JP3030578B2 - Silver halide photographic light-sensitive material for black and white with high sensitivity, high sharpness, and little processing unevenness - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxonol dye.etcTo
Related to silver halide photographic materials, including
Oxonol dyeetcDye specific layers by
Halogen with high sensitivity, sharpness and little processing unevenness
It relates to a silver halide photographic material. 2. Description of the Related Art Silver halide photographic light-sensitive materials have excellent properties.
High image quality characteristics such as sharpness and color reproducibility are required. On the other hand, in recent years, silver halide photographic light-sensitive materials
To counter the immediacy of electrophotographic materials competing in the field
In addition, the processing time is further reduced,
Is required. Required for such photosensitive materials
Realizing the above-mentioned high image quality characteristics and super-rapid processing suitability
Therefore, in the industry, the photographic material
Thinning or optimization of silver halide and additive compound materials
Efforts have been made. By the way, silver halide photographic exposure
Improve image quality or adjust silver halide emulsion sensitivity in materials
It is well known that dyes are included for the purpose.
Such technologies include, for example, halation prevention,
Used in anti-radiation and light absorption filters
You. [0004] Also, recently, the technology for incorporating a dye has been
To replace yellow colloidal silver in color photographic materials
Dyes (hereinafter referred to as “YC dyes”) and radiographic images
Dyeing dyes and marks for crossover cut layers in optical materials
Dyes for dyeing non-photosensitive emulsion layers in printed photographic materials
Etc., and its use has spread
I have. [0005] The dyes used for these purposes are
Depending on 1. 1. have a good absorption spectrum; 2. Do not diffuse from the colored layer to other layers. No photographic effects on photosensitive silver halide emulsion
Thing 4. 4. Stable in silver halide photographic materials. 5. Easy to add Do not affect the solution viscosity in the emulsion coating solution.
And 7. It is required that the color does not remain after processing. In order to satisfy these required characteristics,
Many dyes have been proposed in the past, for example, US Patent
No. 3,540,887, No. 3,544,325, No. 3,560,214,
JP-B-31-10578 and JP-A-51-3623 include benzyl
Den dye, in British Patent No. 506,385 and JP-B-39-22069
Is an oxonol dye; U.S. Pat.
Cyanine dye, styryl dye in U.S. Patent No. 1,845,404
Fees have been proposed. [0007] These dyes are water or an organic solvent miscible with water.
The general method of dissolving in a medium and adding it to the photographic composition
It is. However, if the dye is water-soluble,
It diffuses to all layers without staying. Therefore, the original eyes
To achieve the target, a large amount of dye is diffused to other layers.
Must be added.
Undesirable phenomena such as temperature drop, gradation fluctuation, and fog abnormality
May appear. In particular, the photosensitive material was kept over time
In the case, fogging and desensitization are remarkable and avoid these
Therefore, if the amount used is reduced, the original light absorption effect
Will not be able to. Specific layers are dyed for such problems.
Spread like wearingRestraintDyes are also known,
Disperse dyes such as U.S. Pat.Nos. 2,538,008 and 2,5
Nos. 39,009 and 4,420,555, JP-A-61-204630
No. 61-205934, No. 62-32460, No. 62-56958, No. 6
2-92949, 62-222248, 63-40143, 63-18474
Nos. 9 and 63-316852 describe YC dyes.
You. Further, these dyes are used for color photographic light-sensitive materials.
Carey Lea Silver, commonly used in
The yellow colloidal silver called is not only in the blue light region but also in part length
Absorbing the wavelength side may reduce green sensitivity.
And the disadvantage of increasing fog on adjacent landings
Good and to save valuable silver resources.
Many have been proposed. However, these diffusion resistant dyes
According to the report, the above disadvantages are improved to some extent, but the storage stability is poor.
Desensitization occurs over time. In addition, due to insufficient bleaching properties,
It causes color contamination. In addition, processing unevenness is likely to occur.
In addition, when rapid processing is performed, processing unevenness becomes severe
A new problem has arisen. Therefore, in order to improve these, a new resistance
There is a need for a diffusion type dye. SUMMARY OF THE INVENTION The object of the present invention is to meet the above-mentioned requirements.
Includes diffused dyes for sensitivity and sharpness
Silver halide photographic light-sensitive material with improved processing and unevenness characteristics
To provide a fee. Means for Solving the Problems The present inventors have identified the above problems.
As a result of intensive studies in view of the above, the above object of the present invention,
Contains at least one silver halide emulsion layer on a support
Has a hydrophilic colloid layerFor black and whiteSilver halide photographic exposure
In the material,TheAt least one of the hydrophilic colloid layers
One layer is made of a compound represented by the following general formulas [1] to [8].
Containing at least one kind of solid fine particle dispersion, andTheC
At least the silver logen emulsion layerAlso oneLayersThe following general formula [9]
Wherein the silver halide photographic light-sensitive material contains a compound represented by the formula:
Roller that processes the material under the conditions corresponding to the following formula [1]
-White processed by a transport type automatic processor
For blackWhat can be achieved with silver halide photographic materials
We have found and completed the present invention. [0013]A is a 2-pyrazolin-5-one acidic nucleus,
B represents a 4-aminoaryl group;₁~ L_ThreeRepresents a methine group,
m represents O or 1, and the compound of the general formula [1] is
At least one of the conditions (1) to (4) is satisfied. (1) Carboxyl in BBaseat least
Have one. (2) At least a sulfamoyl group in A
Also has one. (3) Carboxyl group in AOr aliphatic
May have a carboxyl group, may have an aliphatic group
Good sulfamoyl groupAt least one. (4) 2-pyrazolin-5-one acidic mother
Reduce carboxyl and sulfonamide groups bound to the nucleus
Have at least one.However, if only condition (3) is satisfied
At the same time, 2-pyrazolin-5-one acid nucleus
Except when the silphenyl group is directly bonded. Also, the condition
When only (3) and (4) are satisfied, 2-pyrazo
Carboxyphenyl group and carboxylic acid are added to phosphorus-5-one acidic nucleus.
Excludes cases where ruboxyl groups are directly bonded simultaneously. Embedded imageWhere R₁, R_TwoIs an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, hetero
Ring group, alkylcarbonyl group, arylcarbonyl group,
Alkoxycarbonyl group, aryloxycarboxyl
Group, alkylsulfonyl group, arylsulfonyl group,
Rukylsulfinyl group, arylsulfinyl group, car
Bamoyl group, sulfamoyl group, cyano group, amino group,
Sulfonamide group, amide group, ureido group, thiourei
Group, alkoxyl group, aryloxy group, alkylthio
O group, arylthio group, carboxyl group or hydroxy
R_Three, R_FourIsVia a linking groupCarboxyl group
A phenyl group having₁~ L_ThreeRepresents a methine group, and n represents 0
Represents an integer of ~ 2, and when n is 2, each L_Two, L_ThreeAre the same
May also be different. Embedded imageWhere R₁, R_TwoAre -COOH,-
(CH_Two)_nCOOH, -A-NHCOCH_TwoCH_TwoCOO
H, -CONNH (CH_TwoCOOH)_Two, -NHCON
(CH_TwoCOOH) _Two , -CONH-A-COOH
A represents an aryl group, and n represents 1 or 2. R
_Three, R_FourIs an alkyl having no hydrogen atom or carboxyl group
Alkenyl, cycloalkyl, alkynyl
Represents an aryl group, a heterocyclic group. L₁~ L_ThreeIs methine
And n represents an integer of 0 to 2, and when n is 2,
L_Two, L_ThreeMay be the same or different. Embedded imageWhere R₁, R_TwoIsRespectively, an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, hetero
Ring group, alkylcarbonyl group, arylcarbonyl group,
Alkoxycarbonyl group, aryloxycarboxyl
Group, alkylsulfonyl group, arylsulfonyl group,
Rukylsulfinyl group, arylsulfinyl group, car
Bamoyl group, sulfamoyl group, cyano group, amino group,
Sulfonamide group, amide group, ureido group, thiourei
Group, alkoxyl group, aryloxy group, alkylthio
O group, arylthio group, carboxyl group or hydroxy
Represents a group,R_Three, R_FourIs an alkyl having a carboxyl group
Group, cycloalkyl group, naphthyl group or heterocyclic group
Represent. L₁~ L_ThreeRepresents a methine group, and n is an integer of 0 to 2
And when n = 2, each -L_Two= L_Three-Are the same but different
You may. Embedded imageWhere R₁, R_TwoIsRespectively, an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, hetero
Ring group, alkylcarbonyl group, arylcarbonyl group,
Alkoxycarbonyl group, aryloxycarboxyl
Group, alkylsulfonyl group, arylsulfonyl group,
Rukylsulfinyl group, arylsulfinyl group, car
Bamoyl group, sulfamoyl group, cyano group, amino group,
Sulfonamide group, amide group, ureido group, thiourei
Group, alkoxyl group, aryloxy group, alkylthio
O group, arylthio group, carboxyl group or hydroxy
Represents a group,R_Three, R_FourIs an m-carboxyphenyl group or o
-Represents a carboxyphenyl group. L₁, L_Two, L_Three, L_Four,
L_FiveRepresents a methine group, and n₁, N_TwoRepresents 0 or 1. Embedded imageWhere R₁IsAlkyl group, alkenyl group,
Cycloalkyl group, aryl group, heterocyclic group, alkyl
Carbonyl group, arylcarbonyl group, alkoxycal
Bonyl group, aryloxycarboxyl group, alkyls
Rufonyl group, arylsulfonyl group, alkylsulfi
Nil group, arylsulfinyl group, carbamoyl group,
Rufamoyl group, cyano group, amino group, sulfonamide
Group, amide group, ureido group, thioureido group, alkoxy
Sil group, aryloxy group, alkylthio group, aryl
Represents a thio group, a carboxyl group or a hydroxyl group,R
_TwoRepresents a hydrogen atom, an alkyl group, an alkenyl group,
Represents a kill group, an aryl group, or a heterocyclic group. L₁~ L_ThreeRepresents a methine group, and E represents oxono
Represents an acidic nucleus necessary for forming a dye, and n is from 0 to 2
And when n = 2, each -L_Two= L_Three-Is the same
It may be different. Further, the compound of the general formula [6] is at least
2 carboxyl groups, sulfonamide group, sulfamo
It has an yl group. Embedded imageWhere R₁, R_TwoIsRespectively, an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, hetero
Ring group, alkylcarbonyl group, arylcarbonyl group,
Alkoxycarbonyl group, aryloxycarboxyl
Group, alkylsulfonyl group, arylsulfonyl group,
Rukylsulfinyl group, arylsulfinyl group, car
Bamoyl group, sulfamoyl group, cyano group, amino group,
Sulfonamide group, amide group, ureido group, thiourei
Group, alkoxyl group, aryloxy group, alkylthio
O group, arylthio group, carboxyl group or hydroxy
Represents a group,R_Three, R_FourIs hydrogen, alkyl, cyclo
Alkyl group, alkenyl group, aryl group or heterocyclic group
And L₁, L_Two, L_Three, L_Four, L_FiveRepresents a methine group,
n₁, N_TwoRepresents 0 or 1. Where R₁, R_Two, R_Three,
R_FourAt least one of the sulfonamide groups and / or
Having a sulfamoyl group and having a sulfonamide in the compound
Having at least two groups and / or sulfamoyl groups
You. Embedded imageWhere R₁, R_TwoIs an alkyl group, alkenyl
Group, cycloalkyl group, aryl group, heterocyclic group,
Killcarbonyl group, arylcarbonyl group, alkoxy
Carbonyl group, aryloxycarboxyl group, alkyl
Rusulfonyl group, arylsulfonyl group, alkylsulfur
Finyl group, arylsulfinyl group, carbamoyl
Group, sulfamoyl group, cyano group, amino group, sulfone
Amide group, amide group, ureido group, thioureido group,
Lucoxyl group, aryloKiGroup, alkylthio group, a
Represents a reelthio group, carboxyl group or hydroxyl group
Then L₁, L_Two, L_Three, L_Four, L_FiveRepresents a methine group, and n₁,
n_TwoRepresents 0 or 1. A, B, L in the general formula [1]₁, L_Two,
L_ThreeSpecific examples of each group represented by
No. 588, page 8, line 3 to page 18, line 14
Of the compound represented by the general formula [1]
Examples of the compounds include, besides the following compounds, Japanese Patent Application No. 1-331588
(9) to (19), (2
2), (23), (25) to (46), (48) to (51),
(56) to (62), (67) to (80), (82) to (10
2). Embedded imageEmbedded imageEmbedded imageEmbedded imageEmbedded imageR in the general formula [2]₁, R_TwoRepresented by
Examples of the substituent include an alkyl group, an alkenyl group,
Alkyl group, aryl group, heterocyclic group, alkyl carbonyl
Group, arylcarbonyl group, alkoxycarbonyl
Group, aryloxycarbonyl group, alkylsulfonyl
Group, arylsulfonyl group, alkylsulfinyl group,
Arylsulfinyl group, carbamoyl group, sulfamo
Yl group, cyano group, amino group, sulfonamide group,
Groups, ureido groups, thioureido groups, alkoxy groups,
Reeloxy group, alkylthio group, arylthio group,
A ruboxyl group and a hydroxyl group are preferred.
Specific examples include the specification of Japanese Patent Application No. 221-211.
From page 7, line 18 to page 17, line 5
Can be Also, R_Three, R_Four, L₁, L_Two, L_ThreeEach group represented by
As a specific example, Japanese Patent Application No. 2-2211, p.
From line 6 to page 21, line 19, those described are
Specific examples of the compound represented by the general formula [2] include the following compounds
In addition to the products described in Japanese Patent Application No. 2-2211, pages 23 to 35
1, 4, 6, 9 to 12, 14 to 18, 21, 22, 25, 27
From 34, 37 to 43, 45 to 49, 51, 52, 54 to 60, 63 or
73. Embedded imageEmbedded imageEmbedded imageIn the general formula [3], R₁Or R_TwoRepresented by
Specific examples of the group having a carboxyl group include
From page 13, line 4 to page 15, line 20 of Japanese Patent Application No. 2-2212
And those described for R_ThreeOr R_FourKarboki represented by
Examples of the substituent having no sil group include an alkyl group and an alkenyl.
Group, cycloalkyl group, alkynyl group, aryl group,
Heterocyclic groups are preferred, and specific examples thereof
As described in Japanese Patent Application No. 2-2212, page 7, line 12
To page 12, line 16; Also, L
₁, L_Two, L_ThreeSpecific examples of each group represented by
No. 2-2212, page 12, line 17 to page 13, line 3
And a compound represented by the general formula [3]
Specific examples of the product include, in addition to the following compounds, Japanese Patent Application No. 2-2212.
Compounds 1 to 13 and 15 described on pages 17 to 29 of the specification
From 18, 21, 24 to 27, 30 to 40, 43 to 46, 48 to 5
2, 54, 56, 57, 61 to 64, 67 to 82, 85 to 91, 94
105, 108 to 117, 120, 121, 123. Embedded imageEmbedded imageEmbedded imageIn the general formula [4], R₁Or R_TwoRepresented by
As the substituent represented by the general formula [2]₁, R_Two
Preferred examples of the substituent represented by
Specific examples are described in Japanese Patent Application No. 2-62, p.
From line 17 to page 17, line 15 are mentioned. R
_Three, R_Four, L₁, L_Two, L_ThreeSpecific of each group represented by
As described in Japanese Patent Application No. 2-62, page 17, line 16 to page 19
Those described in the second line are mentioned, and represented by the general formula [4].
Specific examples of the compound to be used, in addition to the following compounds,
Compounds 1 and 6 described on pages 20 to 26 of JP-A-62
8, 13 to 21, 24 to 28, 30, 33, 34, 36 to 54, 57
64, 66, 67, 69 to 71, 73, 75 to 88
You. Embedded imageEmbedded imageNext, in the general formula [5], R₁Or R_TwoIn table
Is a substituent represented by the general formula [2]₁,
R_TwoPreferred examples of the substituent represented by
Specific examples and preferred examples are described in Japanese Patent Application No.
No. 335570, page 7, line 11 to page 16, line 13
Those listed. R_ThreeOr R_FourSpecific of the group represented by
As a typical example, Japanese Patent Application No. 1-3335570, page 16, line 14
To the 17th page, 1st line, L.₁,
L_Two, L_Three, L_Four, L_FiveSpecific methine group represented by
As described in Japanese Patent Application No. 2-62, page 18, line 12 to page 19
The methine group described in the second line is exemplified. General formula [5]
Specific examples of the compound represented by, in addition to the following compounds,
Compounds described in Japanese Patent Application No. 1-3335570, pages 18 to 23.
1, 4 to 11, 14, 15, 18, 19, 21 to 23, 25
28, 30, 31, 33, 35 to 44, 46, 48 to 53, 57, 58, 6
0, 62, 63, 65 to 69. Embedded imageEmbedded imageIn the general formula [6], R₁Replace with
As the group, R in the general formula [2]₁Represented by
Preferred examples of the substituent include those exemplified as R.
₁Or R_TwoAs a specific example of the group represented by
Statements described on page 8, line 10 to page 18, line 8
Is mentioned. L₁, L_Two, L_Three, E
As a concrete example, Japanese Patent Application No. 2-386, page 18, line 9
From page 25 to the third line, and the general formula
Specific examples of the compound represented by [6] include the following compounds
Others are described in Japanese Patent Application No. 2-386, pages 26 to 65.
(1), (3) to (5), (7) to (11),
(14) to (16), (19) to (28), (30) to (3
4), (36) to (40), (42), (44) to (46),
(50), (52) to (54), (56) to (68), (7
0), (71), (73), (76), (77), (80), (8
1), (84) to (116). Embedded imageEmbedded imageEmbedded imageEmbedded imageEmbedded imageEmbedded imageIn the general formula [7], A, B, L₁, L_Two,
L_ThreeSpecific examples of each group represented by
No. 348, page 7, line 6 to page 17, line 20
And a compound represented by the general formula [7]:
Examples thereof include the following compounds, as well as Japanese Patent Application No. 1-342348.
(2), (3),
(5), (6), (8) to (11), (13) to (1)
8), (20), (21), (23), (24), (26), (2
From 7), (29), (30), (32) to (35), (37)
(42), (45), (47), (48), (50) to (59),
(62), (64), (66) to (68), (70) to (7
5), (77), (78), (80), (82), (83), (8
5) to (87), (89) to (92), (94), (96)
No. Embedded imageEmbedded imageEmbedded imageEmbedded imageIn the general formula [8], R₁, R_Two, L₁,
L_Two, L_Three, L_Four, L_FiveEach group represented by
In Japanese Patent Application No. 2-1786, from page 7, line 20 to page 17,
The one described in the sixth line is mentioned and represented by the general formula [8].
Specific examples of the compound include, in addition to the following compounds, Japanese Patent Application No. 2-17
No. 86, page 18 to page 23, compounds 1, 4,
6, 8 to 10, 12 to 17, 19, 22, 24, 26 to 28, 30,
32 to 35, 38, 39, 41 to 44, 47, 48, 50, 53 to 55,
57 and 58. Embedded imageEmbedded imageThe compounds represented by the above general formulas [1] to [8]
The compound may be used in the photographic material according to the purpose, for example, optical density.
Is used to be 0.05 to 3.0. Also, solid fine particles
(Preferably an average particle size of 10 μm or less, more preferably 1.0 μm
m or less) in the photographic constituent layer in the state of
Although water-insoluble and stably present in the photosensitive material,
At the pH at the time of treatment (for example, 8 or more), it becomes water-soluble and
Elutes in the liquid. As a method for obtaining a solid fine particle dispersion,
For example, a solid dye is used for ball mill, sand mill, colloid mill
For example, U.S. Pat.
No. 7,446, International Patent Application Publication No. 88-4794
No. In addition, it is preferable to add in the non-photosensitive layer.
Especially in the layer between the silver halide emulsion layer and the support.
Good. Next, 1-phenyl-5-mercaptotetrazo
-Based compounds (hereinafter also referred to as “compound 9”)
explain. As the compound [9], for example, the following general formula
Examples shown in [9] can be given. Embedded imageIn the formula, Y is a hydrogen atom, an alkyl group, OH, -CO
NHR¹, -SO_TwoNHR¹, -NHCOR¹, -COOM^Two, Or -SO_ThreeM^TwoThe table
You. R¹Is an alkyl group, an aryl group, or -N (R^Two) (R^Three)
And R^Two, R^ThreeRepresents a hydrogen atom, an alkyl group, or
Or an aryl group;^Two, R^ThreeAre connected to each other to form a ring
It may be formed.Where R ^Two Is a hydrogen atom and R ^Three Is a methyl group
There is no case. M¹, M^TwoAre hydrogen atoms and alcal gold, respectively.
Represents a group atom or an ammonium group. n is 1 or 2
Represents an integer, and when n is 2, Y may be the same or different
No. The above alkyl group is, for example, one having 1 carbon atom.
And the aryl group is, for example, a phenyl group.
And each group includes those having a substituent. Compounds that are mercaptotetrazole compounds
In the present invention, the compound [9] is such that at least one of the compounds
Light-sensitive material contained in at least one of the silver halide emulsion layers;
It is. Addition of Compound [9] to Silver Halide Emulsion Layer
The addition amount is 2 × 10 5 per mol of silver halide.^-Four~ 2 × 10^-1
Mole is preferred, especially 1 × 10^-3~ 5 × 10^-2Mol is preferred
No. The time of addition is not particularly limited.
It may be at the time of fabric liquid preparation or before, and the addition method is optional.
Yes, for example, dissolved in an appropriate solvent such as methanol and added.
Just do it. Next, preferred representative exemplification of compound [9]
Show compound. However, as a matter of course, it can be used in the present invention.
The compounds that can be obtained are not limited to the following examples. Illustrative examples include M and M in the following general formula [10].
R¹¹~ R¹⁵This is done by specifying Embedded imageEmbedded imageThe light-sensitive material of the present invention is particularly suitable for a roller transport system.
When processed using the automatic processor under the conditions of the following formula [1]
Is preferred. ## EQU2 ##In the formula [1], 1 is a roller transport type automatic expression.
From the core of the first roller at the insertion port of the imager,
By the length (unit: m) of the transport line up to the end roller core
And T is the time required to pass through l (unit:
Seconds). Silver halide milk used in the light-sensitive material of the present invention
As the agent, any of ordinary silver halide emulsions can be used.
Can be. The emulsion can be chemically sensitized by a conventional method.
Optically sensitized to the desired wavelength range using a sensitizing dye
it can. The silver halide emulsion contains an antifoggant,
Additives and the like can be added. As a binder for the emulsion
In some cases, it is advantageous to use gelatin. The emulsion layer and other hydrophilic colloid layers are hardened
Plasticizer, water-insoluble or poorly soluble
It may contain a dispersion (latex) of a synthetic polymer
it can. In the emulsion layer of the color photographic light-sensitive material,
A coupler is used. Color Docker with Further Color Correction Effect
Cups with pullers, competing couplers and oxidized developing agents
Rings for development accelerator, bleach accelerator, developer, halo
Silver Genide Solvent, Toning Agent, Hardener, Fogging Agent, Antifogging
Photos like sensitizers, chemical sensitizers, spectral sensitizers, and sensitizers
Use compounds that release useful fragments
Can be. The photosensitive material includes a filter layer,
Auxiliary layers such as an anti-irradiation layer and irradiation prevention layer are provided.
But in these layers and / or in the emulsion layers
Is bleeding or bleaching from the photosensitive material during development
May be contained. The photosensitive material includes a formalin scavenger.
ー, optical brightener, matting agent, slip agent, image stabilizer, interface
Activators, antifoggants, development accelerators, development retarders and
A white accelerator and the like can be added. The support for the photosensitive material is polyethylene.
Paper, polyethylene terephthalate foil
Use film, baryta paper, cellulose triacetate, etc.
Can be. To obtain an image using the light-sensitive material of the present invention
After exposure, by means of commonly known photographic processing
Can be EXAMPLES Specific examples of the present invention will be described below.
The clear embodiments are not limited to these. Example 1 A silver halide photographic light-sensitive material was prepared as follows.
Was. (A) Preparation of Monodisperse Emulsion The reaction vessel was maintained at 60 ° C., pAg = 8, and pH = 2.
Iodine with an average particle size of 0.3 μm by the double jet method
A monodispersed cubic silver iodobromide emulsion containing 2 mol% of silver was obtained.
According to electron microscope observation, the twin generation rate is 1% or less by number.
it was under. Using this emulsion as a seed crystal,
Grew. Keep the gelatin aqueous solution at 40 ° C. in the reactor
The seed crystal was added, and ammonia water and acetic acid were further added to adjust pH =
Adjusted to 9.5. Adjust to pAg7.3 with ammoniacal silver ion solution
After that, while keeping pH and pAg constant, ammoniacal silver ion
A solution containing potassium iodide and potassium bromide
Silver iodobromide layer containing 30 mol% of silver iodide
It was formed. PH = 9, pAg = 9.0 using acetic acid and silver bromide
Adjustment, followed by ammoniacal silver ion solution and potassium bromide.
And grow to 90% of the grain size after growth
I let it. At this time, the pH was gradually decreased from 9.0 to 8.20. After adding potassium bromide solution to make pAg = 11,
Further, add ammoniacal silver ion solution and potassium bromide to adjust the pH.
And gradually grow it to pH 8, and grow with an average particle size of 0.7.
A silver iodobromide emulsion containing 2 .mu.m of silver iodide was obtained. In the preparation of the emulsion, the following sensitizing dyes
(A) 300 mg / mol of silver in emulsion, sensitizing dye
15 mg of (b) was added to obtain an emulsion. Sensitizing dye (a) 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfop
(Ropyl) anhydride of sodium oxacarbocyanine sensitizing dye (b) 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-
3,3'-di- (4-sulfobutyl) benzimidazolocal
Next, as shown below, a desalting step for removing excess salts is performed.
went. Keep the silver halide emulsion solution at 40 ° C.
Add the formalin condensate of sodium taren sulfonate
To settle the silver halide grains.
Was added with pure water at 40 ° C. And add magnesium sulfate
The silver halide grains are settled again and the supernatant is removed.
You. Do this again and add gelatin, pH 6.0, pAg 8.5
Emulsion was obtained. The emulsion obtained above was kept at 55 ° C.
Chemical sensitization was performed by adding fluorinated gold and hypo, and
Droxy-6-methyl-1,3,3a, 7-tetrazainde
Was added to obtain a photosensitive emulsion. This is called emulsion (A).
You. (B) Preparation of Tabular Grain Emulsion In 1 liter of water, 10.5 g of KBr was added, and HO (CH
_Two)_TwoS (CH_Two)_TwoS (CH_Two)_TwoOH 0.5wt% aqueous solution 10ml, and gelatin
30 g was added to dissolve and kept at 70 ° C. In this solution,
While stirring, an aqueous solution of silver nitrate 0.88 mol / l 30 ml and iodide
Aqueous solution of potassium and potassium bromide (molar ratio 3.5: 96.5)
0.88 mol / l 30 ml was added by the double jet method,
Grains having an average grain size of 0.60 μm and a silver iodide content of 3.5 mol% were obtained.
Was. After the addition of the mixed solution was completed, the temperature was lowered to 40 ° C. Then
The pH was lowered to 4.0 by the same method as in the emulsion (A).
After desalting, add 15 g of gelatin / 1 mol of AgX
Thus, an emulsion (B) containing tabular grains was prepared. (C) Preparation of Polydisperse Emulsion A polydisperse emulsion was prepared from the following four kinds of solutions by a forward mixing method.
Prepared. Solution A 100 g of silver nitrate 100 g ammonia water (28%) 78 ml Add water 240 ml Add solution B 8 g ossein gelatin 8 g Potassium bromide 80 g Potassium iodide 1.3 g Add water 550 ml Solution C ammonia water 6 ml Glacial acetic acid 10 ml water 34 ml D Liquid glacial acetic acid 226 ml Add water 400 ml Add solution B and solution C into the reactor for emulsion preparation,
Stir with a propeller-type stirrer at 300 revolutions / min.
It was kept at 5 ° C. Next, the solution A was divided into a ratio of 1: 2:
One volume, 100 ml, was charged over one minute. Ten
After stirring for 2 minutes, add 200 ml of the remaining 2 volumes of solution A to 1
Charged over 0 minutes. Stirring was continued for another 30 minutes. So
And add solution D to adjust the pH of the solution in the reactor to 6.0.
And the reaction was stopped. The average grain size of the silver halide grains was 0.56 μm.
And the dispersity was 0.32. The silver iodide content is 1.2
Mole%. With respect to the emulsions obtained in the above (B) and (C),
Ammonium thiocyanate and gold chloride as chemical sensitizers
Acid and hypo were added and gold-sulfur sensitized. After completion of the chemical sensitization, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added.
Thereafter, 150 mg of potassium iodide / 1 mol of AgX and the sensitizing dye
(A) and (b) were added in the same amount as in emulsion (A),
Sensitization was performed. Each of the emulsions thus obtained was added to the milk
Agents (B) and (C). Each of the above (A), (B) and (C)
T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl-triphenylphos per mole of silver halide as an additive Phonium chloride 50mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4g 2-Mercaptobenzimidazole-5-sodium sulfonate 5mg nC_FourH₉OCH_TwoCH (OH) CH_TwoN (CH_TwoCOOH)_Two 1 g 1,1-Dimethylol-1-brom-1-nitromethane 10 mgThe emulsion was added to obtain an emulsion coating solution. Further, as a protective layer solution, 1 g of gelatin was used.
The following amounts were added to give a coating liquid for a protective layer. 7 mg of matting agent comprising polymethyl methacrylate having an average particle size of 7 μm 70 mg of colloidal silica having an average particle size of 0.013 μmUsing each of the above coating solutions, the following samples
1-A-1 to 1-A-10, 1-B-1 to 1-B-8 and 1-C-1
~ 1-C-8 was prepared. (Preparation of Sample 1-A-1)
Glycidyl methacrylate 50wt%, methyl methacrylate
10 wt%, butyl methacrylate 40 wt% copolymer,
Water-soluble copolymer diluted to a concentration of 10 wt%
By using a dispersion and applying it to both sides,
A processed support was obtained. Then, the emulsion is placed on the support.
An emulsion layer comprising (A) and a protective layer were provided. That is,
3.2g / m as silver on one side^TwoThe emulsion layer so that
0.98 g / m^TwoProtective layer so that
Both sides were simultaneously coated at a speed of 140 m / min. (Preparation of Samples 1-A-2 to 1-A-10) Sample 1
-A-1 between the emulsion layer and the undercoat layer
Dyes shown in the table as crossover cut substances (comparison dyes)
Or a dye represented by the general formula [1] of the present invention)
Coating to insert a crossover cut layer
Was. Addition amount in the table is 1m on both sides^TwoThe amount per hit. But dye
Can be added by either of the following addition methods (a) or (b)
I decided to adopt this. Addition method (a) (Method of adding as fine solid particles)
The fine particles of the ball mill are dispersed by the following procedure. That is, water and a surfactant were added to a ball mill container.
Lucanol XC (alkyl naphthalene-sulfonate,
And the dyes to be added are added.
Then, put zirconium oxide beads and seal the container.
Disperse in a ball mill for days. Thereafter, an aqueous gelatin solution is added and mixed for 10 minutes.
Then, the beads are removed to obtain a coating solution. Addition method (b) (Comparative addition method) The dye was added with a small amount of triethylamine.
Dissolved in methanol, and added to an aqueous gelatin solution to adjust the pH.
6.0 and use as coating solution. For each sample, the amount of dye added was
Was adjusted to the amount shown in FIG. For samples 1-A-5 to 1-A-10,
The compound of the general formula [9] of the present invention is shown in the table in the emulsion layer of
The sample of the present invention was contained by kinds and amounts. This transformation
The compound is added as a 1% methanol solution when preparing the coating solution.
did. Similarly, samples 1-B-1 to 1-B-8 and 1
-C-1 to 1-C-8 are also shown in the table.
Created. The following evaluation was performed on the obtained sample. (Measurement of Sensitometry) "New Edition, Lighting
The standard light B described in “Data Book”
0.1 seconds, 3.2 cms with non-filter on both sides of film
Exposure was performed so that the same light amount was obtained. The above sample is SRX-
XD-SR developer using 1001 automatic developing machine (manufactured by Konica Corporation)
And 45 seconds using the XF-SR fixing solution, including the drying process.
And the sensitivity of each sample was determined. Note that the above processing conditions
Is T = 45, l = 3.71, l^0.75× T = 120.3.
Sensitivity is the amount of light required to increase the blackening density by 1.0.
Obtain the reciprocal and calculate the relative sensitivity with the sensitivity for sample 1 as 100.
It was expressed by. (Evaluation of MTF) 0.5 to 10 lines / mm of lead
MTF chart with square wave of fluorescent screen KO-250
(Made by Konica Corp.)
Concentration of unshielded part of lead chart on lum surface
However, X-rays were irradiated so that both sides became about 1.0. The samples irradiated with X-rays as described above
After the same development processing as described above, the recorded rectangular wave
Pattern of Sakura Micro Densitometer M-5
(Manufactured by Konica Corporation). At this time,
The aperture size is 300μm in the direction parallel to the rectangular wave
It was 25 μm in the direction, and the magnification was 20 times. M obtained
It represents the TF value and is represented by a value of a spatial frequency of 2.0 lines / mm. (Evaluation of Processing Unevenness)
Expose the entire surface to a density of 0.5, then
Was performed. The evaluation was performed in the following five stages. 1. Very poor 2. Inferior Normal 4. Good 5. Very good The results of each evaluation are shown in the table below. As described above, the general formulas [1] to
A sample was prepared using the dye of [8], and the obtained result was as follows.
Is shown in the table. The following comparative dyes were used. Embedded imageEmbedded image[Table 1][Table 2][Table 3][Table 4][Table 5][Table 6][Table 7][Table 8][Table 9][Table 10][Table 11][Table 12][Table 13][Table 14][Table 15][Table 16][Table 17][Table 18][Table 19][Table 20][Table 21][Table 22][Table 23][Table 24]As is clear from the table, the samples according to the present invention
Indicates that the sensitivity decrease is less than that of the comparative sample.
It can be seen that sharpness is improved and processing unevenness is small. Example 2 In the same manner as in Example 1, the emulsions and dyes shown in the table were used.
A sample was prepared. However, no sensitizing dye was added. Ma
In addition, in the evaluation of MTF sharpness, the fluorescent screen was NR-25.
0 (manufactured by Konica Corporation) was used. Further, the development processing was performed by using the prototype shown in FIG. 1 or FIG.
The processing time was varied using an automatic processor. In FIGS. 1 and 2, reference numeral 1 denotes a photosensitive material insertion port.
1 roller, 2 the last roller at the drying outlet, 3a a developing tank,
3b is a fixing tank, 3c is a washing tank, and 4 is a feeling of being a processing target.
Optical material, 5 is a squeeze part, 6 is a dry part, 7 is a dry air
It is an outlet. The evaluation results are also shown in the table. From the table, it can be seen that the present embodiment also relates to the present invention.
It will be appreciated that the sample has excellent performance. [Table 25][Table 26][Table 27][Table 28][Table 29][Table 30][Table 31][Table 32]As described above, the silver halide photographic sensitivity of the present invention is as described above.
The optical material suppresses the decrease in sensitivity and improves sharpness,
Moreover, it has the effect of reducing processing unevenness.
You.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of an automatic developing machine used in an embodiment of the present invention.

FIG. 2 is a configuration diagram of an automatic developing machine used in an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 First roller at photosensitive material insertion opening 2 Final roller at drying outlet 3a Developing tank 3b Fixing tank 3c Rinse tank 4 Photosensitive material to be processed 5 Squeeze section 6 Drying section 7 Dry air outlet

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasushi Yasushi Konica, Inc. 1 Konica Corporation, Sakura-cho, Hino-shi, Tokyo (72) Inventor Yoshiyoshi Inoue 1 Konica Corporation, Sakura-cho, Hino-shi, Tokyo (72) Inventor Hirofumi Ohashi 1 Konica Co., Ltd. Sakuracho, Hino-shi, Tokyo Investigator Yuko Akiyama (56) References JP-A-3-231240 (JP, A) JP-A-3-23441 (JP, A) JP-A-3-3 7930 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/83 G03C 1/34

Claims (1)

(57) [Claims] 1. A black-and-white silver halide photographic material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, wherein at least one of the hydrophilic colloid layers is as follows: It contains at least one kind of solid fine particle dispersions of the compounds represented by the general formulas [1] to [8], and at least one of the silver halide emulsion layers contains a compound represented by the following general formula [9]. A black-and-white silver halide photographic light-sensitive material containing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material is processed by a roller transport type automatic developing machine which performs processing under the conditions corresponding to the following formula [1]. Embedded image Formula [1] A = L ₁ - a _{(L 2 = L 3) m} -B A is 2-pyrazoline-5-one acidic nucleus, B represents a 4-aminoaryl group, L1 to L3 Represents a methine group, m represents 0 or 1, and the compound of the general formula [1] satisfies at least one of the following conditions (1) to (4). (1) B has at least one carboxyl group. (2) A has at least one sulfamoyl group. (3) A has at least one carboxyl group which may have a carboxyl group or an aliphatic group, and at least one sulfamoyl group which may have an aliphatic group. (4) It has at least one carboxyl group and a sulfonamide group bonded to the 2-pyrazolin-5-one acidic nucleus. However, when only the condition (3) is satisfied, 2-pi
Carboxyphenyl group on acid nucleus of lazoline-5-one
Except when is directly bonded. Also, condition (3) and
When only (4) is satisfied, 2-pyrazolin-5-
Carboxyphenyl group and carboxyl on the acidic nucleus
Except when groups are directly bonded at the same time. Embedded image General formula [2] In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group,
Cycloalkyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarboxyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, R represents a cyano group, an amino group, a sulfonamide group, an amide group, an ureido group, a thioureido group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, a carboxyl group or a hydroxyl group;
₃ and R ₄ represent a phenyl group having a carboxyl group via a linking group , L _{1 to} L ₃ represent a methine group, n represents an integer of 0 to 2, and when n is 2, each of L ₂ and L ₃ May be the same or different. Embedded image General formula [3] In the formula, R ₁ and R ₂ are each —COOH, — (CH ₂ ) _{n
COOH, -A-NHCOCH 2 CH 2} COOH, -CO
_{NHN (CH 2 COOH) 2,} -NHCON (CH 2 CO
OH) ₂ , -CONH-A-COOH, A represents an aryl group, and n represents 1 or 2. R ₃ and R ₄ represent an alkyl group, alkenyl group, cycloalkyl group, alkynyl group, aryl group, or heterocyclic group having no hydrogen atom or carboxyl group. L _{1 to} L ₃ represent a methine group, and n represents 0
Represents an integer of ２2, and when n is 2, each of L ₂ and L ₃ may be the same or different. Embedded image General formula [4] In the formula, R ₁ and R ₂ are an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarboxyl group, an alkylsulfonyl group, and an aryl, respectively. Sulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group, ureido group, thioureido group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, carboxyl R ₃ and R ₄ represent an alkyl group having a carboxyl group, a cycloalkyl group, a naphthyl group or a heterocyclic group. L
_{1 to} L ₃ represent a methine group; n represents an integer of 0 to 2;
When = 2, each of -L ₂ = L ₃ -may be the same or different. Embedded image General formula [5] In the formula, R ₁ and R ₂ are an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarboxyl group, an alkylsulfonyl group, and an aryl, respectively. Sulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group, ureido group, thioureido group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, carboxyl Represents a group or a hydroxyl group, and R ₃ and R ₄ represent an m-carboxyphenyl group or an o-carboxyphenyl group. L ₁ , L ₂ , L ₃ , L ₄ , and L ₅ represent a methine group, and n ₁ and n ₂ represent 0 or 1. [Formula 6] In the formula, R ₁ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group,
Aryloxycarboxyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group,
Arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group, ureido group, thioureido group, alkoxyl group,
Aryloxy group, alkylthio group, arylthio group,
R2 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group. L _{1 to} L ₃ each represent a methine group; E represents an acidic nucleus necessary for forming an oxonol dye; n represents an integer of 0 to 2;
L ₂ = L ₃ -may be the same or different. Furthermore, the general formula [6]
Has at least two carboxyl groups, sulfonamide groups, and sulfamoyl groups. Embedded image General formula [7] In the formula, R ₁ and R ₂ are an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarboxyl group, an alkylsulfonyl group, and an aryl, respectively. Sulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group, ureido group, thioureido group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, carboxyl R ₃ , R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group;
L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group, and n1, n
2 represents 0 or 1. However, at least one of R ₁ , R ₂ , R ₃ , and R ₄ has a sulfonamide group and / or a sulfamoyl group, and the compound has a sulfonamide group and / or a sulfamoyl group.
Or it has at least two sulfamoyl groups. Embedded image General formula [8] In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group,
Cycloalkyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarboxyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, L represents a cyano group, an amino group, a sulfonamide group, an amide group, an ureido group, a thioureido group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, a carboxyl group or a hydroxyl group;
₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group, and n ₁ and n ₂ represent 0 or 1. Embedded image General formula [9] In the formula, Y is a hydrogen atom, an alkyl group, OH, -CONHR ¹ , -SO ₂
NHR ^1, represents an -NHCOR ^1, -COOM ² or -SO ₃ M ^2,. R ¹
Represents an alkyl group, an aryl group or a ^{-N, (R 2) (R} 3),
R ² and R ³ each represent a hydrogen atom, an alkyl group, or an aryl group, and R ² and R ³ may combine with each other to form a ring. However, there is no case where R ² is a hydrogen atom and R ³ is a methyl group. M ¹ and M ² each represent a hydrogen atom, an alkali metal atom or an ammonium group. n represents an integer of 1 or 2, and when n is 2, Y may be the same or different. Examples of the alkyl group include those having 1 to 3 carbon atoms, and examples of the aryl group include a phenyl group. Each group includes those having a substituent. [Equation 1] l ^0.75 × T = 50-125 0.7 <l <4.0 where l is the distance from the core of the first roller at the insertion opening of the roller transport type automatic developing machine to the drying outlet. It is the length (unit: m) of the transport line up to the core of the final roller, and T is the time (unit: second) required to pass through l.