JPH0934068A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material low in fog and superior in color developing density and processing stability and little in characteristic change depending on temperature at the time of exposure by incorporating a specified cyan coupler in a red-sensitive silver halide emulsion layer and a specified compound in a photographic constituent layer. SOLUTION: The red-sensitive silver halide emulsion layer contains a cyan coupler represented by formula I or II and at least one of the photographic constituent layer contains the magenta coupler represented by formula III, and in the formulae I-III, each of R1 and R3 is a branched alkyl or substituted alkyl or such aryl or the like; each of R2 and R4 is a substituent; each of X1 and X2 is H atom or a group to be released by the reaction with the oxidation product of a color developing agent; each of R11 and R12 is an optionally substituted alkyl or aryl group or the like; each of R13 and R14 is a cyano or -COOR15 or the like; R15 is an optionally substituted alkyl or aryl group or the like, but at least one of R11 -R14 is a sulfo or carboxy group or the like; and each of L1 -L5 is an optionally substituted methine group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material. More specifically, it is a silver halide color photographic material having low fog, excellent color development and processing variability, and excellent temperature dependence during exposure. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a "light-sensitive material") for direct viewing, for example, a color photographic paper, a yellow coupler is usually used as a color forming agent for forming a dye image. , Magenta couplers and cyan couplers. These couplers are required to have basic properties such as color reproducibility, color developability and storage durability of the dye image to be obtained. In recent years, in particular, in order to faithfully reproduce the original color of the object, color reproduction There is a growing demand from users to improve the quality.

[0003] As a cyan image forming coupler, a phenol or naphthol coupler has been widely used. However, cyan images obtained from these phenol or naphthol couplers have a serious problem in color reproduction. That is, the absorption on the short-wave side of the absorption is poor, and the green region also has unnecessary absorption, that is, irregular absorption. For this reason, in the negative film, irregular absorption due to masking or the like must be corrected, and in the case of paper, there is no correction means, and the color reproducibility is considerably deteriorated at present.

For the purpose of improving color reproducibility, Japanese Patent Application Laid-Open
250649, 63-250650, 64-5
No. 54 and the like propose a pyrazoloazole type cyan coupler. However, these couplers have an electron-withdrawing group and a hydrogen-bonding group introduced in order to satisfy the absorption wavelength of the coloring dye to be formed. It was not a satisfactory level.

Further, in recent years, in light-sensitive materials for color photography and printing, the printing process and the developing process have been shortened and speeded up, and stability at the time of processing has been increasingly required.

Further, when the temperature and humidity at the time of exposure of the light-sensitive material are different, photographic characteristics such as sensitivity and gradation (γ) are changed, and it is strongly desired that the change width is small. In particular, changes in photographic characteristics due to changes in the concentration of processing liquid components during continuous processing have become an increasingly serious problem in rapid processing.

However, the present situation is that no photosensitive material satisfying these requirements has been found yet.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having low fog, excellent color developability and processing variability, and excellent temperature dependence during exposure. It is in.

[0009]

The above object of the present invention is to provide a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. The red-sensitive silver halide emulsion layer contains at least one cyan coupler represented by the following general formula (I) or (II), and at least one of the photographic constituent layers has the following general formula: It is achieved by a silver halide color photographic light-sensitive material containing at least one compound represented by (III).

[0010]

Embedded image

In the formula, R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, and R ₂ and R ₄ each represent a substituent. X ₁ and X ₂ each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

[0012]

Embedded image

In the formula, R ₁₁ and R ₁₂ are each an alkyl group,
It represents an aryl group or a heterocyclic group, and these groups may be substituted. R ₁₃ and R ₁₄ are each a cyano group, —COOR
₁₅ groups (R ₁₅ represents an alkyl group, an aryl group or a heterocyclic group, and these groups may be substituted), -CON
(R ₁₆ ) (R ₁₇ ) group (R ₁₆ and R ₁₇ are each a hydrogen atom,
Represents an alkyl group, an aryl group or a heterocyclic group, and these groups may be substituted) or —COR ₁₈ (R ₁₈ represents an alkyl group, an aryl group or a heterocyclic group, and these groups may be substituted) Good). However, at least one of R _{11 to} R ₁₄ represents a sulfo group, a carboxyl group, a phosphono group, a phosphoryl group, a carboxyl group or a sulfate ester group. L _{1 to} L ₅ each represent an optionally substituted methine group.

Hereinafter, the present invention will be described in detail.

First, the cyan couplers represented by formulas (I) and (II) of the present invention will be described in detail.

In the above general formulas (I) and (II), the branched alkyl group represented by R ₁ and R ₃ is i-propyl, t-butyl, sec-butyl, i-butyl, t.
Each group such as -octyl can be mentioned.

As the alkyl component of the substituted alkyl group,
It may be linear, branched or cyclic, and may be methyl, ethyl,
Butyl, i-propyl, t-butyl, sec-butyl,
Each group such as i-butyl, t-octyl and cyclohexyl can be mentioned.

As the aryl component of the substituted aryl group,
Examples thereof include phenyl and the like.

Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-imidazolyl, 2-thiazolyl, 3-isoxazolyl, 3-pyridyl, 2-pyridyl, 2-pyrimidyl, 3-pyrazolyl, 2-benzothiazolyl and the like. Each group can be mentioned.

However, when R ₁ and R ₃ represent a substituted alkyl group or a substituted aryl group, these alkyl and aryl components always have a substituent.

Even when R ₁ and R ₃ represent a branched alkyl group or a heterocyclic group, these groups may have a substituent, if necessary.

The substituents are not particularly limited, but typically include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. Halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hetero Examples include groups such as ring thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues. These groups may be further substituted by the above substituents.

In the general formulas (I) and (II), the substituent represented by R ₂ and R ₄ is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, Examples of the groups include alkenyl and cycloalkyl groups. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino,
Alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo, etc., and spiro Compound residues and bridged hydrocarbon compound residues are also included.

In the above-mentioned substituents for the branched alkyl group represented by R ₁ and R ₃ , the substituted alkyl group, the substituted aryl group or the heterocyclic group, and the substituents represented by R ₂ and R ₄ ,
The alkyl group preferably has 1 to 32 carbon atoms,
It may be linear or branched.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the alkyl group and the aryl group in the substituent represented by R ₂ and R ₄ .

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7 are preferred.

The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc. A carbamoyloxy group as an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group as an alkylureido group, an arylureido group, etc .; sulfamoylamino As alkylsulfamoyl group, an aryl sulfamoylamino group such as, is preferably a 5- to 7-membered as heterocyclic group, specifically 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl, 1-tetrazolyl group, etc .; The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,5. 6-Tetrahydropyranyl-2-oxy, 1-phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio, 2-benzothiazoli Ruthio, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group as succinimide, 3
-Heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; spiro compound residue as spiro [3.3] heptane-1-yl etc .; bridged hydrocarbon compound residue as bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

The substituent represented by R ₂ and R ₄ is preferably an alkyl group or an aryl group, and particularly preferably an aryl group.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Examples of the group represented by X ₁ and X ₂ which can be split off by the reaction with the oxidized product of the color developing agent are, for example, halogen atom (chlorine, bromine, fluorine, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocycle thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom,
Examples include groups such as alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl.

X ₁ and X ₂ are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a nitrogen-containing heterocyclic group bonded by an N atom.

Of the cyan couplers represented by the general formulas (I) and (II), those represented by the general formula (I) are preferable.

The specific compounds of the cyan couplers represented by the general formulas (I) and (II) (referred to as the cyan coupler of the present invention) are shown below, but the present invention is not limited thereto.

[0038]

Embedded image

[0039]

[Chemical 6]

[0040]

[Chemical 7]

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

[Chemical 12]

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

The cyan coupler of the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 ×, per mol of silver halide.
It can be used in the range of 10 ⁻² to 8 × 10 ⁻¹ mol.

The amount of the compound represented by formula (III) used in the present invention is in the range of 1 to 100 mg / m ² , more preferably ² to 50 mg / m ² . If the amount used is less than 1 mg / m ² , irradiation cannot be prevented and sharpness deteriorates. On the other hand, 100 mg / m
^If it exceeds ² , the decolorizing property becomes insufficient especially in rapid processing, resulting in color contamination.

In the following, the general formula (II
Specific examples of the anti-irradiation dye represented by I) will be given below, but the invention is not limited thereto.

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

[Chemical 21]

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

[Chemical formula 26]

[0063]

Embedded image

[0064]

Embedded image

[0065]

[Chemical 29]

The compounds of the general formula (III) of the present invention are disclosed in JP-B-52-38056 and JP-B-54-38129, respectively.
No. 55-10059, JP-A-51-77327.
No. 58-143342 and 59-111640.
No. 59-111641 and 59-168438.
No. 60-218641, No. 62-273527
No. 63-139949, No. 63-262649
And the compounds described in Japanese Patent Application Nos. 63-2591 and 63-2592, and can be synthesized by the methods described therein.

The cyan coupler of the present invention can be used in combination with other types of cyan couplers.

In order to incorporate the cyan coupler of the present invention into a light-sensitive material, known techniques used in ordinary cyan couplers can be applied. That is, it is preferable that the coupler is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, dispersed in the form of fine particles and added to the silver halide emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

When the color light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler and a yellow coupler are used in addition to the cyan coupler of the present invention. The magenta coupler and the yellow coupler are not particularly limited, and known ones can be used.

As the magenta coupler, for example, a 5-pyrazolone type coupler, a pyrazolobenzimidazole type coupler, a pyrazolotriazole type coupler and a closed acylacetonitrile type coupler can be used.

As the yellow coupler, for example, an open chain ketomethylene type coupler can be used.

The silver halide grains contained in the silver halide emulsion layer include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like in the art. It may be any silver halide grain used and is not particularly limited.

The composition of the silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Also, when the composition inside and outside the particle is different, the composition may change continuously,
It may be discontinuous.

The grain size of the silver halide grains is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to It is in the range of 1.2 μm. The particle diameter can be measured by various methods generally used in the technical field. As a typical method, Lapland's “particle size analysis method” (ASTM.
Symposium on Right Microscopy, 19
55, pp. 94-122) or "The Theory of Photographic Process"
(Co-written by Mies and James, 3rd edition, published by Macmillan, Inc. (1966), Chapter 2).

The particle diameter can be measured by using the projected area of the particle or an approximate diameter value. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately represented as diameter or projected area.

The grain size distribution of the silver halide grains may be polydisperse or monodisperse. Preferably, they are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, in the particle size distribution of the silver halide grains. The coefficient of variation is calculated as follows.

Coefficient of variation = standard deviation of grain size distribution / average grain size The silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time, or may be grown after seed particles have been produced. The method for producing seed particles and the method for growing seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any of a forward mixing method, a back mixing method, a double mixing method, or a combination thereof, but the double mixing method is preferable. Furthermore, as one form of the simultaneous mixing method,
The pAg controlled double jet method described in JP-A-54-48521 may also be used.

If necessary, a silver halide solvent such as thioether 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 during the formation of silver halide grains or after the completion of grain formation.

The silver halide grains may have any shape. One preferable example is a cube having a {100} plane as a crystal surface.

Further, particles having a shape of octahedron, tetrahedron, dodecahedron or the like can also be used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains have a grain-forming process and / or
Alternatively, during the growth process, metal ions are added using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt or a complex salt, and are contained inside the particles and / or on the surface of the particles. The reduction sensitization nucleus can be provided inside the grains and / or on the grain surface by placing the grains in an appropriate reducing atmosphere.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained therein. The removal of the salts can be carried out according to the method described in Research Disclosure (RD) 17643.

The silver halide grains used in the present invention are preferably grains in which a latent image is mainly formed on the surface,
The particles may have a latent image formed inside the particles.

In the present invention, a chalcogen sensitizer can be used. Chalcogen sensitizer is sulfur sensitizer,
It is a general term for selenium sensitizers and tellurium sensitizers, but sulfur sensitizers and selenium sensitizers are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like. Others, US Pat. Nos. 1,574,944 and 2,410,689
No. 2,278,947 and No. 2,728,668
Nos. 3,501,313, 3,656,955
The sulfur sensitizers described in, for example, Japanese Laid-Open Patent Application (OLS) 1,422,869, JP-A-56-24937 and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is 10 ^-7 per mol of silver halide.
It is preferably about 10 ^-1 mol.

The emulsion of the present invention can be used in combination with a reduction sensitization method using a reducing substance and a noble metal sensitization method using a noble metal compound.

The light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation.

The photographic material can contain various photographic additives in addition to the above. For example, antifoggants, development accelerators, development retarders, bleaching accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants Agents, plasticizers, wetting agents and the like can be used (for these, see RD 17643).

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fog agent, an antifoggant and a chemical sensitizer are prepared by coupling with a competing coupler and an oxidized product of a developing agent. Compounds that release photographically useful fragments such as sensitizers, spectral sensitizers and desensitizers can be used.

The support of the light-sensitive material of the present invention is, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
There are glass plates, polyester films such as cellulose acetate, cellulose nitrate and polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films and the like, and in the case of a transparent support, a reflective layer may be used together. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

For coating the emulsion layer and other constituent layers, dipping coating, air doctor coating, curtain coating,
Various coating methods such as hopper coating can be used.
Also, US Pat. Nos. 2,781,791 and 2,941,8
A simultaneous coating method of two or more layers according to the method described in No. 98 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. However, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion are sequentially provided from the support side. The arrangement of layers is preferable.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and various layers such as a filter layer, a curl preventing layer, a protective layer and an antihalation layer are constituted. The layers can be appropriately combined and used.

A hydrophilic colloid can be used as a binder in these constituent layers, and gelatin is preferably used. Further, the various photographic additives mentioned in the above description of the emulsion layer can be contained in the layer.

The processing method of the light-sensitive material of the present invention is not particularly limited, and any generally known processing method can be applied. For example, as a typical example thereof, a method of performing bleach-fixing treatment after color development, and further performing washing and / or stabilizing treatment if necessary, a method of performing bleaching and fixing separately after color development, and further performing as necessary. The method for carrying out washing and / or stabilizing treatment may be carried out by any method, but the color light-sensitive material of the present invention is rapidly treated in the steps of color development, bleach-fixing and washing (or stabilization). It is suitable for

[0097]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 A polyethylene substrate containing titanium oxide was prepared by laminating polyethylene on one side of a paper support and polyethylene on the other side of the paper support, and then by laminating polyethylene having titanium oxide on the other side. Sample 1 of a multilayer silver halide color photographic light-sensitive material was prepared by coating on the side of. The coating liquid was prepared as follows.

First layer coating liquid: 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), (ST-2) 6.67.
g, additive (HQ-1) 0.67 g, irradiation prevention dye (AI-3) 0.33 g, high boiling organic solvent (D
NP) 6.67 g was dissolved by adding 60 cc of ethyl acetate.
This solution was emulsified and dispersed in 220 cc of a 10% aqueous gelatin solution containing 7 cc of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions 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, the second and fourth layers (H
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount of addition in the light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0102]

[Table 1]

[0103]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) -sodium salt DBP: dibutyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2 , 5-Di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-Dimethyl-4-hexyloxycarbonyl) butylhydroquinone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0105]

Embedded image

[0106]

[Chemical 31]

[0107]

Embedded image

[0108]

[Chemical 33]

(Method for preparing blue-sensitive silver halide emulsion) 4
In 1000 cc of a 2% aqueous gelatin solution kept at 0 ° C,
The following (solution A) and (solution B) were subjected to pAg = 6.5, pH =
At the same time over 30 minutes while controlling to 3.0,
Solution) and (Solution D) were added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH is controlled using an aqueous solution of sulfuric acid or sodium hydroxide, and pAg
For the control, a control liquid having the following composition was used. The composition of the control liquid is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control liquid is solution A,
When mixing liquid B, 0.1 mol / liter, liquid C,
The amount was 1 mol / liter when the liquid D was mixed.

(Liquid A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make up to 200 cc.

(Liquid B) Silver nitrate 10 g Water was added to finish to 200 cc.

(Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to finish to 600 cc.

(Liquid D) Silver nitrate 300 g Water was added to finish to 600 cc.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
After desalting using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to have an average particle diameter of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound 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 BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a size of 3 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

For EMP-2, the following compounds were used:
Chemical ripening was carried out at 5 ° 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 GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation method of red-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 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:
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

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 RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- (3-acetamido) phenyl-5-mercaptotetrazole

[0121]

Embedded image

Next, in Sample 1, cyan couplers C-1 and C-2 of the fifth layer are shown in Table 3 (the addition amount is the same molar amount as the total number of moles of comparative couplers C-1 and C-2). Alternatively, Samples 1 to 22 were prepared in exactly the same manner except that the same amount of the dye for preventing irradiation AI-2 as the sixth layer was changed to the dye shown in Table 3.

The obtained sample was subjected to wedge exposure by a conventional method, and then developed according to the following processing conditions to obtain the fog (Fog) and the maximum density (D) of the red-sensitive photosensitive layer.
max) was measured.

(Processing conditions) Processing step Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 C. 60 seconds Color developing solution Pure water 800 cc Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine Tetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4 0.5g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0g Potassium carbonate Um 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc Ammonium sulfite (40% aqueous solution) 27.5 cc Add water to make 1 liter, and add carbonic acid. Adjust to pH = 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Further, the obtained sample was subjected to wedge exposure by a conventional method, and thereafter, the amount of CD-3 as a color developing agent in the color developing solution in the processing step was set to 3.8 g / liter. Processing was performed by the same process, and the maximum density (Dmax ') of the red-sensitive photosensitive layer was measured.

Further, the temperature-humidity dependency at the time of exposure was evaluated for each sample by the following method.

First, a color negative film (Konica Color LV-400: manufactured by Konica) and a camera (Konica FT-1).
MOTOR: manufactured by Konica) was used to photograph a color checker manufactured by Macbeth. Subsequently, color negative development processing (CNK-4: manufactured by Konica Corporation) is performed, and the obtained negative image is subjected to a Konica Color Printer CL-P2000 (manufactured by Konica Corporation) under conditions of 20 ° C. and 40% RH. Each sample was printed in a size of 82 mm × 117 mm, and a practical print was obtained in the same manner as described above. Printer conditions at the time of printing were set for each sample so that the gray on the color checker became gray on the print.

Further, printing was similarly performed under the same setting under the conditions of 25 ° C. and 80% RH, and the temperature dependence of exposure was visually evaluated for each of the obtained two practical prints.

The results are summarized in Table 3.

[0132]

[Table 3]

[0133]

Embedded image

As is clear from the table, Samples 1, 2 and 3 using the cyan coupler outside the present invention and the dye outside the present invention have high fog, insufficient color developability, process variability and exposure. The temperature-humidity dependency of time is also insufficient. On the other hand, Samples 4, 5 and 6 using the cyan coupler other than the present invention and the dye of the present invention show a slight improvement in fog and temperature / humidity dependency at the time of exposure, but color development and processing variability are sufficient. It is hard to say.

On the other hand, Sample 7 using the cyan coupler of the present invention and the dye other than the present invention has improved process variability, but it cannot be said that fog and temperature / humidity dependency during exposure are sufficient.

On the other hand, Samples 8 to 22 using the cyan coupler of the present invention and the dye of the present invention all have low fog and good color developability, and also have processing variability and temperature / humidity dependence during exposure. The sex is very good.

[0137]

According to the present invention, the fog is low, the color developability,
It was possible to provide a silver halide color photographic light-sensitive material having excellent processing variability and excellent temperature-humidity dependency during exposure.

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the cyan represented by the following general formula (I) or general formula (II) is contained in the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material containing at least one coupler and at least one compound represented by the following formula (III) in at least one of the photographic constituent layers. Embedded image [In the formula, R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, and R ₂ and R ₄ each represent a substituent. X ₁ and X ₂ each represent a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. [Chemical formula 2] [In the formula, R ₁₁ and R ₁₂ each represent an alkyl group, an aryl group or a heterocyclic group, and these groups may be substituted.
R ₁₃ and R ₁₄ are a cyano group and a —COOR ₁₅ group (R
₁₅ represents an alkyl group, an aryl group or a heterocyclic group, and these groups may be substituted), -CON (R ₁₆ ) (R
₁₇ ) group (R ₁₆ and R ₁₇ are each a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group, and these groups may be substituted) or —COR ₁₈ (R ₁₈ represents an alkyl group, an aryl group or a heterocyclic group, and these groups may be substituted) Represent However, at least one of R _{11 to} R ₁₄ is a sulfo group, a carboxyl group, a phosphono group, a phosphoryl group,
Represents a carboxyl group or a sulfate ester group. L _{1 to} L ₅ each represent an optionally substituted methine group. ]