JPH0545790A - Silver halide photographic sensitive material high in sensitivity and sharpness and small in uneven processing - Google Patents

Abstract

PURPOSE:To enhance sensitivity and sharpness and to improve uneven processing characteristics by incorporating a dispersion of the fine solid particles of a specified compound in a hydrophilic colloidal layer and a specified compound in a silver halide emulsion layer. CONSTITUTION:At least one of the hydrophilic colloidal layers contains at least one kind of a dispersion of the fine solid particles of at least one of the compounds represented by formulae I-V, and at least one of the silver halide emulsion layers contains at least one of 1-phenyl-5-mercaptotetrazole derivatives. In formulae I and II, A is the fundamental nucleus of 2-pyrazolin-5-on acid: B is 4-amino-aryl; each of L1-L3 is methine; (m) is 0 or 1: each of R1 and R2 is a substituent or carboxy or the like; each of R3 and R4 is phenyl having COOH combined through a bonding group, or H or the like; and (n) is 0 or 1 or 2.

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 light-sensitive material containing an oxonol dye, more specifically, a high-sensitivity, high-sharpness and process-unevenness obtained by dyeing a specific layer with an oxonol dye. It relates to less silver halide photographic light-sensitive materials.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are required to have high image quality characteristics such as excellent sharpness and color reproducibility.

On the other hand, in recent years, in order to counter the immediacy of electrophotographic materials, which are competing in the field of silver halide photographic light-sensitive materials, further shortening of processing time, that is, ultra-rapid processing suitability is required. In order to realize the above-mentioned high image quality characteristics and ultra-rapid processing suitability required for such photographic light-sensitive materials, in the industry, further thinning of photographic light-sensitive materials, or the use of silver halide or additive compound materials Efforts such as optimization have been made. By the way, it is well known that a dye is contained in a silver halide photographic light-sensitive material for the purpose of improving image quality or adjusting the sensitivity of silver halide emulsion, and such techniques include, for example, halation prevention, irradiation prevention, and light absorption. Used in filters.

Further, recently, the technique of incorporating a dye has been used for a dye (hereinafter referred to as "YC dye") for the purpose of substituting yellow colloidal silver in a color photographic light-sensitive material and a crossover cut layer in an X-ray photographic light-sensitive material. The use of dyeing dyes, dyes for dyeing non-photosensitive emulsion layers in printed photographic light-sensitive materials, and the like are widespread.

The dyes used for these purposes are 1. Have a good absorption spectrum 1. 2. Do not diffuse from the colored layer to other layers. 3. Do not have a photographic effect on the photosensitive silver halide emulsion. 4. Stable in silver halide photographic light-sensitive material. Easy to add 6. 6. It is in the emulsion coating solution and does not affect the solution viscosity. It is required as a property that no color remains after processing.

A large number of dyes have been proposed in the past for the purpose of satisfying these desired characteristics. For example, US Pat. Nos. 3,540,887, 3,544,325, and 3,560,214,
Japanese Patent Publication No. 31-10578 and Japanese Patent Publication No. 51-3623, benzylidene dyes, British Patent No. 506,385 and Japanese Patent Publication No. 39-22069 oxonol dyes, U.S. Pat. The styryl dyes and the like are proposed in the issue.

These dyes are generally dissolved in water or an organic solvent miscible with water and added to the photographic composition. However, when the dye is water-soluble, it does not stay in the layer to be dyed, but diffuses in all layers. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye as much as it diffuses to other layers, which is an unfavorable phenomenon such as sensitivity decrease, gradation variation, and fogging abnormality in both the own layer and other layers. May appear. In particular, when the light-sensitive material is held for a long time, fog is significantly generated or desensitized, and if the amount used is reduced to avoid these, the original light absorption effect cannot be sufficiently obtained. Dyes that have a diffusive property for dyeing a specific layer against such a problem are also known, and as a diffusion-resistant dye, for example, U.S. Patent Nos. 2,538,008 and 2,5,5
39,009, 4,420,555, each specification, JP-A-61-204630
Issue 61-205934, Issue 62-32460, Issue 62-56958, Issue 6
2-92949, 62-222248, 63-40143, 63-18474
No. 9, 63-316852, YC dyes are described.

Further, these dyes lower the green sensitivity because yellow colloidal silver called Carey Lea Silver, which is generally used in color photographic light-sensitive materials, absorbs not only the blue light region but also a part of long wavelength side. Many proposals have been made, partly for the purpose of improving the drawbacks of increasing the fog of adjacent layers and for saving precious silver resources.

However, these diffusion-resistant dyes alleviate the above-mentioned drawbacks to some extent, but their storage stability is poor and desensitization occurs over time. Also, because the bleaching property is insufficient,
Causes color contamination. In addition, there is a new problem that processing unevenness is likely to occur, and particularly when rapid processing is performed, the processing unevenness becomes severe.

Therefore, in order to improve these, new diffusion-resistant dyes are required.

[0011]

OBJECT OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material containing a diffusion resistant dye which meets the above-mentioned requirements, thereby improving the sensitivity, sharpness and uneven processing property. It is in.

[0012]

Means for Solving the Problems As a result of intensive studies made by the present inventors in view of the above problems, the above object of the present invention was as follows.
In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, at least one of the hydrophilic colloid layers is represented by the following general formulas [1] to [8]. A silver halide containing at least one kind of solid fine particle dispersion of the compound shown in and at least one of the silver halide emulsion layers contains at least one 1-phenyl-5-mercaptotetrazole compound The present invention has been completed by finding out what is achieved by a photographic light-sensitive material.

[0013]

[Chemical 9]

A is a 2-pyrazolin-5-one acidic mother nucleus,
B is a 4-aminoaryl group, L _{1 to} L ₃ are methine groups,
m represents O 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, sulfonamide group, aminosulfonylamino group or sulfamoyl group.

(2) A has at least one sulfamoyl group.

(3) A contains at least one carboxyl group, sulfonamide group or aminosulfonylamino group.
It has at least one aliphatic group, heterocyclic group or naphthyl group.

(4) 2-Pyrazolin-5-one It has at least one carboxyl group, sulfonamide group or aminosulfonylamino group bonded to the acidic mother nucleus.

[0019]

[Chemical 10]

In the formula, R ₁ and R ₂ are substituents, R ₃ and R ₄ are phenyl groups having a carboxyl group via a linking group, and L
_{1 to} L ₃ are methine groups, n is an integer of 0 to 2, and n is 2
At this time, each L ₂ and L ₃ may be the same or different.

[0021]

[Chemical 11]

In the formula, R ₁ and R ₂ are a carboxyl group or a group having a carboxyl group, R ₃ and R ₄ are substituents having no hydrogen atom or a carboxyl group, and L _{1 to} L ₃ are methine groups, n represents an integer of 0 to 2, and when n is 2, each L ₂ ,
L ₃ may be the same or different.

[0023]

[Chemical formula 12]

In the formula, R ₁ and R ₂ represent substituents, and R ₃ and R ₄
Represents 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, and when n = 2,
Each −L ₂ = L ₃ − may be the same or different.

[0025]

[Chemical 13]

In the formula, R ₁ and R ₂ represent a substituent, 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,
n ₁ and n ₂ represent 0 or 1.

[0027]

[Chemical 14]

In the formula, R ₁ represents a substituent, and R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

L _{1 to} L ₃ represent a methine group, E represents an acidic nucleus necessary for forming an oxonol dye, and n is 0 to 2
, And when n = 2, each −L ₂ = L ₃ − may be the same or different. Furthermore, the compound of the general formula [6] has at least two carboxyl groups, sulfonamide groups and sulfamoyl groups.

[0030]

[Chemical 15]

In the formula, R ₁ and R ₂ represent a substituent, and R ₃ and R ₄
Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and 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. Provided that at least one of R ₁ , R ₂ , R ₃ and R ₄ has a sulfonamide group and / or a sulfamoyl group,
Further, the compound has at least two sulfonamide groups and / or sulfamoyl groups.

[0032]

[Chemical 16]

In the formula, R ₁ and R ₂ are alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarboxyl groups, alkylsulfonyl groups, 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, carboxyl A group or a hydroxyl group, L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group, and n ₁ ,
n ₂ represents 0 or 1.

In the general formula [1], A, B, L ₁ , L ₂ ,
Specific examples of each group represented by L ₃ include Japanese Patent Application No. 1-331
Nos. 588, page 8, line 3 to page 18, line 14 are specific examples of compounds represented by general formula [1], in addition to the following compounds: (9) to (19) and (2
2), (23), (25) to (46), (48) to (51),
(56) to (62), (67) to (80), (82) to (10
2) is mentioned.

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

[Chemical 21]

The substituent represented by R ₁ and R ₂ in the general formula [2] 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. Group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group,
Preferred are arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group, ureido group, thioureido group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carboxyl group and hydroxyl group. And specific examples thereof include those described in Japanese Patent Application No. 2-2211, page 7, line 18 to page 17, line 5. Specific examples of the groups represented by R ₃ , R ₄ , L ₁ , L ₂ and L ₃ include Japanese Patent Application No. 2-2211, page 17, line 6 to page 21, Examples of the compound represented by the general formula [2] include those described below, and in addition to the compounds 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
To 34, 37 to 43, 45 to 49, 51, 52, 54 to 60, 63 to 73.

[0041]

[Chemical formula 22]

[0042]

[Chemical formula 23]

[0043]

[Chemical formula 24]

Specific examples of the group having a carboxyl group represented by R ₁ or R ₂ in the general formula [3] include Japanese Patent Application No. 2-2212, page 13, line 4 to page 15, Examples of the substituents having no carboxyl group represented by R ₃ or R ₄ include those described in the 20th line, an alkyl group, an alkenyl group, a cycloalkyl group, an alkynyl group, an aryl group,
Heterocyclic groups are mentioned as preferable ones, and specific examples thereof include those described in Japanese Patent Application No. 2-2212, page 7, line 12 to page 12, line 16. Also, L
Specific examples of the groups represented by ₁ , L ₂ and L ₃ include those described in Japanese Patent Application No. 2-2212, page 12, line 17 to page 13, line 3. Specific examples of the compound represented by the general formula [3] include, in addition to the following compounds, compounds 1 to 13 and 15 described in Japanese Patent Application No. 2-2212, pages 17 to 29.
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 to 105, 108 to 117, 120, 121, 123.

[0045]

[Chemical 25]

[0046]

[Chemical formula 26]

[0047]

[Chemical 27]

The substituent represented by R ₁ or R ₂ in the general formula [4] includes R ₁ and R ₂ in the general formula [2].
The preferred examples of the substituents represented by are: Specific examples include Japanese Patent Application No. 2-62, page 8, page 6
From line 15 to page 17, line 15 can be mentioned. R
Specific examples of the groups represented by ₃ , R ₄ , L ₁ , L ₂ and L ₃ include Japanese Patent Application No. 2-62, page 17, line 16 to page 19, line 2 In addition to the compounds described below, specific examples of the compound represented by the general formula [4] include those described in Japanese Patent Application No.
No. 62, 1, 6 to 8, 13 to 21, 24 to 28, 30, 33, 34, 36 to 54, 57 of the compounds described on pages 20 to 26.
To 64, 66, 67, 69 to 71, 73, 75 to 88.

[0049]

[Chemical 28]

[0050]

[Chemical 29]

[0051] Then R ₁ in Examples of the substituent in the general formula [5] represented by R ₁ or R ₂ the general formula [2],
The preferred ones of the substituents represented by R ₂ are mentioned, and specific examples and preferred ones are as follows:
No. 335570, page 7, line 11 to page 16, line 13 may be mentioned. Specific examples of the group represented by R ₃ or R ₄ include those described in Japanese Patent Application No. 1-335570, page 16, line 14 to page 17, line 1. ₁ ,
Specific examples of the methine group represented by L ₂ , L ₃ , L ₄ , and L ₅ are described in Japanese Patent Application No. 2-62, page 18, line 12 to page 19, line 2. The methine group of is mentioned. General formula [5]
In addition to the following compounds, specific examples of the compound represented by
From Japanese Patent Application No. 1-335570, the compounds 1 to 4 to 11, 14, 15, 18, 19, 21 to 23, 25 of pages 18 to 23
28, 30, 31, 33, 35 to 44, 46, 48 to 53, 57, 58, 6
0, 62, 63, 65 to 69 are included.

[0052]

[Chemical 30]

[0053]

[Chemical 31]

Examples of the substituent represented by R ₁ in the general formula [6] include those enumerated as preferable examples of the substituent represented by R ₁ in the general formula [2].
Specific examples of the group represented by ₁ or R ₂ include those described in Japanese Patent Application No. 2-386, page 8, line 10 to page 18, line 8. Specific examples of the groups represented by L ₁ , L ₂ , L ₃ , and E are described in Japanese Patent Application No. 2-386, page 18, line 9 to page 25, line 3. Specific examples of the compound represented by the general formula [6] include the following compounds, as well as the compounds (1) described in Japanese Patent Application No. 2-386, pages 26 to 65, (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).

[0055]

[Chemical 32]

[0056]

[Chemical 33]

[0057]

[Chemical 34]

[0058]

[Chemical 35]

[0059]

[Chemical 36]

[0060]

[Chemical 37]

In the general formula [7], A, B, L ₁ , L ₂ ,
Specific examples of each group represented by L ₃ include Japanese Patent Application No. 1-342.
Nos. 348, page 7, line 6 to page 17, line 20, can be mentioned, and specific examples of the compound represented by the general formula [7] include: Compounds (2), (3), described in pages 19 to 35 of the specification of JP-A-1-342348,
From (5), (6), (8) to (11), (13) to (1
8), (20), (21), (23), (24), (26), (2
7), (29), (30), (32) to (35), (37) to (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), and (96).

[0062]

[Chemical 38]

[0063]

[Chemical Formula 39]

[0064]

[Chemical 40]

[0065]

[Chemical 41]

In the general formula [8], R ₁ , R ₂ , L ₁ ,
Specific examples of the groups represented by L ₂ , L ₃ , L ₄ and L ₅ are described in Japanese Patent Application No. 2-1786, page 7, line 20 to page 17, line 6. In addition to the following compounds, specific examples of the compound represented by the general formula [8] include Japanese Patent Application No. 2-17
Nos. 1 to 4 of the compounds described in pages 18 to 23 of the specification No. 86;
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 are mentioned.

[0067]

[Chemical 42]

[0068]

[Chemical 43]

The compounds represented by the above general formulas [1] to [8] are used in the photographic light-sensitive material so as to have an optical density of 0.05 to 3.0 depending on the purpose. In addition, solid fine particles (preferably an average particle size of 10 μm or less, more preferably 1.0 μm)
m or less), it is dispersedly contained in the photographic constituent layer,
Although it is water-insoluble and stable in the light-sensitive material, it becomes water-soluble at the pH (for example, 8 or more) during development processing and is eluted into the processing solution. Examples of the method of obtaining a solid fine particle dispersion include a method of treating a solid dye with a ball mill, a sand mill, a colloid mill, and the like, for example, US Pat.
7,446, International Patent Application Publication No. 88-4794. The addition location is preferably in the non-photosensitive layer, and particularly preferably in the layer between the silver halide emulsion layer and the support.

Next, the 1-phenyl-5-mercaptotetrazole compound (hereinafter also referred to as "compound 9") will be described.

Compound

[9] is, for example, the following general formula

The thing shown by [9] can be mentioned.

[0072]

[Chemical 44]

In the formula, Y is a hydrogen atom, an alkyl group, OH or --CO
_{^{NHR 1, -SO 2 NHR 1,}} -NHCOR 1, represents a -COOM ² or -SO ₃ M ^2,. R ¹ is an alkyl group, an aryl group, or —N (R ² ) (R ³ ).
And 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.

M ¹ and M ² each represent a hydrogen atom, an alcar 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.

The above alkyl group has, for example, 1 carbon atom.
Examples of the aryl group include phenyl groups, and each group includes those having a substituent.

Compounds that are mercaptotetrazole compounds

In the present invention, at least one of [9] is contained in at least one of the silver halide emulsion layers of the light-sensitive material.

Compound

The amount of [9] added to the silver halide emulsion layer is 2 × 10 ⁻⁴ to 2 × 10 ⁻¹ per mol of silver halide.
Molar is preferable, and 1 × 10 ^{−3 to} 5 × 10 ⁻² mol is particularly preferable.

The timing of addition is not particularly limited, and may be at the time of preparing the coating solution or before it, and the addition method is arbitrary. For example, it may be dissolved in a suitable solvent such as methanol and added.

Next, the compound

The preferable typical exemplified compounds of [9] are shown below. However, as a matter of course, the compounds that can be used in the present invention are not limited to the following examples.

The exemplification is carried out by specifying M and R ^{11 to} R ¹⁵ in the following general formula [10].

[0081]

[Chemical 45]

[0082]

[Chemical 46]

The light-sensitive material of the present invention is particularly preferable when processed with a roller-conveying type automatic processor under the condition of the following formula [1].

[0084]

[Equation 2]

In the formula [1], 1 is the length (unit: m) of the transport line from the core of the first roller at the insertion port of the roller transport type automatic processor to the core of the final roller at the drying outlet. , T is the time (unit:
Seconds).

As the silver halide emulsion used in the light-sensitive material of the present invention, any of ordinary silver halide emulsions can be used.

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

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

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

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

Further, the development accelerator, the bleaching accelerator, the developer, the silver halide solvent, the toning agent, the hardener, the hardener, the hardener and the hardener, which have the effect of color correction, are coupled with the colored coupler, the competing coupler and the oxidized product of the developing agent. Compounds that release photographically useful fragments such as film agents, fog agents, antifoggants, chemical sensitizers, spectral sensitizers, and sensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer, and these layers and / or the emulsion layer flow out from the light-sensitive material during the development processing. Dyes that are bleached or bleached may be included.

Formalin scavengers, fluorescent whitening agents, matting agents, slip agents, image stabilizers, surfactants, color antifoggants, development accelerators, development retarders and bleaching accelerators can be added to the light-sensitive material. ..

As the support of the photosensitive material, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain an image using the light-sensitive material of the present invention, a generally known means for carrying out photographic processing after exposure can be used.

[0096]

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

Example 1 A silver halide photographic light-sensitive material was prepared as follows.

(A) Preparation of Monodisperse Emulsion Iodine containing 2 mol% of silver iodide having an average grain size of 0.3 μm by the double jet method while maintaining the conditions of the reaction kettle at 60 ° C., pAg = 8, and pH = 2. A monodisperse cubic emulsion of silver bromide was obtained.
According to an electron microscope observation, the generation rate of twins was 1% or less in number. This emulsion was used as a seed crystal and further grown as follows.

The aqueous gelatin solution was kept at 40 ° C. in the reaction vessel, the above seed crystals were added, and further ammonia water and acetic acid were added to adjust the pH =
Adjusted to 9.5.

After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, a solution containing potassium iodide and potassium bromide was added to the ammoniacal silver ion by the double jet method while keeping the pH and pAg constant, and then iodinated. A silver iodobromide layer containing 30 mol% silver was formed.

The pH was adjusted to 9 and pAg = 9.0 using acetic acid and silver bromide, and then an ammoniacal silver ion solution and potassium bromide were added at the same time to grow until the grain size reached 90%. .. At this time, the pH was gradually lowered from 9.0 to 8.20.

After adding potassium bromide solution to pAg = 11, further adding ammoniacal silver ion solution and potassium bromide to adjust pH.
Gradually lowering the pH to 8 and growing it, the average particle size 0.7
A silver iodobromide emulsion containing .mu.m and 2 mol% of silver iodide was obtained.

During the preparation of the emulsion, the following sensitizing dye (a) was added at 300 mg and sensitizing dye (b) at 15 mg per mol of silver in the emulsion to obtain an emulsion.

Sensitizing dye (a) 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride Sensitizing dye (b) 5.5 ′ -Di- (butoxycarbonyl) -1,1′-diethyl-
Anhydrous 3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt Next, a desalting step for removing excess salts was performed as shown below.

The silver halide emulsion solution was kept at 40.degree. C., a formalin condensate of sodium naphthalenesulfonate was added to precipitate silver halide grains, and the supernatant was discharged, and then pure water at 40.degree. C. was added. Then, magnesium sulfate is added to again settle the silver halide grains, and the supernatant is taken. Do this again, add gelatin, pH 6.0, pAg 8.5
An emulsion of was obtained.

The emulsion thus obtained was kept at 55 ° C., chloroauric acid and hypo were added for chemical sensitization to give 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. In addition, a photosensitive emulsion was obtained. This is designated as emulsion (A).

(B) Preparation of tabular grain emulsion KBr 10.5 g and HO (CH) which is a thioether compound in 1 l of water.
₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH (10 ml of 0.5 wt% aqueous solution) and 30 g of gelatin were added and dissolved, and the mixture was kept at 70 ° C. In this solution,
While stirring, an aqueous solution of silver nitrate 0.88 mol / l and an aqueous solution of potassium iodide 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. 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) to desalt, and thereafter 15 g of gelatin / 1 mol of AgX was added to prepare an emulsion (B) containing tabular grains.

(C) Preparation of polydisperse emulsion A polydisperse emulsion was prepared from the following four kinds of solutions by the forward mixing method.

Solution A Silver nitrate 100 g Ammonia water (28%) 78 ml Water is added 240 ml Solution B Oscein gelatin 8 g Potassium bromide 80 g Potassium iodide 1.3 g Water is added 550 ml Solution C aqueous solution 6 ml Glacial acetic acid 10 ml Water 34 ml D Liquid glacial acetic acid 226 ml Water was added and 400 ml Solution B and solution C were poured into the reaction vessel for emulsion preparation, and the rotation speed was changed.
Stir with a propeller stirrer at 300 rpm to bring the reaction temperature to 5
It was kept at 5 ° C.

Next, the solution A is divided into a ratio of 1 volume: 2 volumes,
One volume, 100 ml, was added over 1 minute. Ten
After continuing stirring for 1 minute, add 200 ml of the remaining 2 volumes of solution A to 1
It was put in for 0 minutes. Stirring was continued for another 30 minutes. Then, the liquid D was added to adjust the pH of the solution in the reaction kettle to 6.0 and the reaction was stopped.

The silver halide grains had an average grain size of 0.56 μm and a dispersity of 0.32. The silver iodide content is 1.2
It was mol%.

The emulsions obtained in the above (B) and (C) were subjected to gold-sulfur sensitization by adding ammonium thiocyanate, chloroauric acid and hypo as chemical sensitization.

After completion of this chemical sensitization, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added.
Then, potassium iodide (150 mg / AgX1 mol) and the sensitizing dyes (a) and (b) were added in the same amounts as in the case of the emulsion (A), and spectral sensitization was carried out. The emulsions thus obtained are designated as emulsions (B) and (C), respectively.

Each of (A), (B) and (C) above was added to the light-sensitive emulsion as an additive, per mol of silver halide, 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-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium ammonium sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1g 1,1-Dimethylol-1-bromo-1-nitromethane 10mg

[0115]

[Chemical 47]

[0116] The ingredients described above were added to prepare an emulsion coating solution.

Further, the following amount was added as a protective layer liquid per 1 g of gelatin to obtain a protective layer coating liquid.

Matting agent consisting of polymethylmethacrylate having an average particle size of 7 μm 7 mg Colloidal silica having an average particle size of 0.013 μm 70 mg

[0119]

[Chemical 48]

Using 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 were prepared.
~ 1-C-8 was prepared.

(Preparation of Sample 1-A-1) As the subbing liquid,
Glycidyl methacrylate 50 wt%, methyl methacrylate 10 wt%, butyl methacrylate 40 wt% copolymer,
An aqueous copolymer dispersion diluted to a concentration of 10 wt% was used and applied on both sides to obtain an undercoated support. Then, an emulsion layer comprising emulsion (A) and a protective layer were coated on the support. That is,
An emulsion layer having a silver amount of 3.2 g / m ^{2 on} one side and a protective layer having a gelatin amount of 0.98 g / m ^{2 on} one side were simultaneously coated on both sides at a coating speed of 140 m / min.

(Preparation of Samples 1-A-2 to 1-A-10) Sample 1
-The photographic constitutional layer of A-1 further contains a dye (comparative dye or a dye represented by the general formula [1] of the present invention) shown in the table as a crossover cut substance between the emulsion layer and the subbing layer. The coating was performed so as to insert the crossover cut layer. The addition amount in the table is the amount per 1 m ^{2 on} both sides. However, as a method of adding the dye, any one of the following addition methods (a) and (b) was adopted.

Addition Method (a) (Method of Adding as Solid Fine Particles) The dye used is dispersed in ball mill solid fine particles by the following procedure.

That is, water and a surfactant alkanol XC (alkylnaphthalene-sulfonate, manufactured by DuPont) were put in a ball mill container, each dye to be added was added, and zirconium oxide beads were put and the container was sealed.
Disperse on a ball mill for a day.

Then, an aqueous gelatin solution is added and mixed for 10 minutes, and the beads are removed to obtain a coating solution.

Addition Method (b) (Comparative Addition Method) The dye was dissolved in methanol containing a small amount of triethylamine and then added to an aqueous gelatin solution to adjust the pH.
Set to 6.0 and use as the coating liquid.

The amount of the dye added to each sample was set to the amount shown in the table.

For Samples 1-A-5 to 1-A-10, the emulsion layer was prepared according to the general formula of the present invention.

The compound of [9] was contained in the types and amounts shown in the table to prepare a sample of the present invention. This compound was added as a 1% methanol solution when the coating solution was prepared.

Similarly, samples 1-B-1 to 1-B-8 and 1
-C-1 to 1-C-8 were also prepared as shown in the table.

The following evaluations were performed on the obtained samples.

(Measurement of sensitometry) Using the standard light B described in "New Edition, Lighting Data Book" as a light source, exposure time 0.1 seconds, 3.2 cms non-filter so that the same light quantity is obtained on both sides of the film. Exposed. The above sample is SRX-
The sensitivity of each sample was determined by using an 1001 automatic developing machine (manufactured by Konica Corporation), using the XD-SR developer and the XF-SR fixer for 45 seconds including the drying step. The conditions of the treatment, T = 45, l = 3.71 , was l ^0.75 × T = 120.3.
The sensitivity was expressed as a relative sensitivity with the sensitivity in the case of Sample 1 being 100, by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0.

(Evaluation of MTF) An MTF chart containing a rectangular wave made of lead of 0.5 to 10 lines / mm was used as a fluorescent screen KO-250.
It was brought into close contact with the back surface of the front side (made by Konica Corp.) and irradiated with X-rays so that the density of the area not shielded by the lead chart on the film surface was about 1.0 on both surfaces.

After the development treatment similar to that described above was performed on the sample irradiated with X-rays as described above, the recorded rectangular wave pattern was recorded on a Sakura Microdensitometer M-5 type (manufactured by Konica Corp.). Used and measured. The aperture size at this time was 300 μm in the parallel direction of the rectangular wave and 25 μm in the perpendicular direction, and the magnification was 20 times. Obtained M
The TF value is representatively shown by the value of spatial frequency 2.0 line / mm.

(Evaluation of Processing Unevenness) The same processing as above was carried out after the four-section sample was entirely exposed to a density of 0.5 after the processing.

The evaluation was carried out in the following 5 stages.

1. Very inferior 2. Inferior 3. Normal 4. Good 5. Very good The results of each evaluation are shown in the table below.

In this way, the general formulas [1] to
The following table shows the results obtained by preparing a sample using the dye of [8]. The following dyes were used for comparison.

[0138]

[Chemical 49]

[0139]

[Chemical 50]

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

[Table 5]

[0145]

[Table 6]

[0146]

[Table 7]

[0147]

[Table 8]

[0148]

[Table 9]

[0149]

[Table 10]

[0150]

[Table 11]

[0151]

[Table 12]

[0152]

[Table 13]

[0153]

[Table 14]

[0154]

[Table 15]

[0155]

[Table 16]

[0156]

[Table 17]

[0157]

[Table 18]

[0158]

[Table 19]

[0159]

[Table 20]

[0160]

[Table 21]

[0161]

[Table 22]

[0162]

[Table 23]

[0163]

[Table 24]

As is apparent from the table, the sample according to the present invention has improved sharpness and less unevenness in processing, although the sensitivity is less decreased than the comparative sample.

Example 2 In the same manner as in Example 1, a sample was prepared using the emulsions, dyes and the like shown in the table. However, the sensitizing dye was not added. In the evaluation of MTF sharpness, the fluorescent screen is NR-25.
0 (manufactured by Konica Corporation) was used.

For the developing treatment, the trial automatic developing machine shown in FIG. 1 or 2 was used, and the treating time was changed.

In FIGS. 1 and 2, 1 is the first roller for the photosensitive material insertion port, 2 is the final roller for the drying outlet, 3a is the developing tank,
3b is a fixing tank, 3c is a washing tank, 4 is a photosensitive material to be processed, 5 is a squeeze part, 6 is a drying part, and 7 is a blowout port for dry air.

The evaluation results are also shown in the table.

From the table, it can be understood that the sample according to the present invention also has excellent performance in this example.

[0170]

[Table 25]

[0171]

[Table 26]

[0172]

[Table 27]

[0173]

[Table 28]

[0174]

[Table 29]

[0175]

[Table 30]

[0176]

[Table 31]

[0177]

[Table 32]

[0178]

As described above, the silver halide photographic light-sensitive material of the present invention suppresses deterioration of sensitivity and improves sharpness,
In addition, it has an effect that there is little processing unevenness.

[Brief description of 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]

 1 first roller for photosensitive material insertion port 2 final roller for drying outlet 3a developing tank 3b fixing tank 3c water washing tank 4 photosensitive material to be processed 5 squeeze portion 6 drying portion 7 dry air outlet

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiko Kawashima 1 Konica Stock Company, Sakura Town, Hino City, Tokyo (72) Inventor Yasushi Usagawa 1 Konica Stock Company, Sakura Town, Hino City, Tokyo (72) Inventor Kiyoshi Inoue Konica Stock Company, Hino City, Tokyo 1 Konica Stock Company In-house (72) Inventor Hirofumi Ohashi 1 Sakura City, Hino City, Tokyo Konica Stock Company In-house

Claims (2)

[Claims] 1. In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, at least one of the hydrophilic colloid layers has the following general formula: 1] to [8] containing at least one kind of solid fine particle dispersion of the compound,
At least one of the silver halide emulsion layers contains at least one 1-phenyl-5-mercaptotetrazole compound.
A silver halide photographic light-sensitive material characterized by containing one of the following. [Chemical 1] A is a 2-pyrazolin-5-one acidic mother nucleus, B is a 4-aminoaryl group, L _{1 to} L ₃ are methine groups, m is O or 1, and the compound of the general formula [1] is , The following condition (1)
At least one of (4) is satisfied. (1) B has at least one carboxyl group, sulfonamide group, aminosulfonylamino group or sulfamoyl group. (2) A has at least one sulfamoyl group. (3) A has at least one aliphatic group, heterocyclic group or naphthyl group having at least one carboxyl group, sulfonamide group or aminosulfonylamino group. (4) 2-pyrazolin-5-one It has at least one carboxyl group, sulfonamide group or aminosulfonylamino group bonded to the acidic mother nucleus. [Chemical 2] In the formula, R ₁ and R ₂ are substituents, R ₃ and R ₄ are phenyl groups having a carboxyl group via a linking group, L _{1 to} L ₃ are methine groups, and n is an integer of 0 to 2. When n is 2, each L
₂ and L ₃ may be the same and different. [Chemical 3] In the formula, R ₁ and R ₂ are a carboxyl group or a group having a carboxyl group, R ₃ and R ₄ are hydrogen atom or a substituent having no carboxyl group, L _{1 to} L ₃ are methine groups, and n is 0. ~ 2
When n is 2, L ₂ and L ₃ may be the same or different. [Chemical 4] In the formula, R ₁ and R ₂ represent a substituent, and 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, and when n = 2, each -L ₂ = L _3-
May be the same or different. [Chemical 5] In the formula, R ₁ and R ₂ represent a substituent, 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
Represents 0 or 1. [Chemical 6] In the formula, R ₁ represents a substituent, and R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. L _{1 to} L ₃ represent a methine group, E represents an acidic nucleus necessary for forming an oxonol dye, and n is 0.
Represents an integer of 2 and when n = 2, each -L ₂ = L ₃ -may be the same or different. Furthermore, the compound of the general formula [6] has at least two carboxyl groups, sulfonamide groups and sulfamoyl groups. [Chemical 7] In the formula, R ₁ and R ₂ represent a substituent, R ₃ and R ₄ are hydrogen atoms,
It represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and is L ₁ , L ₂ , L ₃ , L ₄ , L ₅
Represents a methine group, and n ₁ and n ₂ represent 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 at least two sulfonamide groups and / or sulfamoyl groups. [Chemical 8] In the formula, R ₁ and R ₂ are alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarboxyl groups, alkylsulfonyl groups, arylsulfonyl groups. , An alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an amino group, a sulfonamide group,
An amide group, a ureido group, a thioureido group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, a carboxyl group or a hydroxyl 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. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is processed by a roller-conveying type automatic developing machine which performs processing under conditions corresponding to the following formula [I]. [Equation 1] In the formula, l is the length (unit: m) of the transport line from the core of the first roller at the insertion port of the roller transport type automatic processor to the core of the final roller at the drying outlet, and T passes through the above l. It is the time (unit: second) required to do.