. Surfactants (SU-1) and (SU-3) were added as coating aids to adjust the surface tension.

[0109]

[Table 1]

[0110]

[Table 2]

The additives used for each layer are as follows.

HH-1: tetrakis (vinylsulfonylmethyl) methane HH-2: 2,4-dichloro-6-hydroxy-s-triazine.
Sodium SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium SU-3: di (2,2,3,3,4,4) sulfosuccinate , 5,5-octafluoropentyl) ester sodium DOP: dioctyl phthalate DNP: dinonyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone HBS-1: 1-dodecyl-4- (p-toluenesulfonamide) Benzene HBS-2: 2: 1 (volume ratio) mixture of tri (2-ethylhexyl) phosphate and tricresyl phosphate HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2-hexadecyl-5- Methylhydroquinone F-1: 5-chloro-2-methylisothiazolin-3-one

[0113]

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[0114]

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[0115]

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Tone of blue-sensitive silver halide emulsion (Em-B)
Below 2% aqueous solution of gelatin 1000ml was kept in manufacturing 40 ° C. (A
Solution) and (solution B) while controlling pAg = 6.5 and pH = 3.0.
At the same time, and further add the following (Solution C) and (Solution D)
The co-addition was performed over 180 minutes while controlling pAg = 7.3 and pH = 5.5. At this time, pAg was controlled according to the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added and 200 ml (Solution B) 10 g of silver nitrate was added and 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added and 600 ml (D solution) Silver nitrate 300g Water was added and 600ml was added. After completion of the addition, desalting was performed using 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. A monodispersed cubic emulsion EMP-1 having a diameter of 0.85 µm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye D-1 4 × 10 ^-4 mol / mol AgX sensitization Dye D-4 Preparation of 1 × 10 ^-4 mol / mol AgX green-sensitive silver halide emulsion (Em-G) Addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
Except for changing the addition time of EMP-1,
A monodispersed cubic emulsion EMP-2 having an average particle size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% was obtained.

EMP-2 was reacted with the following compound using 55
Chemical ripening was performed at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye D-2 4 × 10 ⁻⁴ mol / mol AgX red sensitivity Preparation of silver halide emulsion (Em-R ): Addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
Except for changing the addition time of EMP-1,
A monodispersed cubic emulsion EMP-3 having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-3
At 90 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (E
mR).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye D-3 1 × 10 ^-4 mol / mol AgX STAB- 1: 1- (3-acetamidophenyl) -5-mercaptotetrazole

[0124]

Embedded image

Next, the gelatin A contained in Sample 101 was replaced with an equal amount of gelatin shown in Table 3, and the magenta coupler MM-1 contained in the third layer was replaced with an equimolar magenta coupler shown in Table 3. Sample 102 was prepared in the same manner as Sample 101 except that it was changed.
Created ~ 129.

The following evaluation was performed using the obtained sample.

<Lightfastness> After wedge exposure with green light according to a conventional method, a sample processed according to the following processing steps was stored in sunlight for 2 months, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined. .

<Raw storage stability> The samples were stored under high-temperature conditions (55 ° C.) for 3 days, wedge-exposed with green light simultaneously with the samples not stored at high temperature, and processed according to the following processing steps to determine the sensitivity of each sample. And the change in sensitivity ΔS due to high-temperature storage.

[0129] _{ΔS = (│S t -S o │} / S o) × 100 However, S _t: temperature storage sensitivity of sample S _o: were wedge exposed by high-temperature storage sensitivity of sample without <Running variation resistance> green light The sample was processed according to the following processing steps to evaluate the gradation γ, immediately after the start of running, and after performing the running process until replenishing the color developing replenisher twice the tank capacity of the color developing solution, Variation of γ due to running Δγ
I asked.

Δγ = │γ immediately after the start of running--γ of running││ Here, γ is a value represented by the reciprocal of the difference between the logarithms of the respective exposures required to obtain the densities of 0.8 and 1.8. .

Shown [0131] The compositions of the processing steps the treatment temperature during between color development 35.0 ± 0.3 ° C. 45 seconds blix 35.0 ± 0.5 ° C. 45 seconds stabilized 30 to 34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds each processing solution below . The replenishment amount of each processing solution is 80 ml per 1 m ² of the photosensitive material.

Color developing solution tank replenisher Pure water 800 ml 800 ml triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g potassium chloride 2.4 g-1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1.8 g N- Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 5.4 g 8.2 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g 1.8 g Potassium carbonate 27 g 27 g Water To make the total volume 1 liter.
To 0, the replenisher adjusts the pH to 10.60.

Bleaching / fixing solution (tank solution and replenisher are the same) Ferric ammonium diaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added. To a total volume of 1 liter, and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenishing solution are the same) F-1 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Table 3 shows the results.

[0136]

[Table 3]

Gelatin A: Alkali-treated gelatin from bovine bone (iron content: 8.2 ppm) Gelatin B: Gelatin obtained by subjecting gelatin A to ion exchange treatment (iron content: 5.8 ppm) Gelatin C: Ion exchange to gelatin A Treated gelatin (iron content 4.1 ppm) Gelatin D: Gelatin A treated with a chelating resin Gelatin (iron content 2.5 ppm) As is clear from Table 3, a sample using the magenta coupler of the present invention. Samples 105 to 129 exhibit improved light fastness as compared with Samples 101 to 104 using the magenta coupler outside the present invention, but the samples using gelatin (A, B) outside the present invention are:
In each case, the sensitivity fluctuation (ΔS) at the time of raw storage and the gradation fluctuation Δγ at the time of running processing increase.

On the other hand, the gelatin of the present invention (C,
It can be seen that all of the samples of the present invention using D) are excellent in light resistance, raw storage stability and running fluctuation resistance. Especially iron content in gelatin is 3pp
It can be seen that the sample using gelatin D of less than m is excellent in raw storage stability and running fluctuation resistance.

Also, among the magenta couplers of the present invention,
It can be seen that the sample using the magenta couplers represented by the general formulas [M-II] and [M-III] is a sample excellent in light resistance, raw storage stability and running fluctuation resistance.

Example 1 Samples 101 to 120 and Sample 10 prepared in Reference Example 1
Samples 204, 208, and 4 were prepared by reducing the amount of gelatin used for each of the layers 4, 108, 112, 116, and 120 by 5%.
Using 212, 216 and 220, the running fluctuation resistance was evaluated in the same manner as in Reference Example 1 except that the processing steps were changed to the following processing steps. Table 4 shows the results.

Processing process Temperature Time Replenishment amount Color development 39.0 ± 0.3 ° C 45 seconds 40ml Bleaching and fixing 35.0 ± 0.3 ° C 45 seconds 51ml Stability 30-34 ° C 90 seconds 250ml (3-tank cascade) Drying 60-80 ° C 60 seconds Processing The composition of the liquid is shown below. The replenishment amount of each processing solution is an amount per 1 m ² of the photosensitive material. The stabilization treatment was replenished by a countercurrent method to the stabilization tank 3 → 1.

Color developer tank liquid Replenisher Pure water 800 ml 800 ml Triethanolamine 10 g 14 g N, N-diethylhydroxylamine 3.6 g 5 g Potassium chloride 4.5 g-Diethylenetriaminepentaacetic acid 5.0 g-Potassium sulfite 0.4 g-N-ethyl-N -β-methanesulfonamide ethyl-3-methyl-4-aminoaniline sulfate 6.0 g 12 g potassium carbonate 25 g 35 g Add water to make 1 liter, and add potassium hydroxide or sulfuric acid.
Adjust the pH to 10.10 for the tank solution and 11.50 for the replenisher.

Bleaching / fixing tank solution and replenisher Ferric ammonium salt of ethylenediaminetetraacetic acid 53 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70%) solution 123 g Ammonium sulfite (40%) solution 51 g Adjusted to pH 5.4 with ammonia water or glacial acetic acid Adjust and add water to bring the total volume to 1 liter.

Stabilizing tank solution and replenisher o-phenylphenol 0.1 g Ubitex (Ciba-Geigy) 1.0 g Zinc sulfate heptahydrate 0.1 g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1, 1-Diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or glacial acetic acid, and add water to make the total volume 1 liter.

[0145]

[Table 4]

Also in this example, it is found that the sample of the present invention shows excellent running fluctuation resistance. Further, it can be seen that the sample of the present invention in which the total amount of gelatin in the light-sensitive material is less than 7.0 g / m ² has further excellent running fluctuation resistance.

[0147]

According to the present invention, a silver halide photographic light-sensitive material and a color developing solution which are excellent in color reproducibility, dye image preservability, unexposed preservability and performance stability in continuous processing are reduced. It is possible to provide a method for processing the photosensitive material which can be replenished.

Claims (2)

(57) [Claims] In a silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion layer on a support, at least one of said silver halide emulsion layers is provided.
Layers contains a magenta coupler represented by the following general formula (M-I), and total amount of gelatin contained in said silver halide photographic material is less than 7.0 g / m ^2,
And a silver halide photographic light-sensitive material characterized in that gelatin contained in the silver halide photographic light-sensitive material has an iron content of less than 5 ppm. Embedded image Wherein, J is -O -, - S- or -N (R ₃₎ - represents, R3 represents a hydrogen atom or a substituent, n represents 0 or 1. When n = 0, R ₁ represents an alkyl group or an aryl group having 2 or more carbon atoms, and when n = 1, R ₁ represents an alkyl group or an aryl group. R ₂ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent. ] 2. The method according to claim 1, wherein the silver halide photographic light-sensitive material is continuously processed with a color developing solution containing a color developing agent, wherein the replenishment amount of the color developing solution is per 1 m ^{2 of the} silver halide photographic light-sensitive material. 20. A processing method for a silver halide photographic light-sensitive material, wherein the amount is 20 to 60 ml.