JPS61256345A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent deterioration of photographic performance during storage stability and, especially to restrain occurrence of fog by incorporating a specified compd. in a silver halide photographic sensitive material. CONSTITUTION:The photographic sensitive material contains at least one of compds. represented by formula I in which R<1>, R<2> are each H, alkyl, cycloalkyl, or aryl, and each is not simultaneously H; R<3>, R<4> are each alkyl, cycloalkyl, aryl, or amino; R<5> is alkyl or aryl; X<1>, X<2> are each H, alkyl, or aryl, or each may combine with each other to form a benzene ring; and Y is formula II, III, IV, or V. The photographic sensitive material thus obtained can be evented from fogging, deterioration of sensitivity and the gamma value even under severe conditions, and in the case of a color photographic sensitive material, silver removal and bleaching performances are improved.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material in which fogging is prevented during storage of the light-sensitive material over time. It's about materials.

[Background of the Invention] Silver halide photographic materials tend to produce fog due to the presence of nuclei that can be developed without being exposed to light, and the occurrence of fog, especially during storage over time, can cause a decrease in sensitivity or This very often leads to deterioration of gradation.

Since it is desirable to minimize such undesirable phenomena, it has been known to add antifoggants, stabilizers, etc. to silver halide emulsions. For example, U.S. Pat. No. 2,403,927, U.S. Pat.
04,633, 1-phenyl-5-mercaptotetrazoles described in Japanese Patent Publication No. 39-2825 Tan, or 5
-Methyl-7-hydroxy-1°3.4-tetrazaindene and the like have been used as fog suppressants.

However, these compounds do not necessarily have a sufficient fog-inhibiting effect during storage over time, and have drawbacks such as a decrease in sensitivity and softening of gradations, so that they are not yet satisfactory.

In addition, in the case of color photosensitive materials, an antifoggant lTh agent that has good shelf life and does not delay the bleaching time is required. When the conventionally known 1-phenyl-5-mercaptothi[.razole is used as an antifoggant in a silver halide emulsion, it tends to deteriorate the desilvering and bleaching properties, and a high silver content may cause the filter layer or antihalation layer to deteriorate. It was unsuitable for color photosensitive materials used in photography.

This tendency becomes a particularly fatal drawback when bleaching baths with weak bleaching blades, such as persulfate salts, are used.

Therefore, there is a desire for a fog suppressant that does not deteriorate the desilvering bleaching properties and does not cause the aforementioned deterioration of photographic performance during storage over time.

[Objective of the Invention 1 Therefore, the present invention has been made in view of the above-mentioned circumstances, and its first object is to prevent the deterioration of photographic performance that occurs during storage of silver halide photographic materials over time. It is an object of the present invention to provide a silver halide photographic material which prevents the occurrence of fog, and in particular suppresses the occurrence of fog.

A second object of the present invention is to provide a silver halide photographic material containing a fog inhibitor that is less likely to cause a decrease in sensitivity or softening of gradation due to development inhibition.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material stabilized by a fog suppressant that does not cause desilvering bleaching during color development.

[Configuration 1 of the Invention The above-mentioned object of the present invention is achieved by a silver halide photographic material containing at least one compound represented by the following general formula [I].

In the general formula [I'] R2 each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. However, there is no case where R' and R2 are hydrogen atoms at the same time. R3 and R″ are alkyl groups,
cycloalkyl group, aryl group, or amino group, and hydroxyl group represents an alkyl group or aryl group). X and X each represent a hydrogen atom, an alkyl group or an aryl group, or a group in which X' and x2 combine with each other to form a benzene ring. ] 14=R' and R represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R and R2 may not be hydrogen atoms at the same time.

The alkyl group represented by R and R2 is preferably an alkyl group having 1 to 8 carbon atoms (particularly preferably 1 to 8 carbon atoms).
In 6), these alkyl groups may have a substituent, and examples of the substituent include a hydroxy group, a cyano group,
Examples include an alkoxy group, a substituted (eg, 2-aminobenzimidazole group) or unsubstituted amino group, an aryl group, and a heterocycle.

Examples of the alkyl group represented by R' and R2 include methyl group, ethyl group, butyl group, etc. Examples of the alkyl group having a substituent include hydroxypropyl group, diethylaminomethyl group, benzyl group, etc. , phenethyl group, morpholinomethyl group, 4-imidazoleethyl group, and the like.

Furthermore, examples of the cycloalkyl group represented by R-R'' include a cyclohexyl group.

As the aryl group represented by R and R, for example,
Examples include phenyl group and naphthyl group. These aryl groups can have substituents, and the substituents include:
Examples include halogen atoms, alkyl groups, and alkoxy groups.

In general formula [1], Y represents preferably an alkyl group having 1 to 8 carbon atoms (particularly preferably 1 to 6 carbon atoms), a cycloalkyl group, an aryl group, or a substituted or unsubstituted amino group.

-゛ preferably has 1 to 8 carbon atoms (particularly preferably 1
~6) represents an argyl group or an aryl group.

Specific examples of Y in general formula [I] as R3, R″ and R′ include benzamide group, acetamide group, propionylamide group, ureido group, phenylureido group, thioureido group, tansulfoamide group,
Examples include benzenesulfonylamide group and cyclohexanecarbonamide group.

The alkyl group represented by X' and is preferably a phenyl group. And these alkyl groups and aryl groups are @pAM
It may have.

In addition, when X and x2 combine with each other to form a benzene ring, this benzene ring has an it group (for example, an alkyl group, an aryl group, a halogen atom, an ano group, a carboxyl group, a sulfo group, etc.). This benzene ring may also be condensed to form a naphthalene ring.

In the present invention, particularly preferred results are obtained in the case of a compound represented by the general formula rI which is bonded to form a benzene ring.

In the following margin, specific examples of compounds used in the present invention are shown, but the present invention is not limited to these. An example of compound synthesis is shown.

Synthesis Example-1 (Synthesis of Exemplary Compound-4) 2-Aminobenzimidazole i, s manufactured by Aldrich
g (0,012 mol) was dissolved in 30IIIL of N,N-dimethylformamide, and while stirring at room temperature, 1.3σ (0,012 mol) of potassium butoxide and 1,6 L of n-hexyl bromide; After stirring for 1 hour, the mixture was diluted with 200 ml of water.

When stirring was continued and 10111 of common salt was added, white powder crystals precipitated, which were collected by filtration and recrystallized with an 80% aqueous methanol solution to obtain the desired product. Yield 70%. The structure of the target product was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

Synthesis Example-2 (Synthesis of Exemplary Compound-7) 2-Aminobenzimidazole 1.50 (0,01
2 mol) was dissolved in 3oral pyridine, and while stirring at both temperatures, benzoyl chloride 1,4(J (0°01 mol)
was added little by little, stirring was continued for 1 hour, and then diluted with ice water, the precipitated crystals were collected by filtration, and recrystallized with an 80% aqueous methanol solution to obtain the target product in the form of a white powder.

Yield 75%. The structure of the target product was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

The above-mentioned compound of general formula [I] according to the present invention may be added to any of the constituent layers of the silver halide photosensitive material, and the amount added depends on the type of compound used and the layer to which it is added. It may be changed as appropriate, and generally when added to a silver halide emulsion layer, per mole of silver halide,
The amount ranges from 10-g mol to 10 mol, with a more preferred amount being 10 mol to 10-3 mol.

Layers of a photosensitive material to which the compound of the present invention can be added include silver halide emulsion layers, protective layers, intermediate layers, filter layers, antihalation layers, undercoat layers, and other structures provided in ordinary photosensitive materials. added to the layer. A particularly preferred layer is a silver halide emulsion layer.

The photographic emulsion in which the present invention can be carried out may use any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, and silver chloroiodobromide as the type of silver halide. .

The silver halide emulsion used in the silver halide photographic material of the present invention can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion used in the silver halide photographic material of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

In addition, this silver halide emulsion is used in the manufacturing process of photosensitive materials.
Silver halide emulsion is applied during, at the end of, and/or after chemical ripening for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. Before this, an antifoggant or a stabilizer can be contained in combination with the compound represented by the general formula [I].

Antifoggants or stabilizers that can be used include:
Examples of azoles include benzothiazole, nitroindazole, benzotriazole, and nitrobenzimidazole; examples of mercapto-substituted heterocyclic compounds include mercaptothiazole, mercaptobenzothiazole, captobenzimidazole, mercaptobenzoxazole, mercaptooxadiazole, Mercaptothiadiazole, mercaptotriazole, mercaptotriazine, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), the above-mentioned mercaptoheterocyclic compounds into which a sulfonic acid group or carboxyl group is introduced, and azaindenes, such as 4 Fogging suppressants or stabilizers well known in the art, such as -hydroxy-1.3.3a and 7-titrazaindene, can be used in combination.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminephenol derivative) during color development processing. A dye-forming coupler is used that acts to form a dye. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence is acceptable. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, and chemical sensitizers by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments can be included, such as spectral sensitizers, spectral sensitizers, and desensitizers. Colored couplers that have a color correction effect on these dye-forming couplers, or OrR that releases a development inhibitor during development and improves the unlockability and graininess of images.
A coupler may also be used in combination. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction in the makuuchi separated by the coupling reaction (timing DIR couplers, and timing DIR compounds). Further, as for the inhibitor, one having a diffusivity after sharpening and another having a less diffusivity can be used alone or in combination depending on the purpose. Although the coupling reaction is carried out with the oxidized product of the aromatic Is primary amine developer, colorless couplers that do not form dyes can also be used in combination with dye-forming couplers.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is British Patent No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 48-94432, No. 50-87650, No. 51-3631M, No. 52-1
No. 15219, No. 54-99433, No. 54-13
No. 3329, No. 5B-30127, US Patent $2,
No. 875,057, No. 3.253.924, No. 3.2
No. 65,506, No. 3,408,194, No. 3,
No. 551,155, No. 3,551,156, No. 3,6
No. 64,841, No. 3,725,072, No. 3,73
No. 0,722, No. 3,891,445, No. 3,900
．． No. 483, No. 3,929,484, No. 3,93
No. 3,500, No. 3.973,968, No. 3,99
No. 0,896, No. 4,012,259, No. 4,02
No. 2,620, No. 4,029,508, No. 4,057
, No. 432, No. 4,106,942, No. 4,133,
No. 958, No. 4,269.936, No. 4,286,
No. 053, No. 4,304,845, No. 4.314,
No. 023, No. 4,336,327, No. 4,356
, No. 258, No. 4,386,155, No. 4,401,
7524 etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolonebenzimidazole couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application No. 58-164882, Japanese Patent Application No. 58-167326, and Japanese Patent Application No. 58-167326.
No. 8-206321, No. 58-214863, No. 58
-217339, No. 59-24653, Special Publication No. 40-6031jJ, No. 40-6035, (EJ45-4
No. 0757, ff1J47-27411, 49-3
No. 7854, JP 50-13041@, JP 51-26
No. 541, No. 51-37646, No. 51-1058
No. 20, No. 52-42121, No. 53-12312
No. 9, No. 53-125835, No. 53-12903
No. 5, No. 54-48540, No. 56-29236,
No. 56-75648, No. 57-17950, No. 57
-35858, 57-146251, 59-9
9437, British Patent No. 1, 252.418, U.S. Patent No. 2,600,788, U.S. Patent No. 3,005,712, U.S. Patent No. 3,062,653, U.S. Patent No. 3,127,269,
3,214, 437%, 3,253,924, 3,311,478, 3,419,391, 3
, No. 519,429, No. 3,558,319, No. 3,
No. 582,322, No. 3,615,506, No. 3,6
No. 58,544, No. 3,705,896, No. 3,72
No. 5,067, No. 3.758.309, No. 3,82
No. 3,156, No. 3,834,908, No. 3.89
1,445@, 3,907,571, 3,926
, No. 631, No. 3,928,044, No. 3,935,
No. 015, No. 3,960,571, No. 4,076.5
No. 33, No. 4,133,686, No. 4,237.21
No. 1, No. 4,241,168, No. 4,264,7
No. 23, No. 4.301.235, No. 4,310,62
This is what is described in No. 3, etc.

As the cyan dye-forming coupler, known naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1,038,331, British Patent No. 1,543,040, Japanese Patent Publication No. 4B-36894, and Japanese Patent Publication No. 48-59838.
No. 50-137137, No. 51-14682
No. 8, No. 53-105226, No. 54-1152
No. 30, No. 56-29235, No. 56-104333
No. 56-126833, No. 57-13365
No. 0, No. 57-155538, No. 57-204545
No. 58-118643, No. 59-31953,
No. 59-31954, No. 59-59656, No. 59
-124341, US Patent No. 59-166956, US Patent No. 2,369,929, US Patent No. 2,423,730,
2,434,272, 2,474,293,
No. 2,698,794, No. 2,772,162, No. 2,801,171, No. 2,895,826, No. 3
, 253.924, 3,311,476, 3,
No. 458,315, No. 3.476.563, No. 3,
591,383%, No. 3,737,316, No. 3,
No. 758,308, No. 3,767.411, No. 3,7
No. 90,384, No. 3,880,661, No. 3,92
6,634 April, No. 4,004.929, No. 4,00
No. 9,035, No. 4,012,258, No. 4.05
No. 2,212, No. 4,124,396, No. 4,1
No. 34,766, No. 4,138,258, No. 4,14
No. 6,396, No. 4,149,886, No. 4,178
, No. 183, No. 4,205,990, No. 4,254.
No. 212, No. 4,264,722, No. 4,288
, No. 532, No. 4.296, No. 199, No. 4,296
, No. 200, No. 4,299,914, No. 4,333
, No. 999, No. 4,334,011, No. 4,386,
No. 155, No. 4,401,752, No. 4,427.7
This is described in No. 67, etc.

As a colored coupler, for example, British Patent No. 937.
No. 621, No. 1,035,959, No. 1,255,
No. 111, JP-A-48-22028, JP-A No. 52-421
No. 21, Special Publication No. 38-22335, No. 44-2016
No. 44-15754, U.S. Patent No. 2.449,9
No. 66, No. 2,521,908, No. 2,543,
No. 691, No. 2,801,171, No. 2,983,6
No. 08, No. 3,005,712, No. 3,034,8
No. 92, No. 3,061,432, No. 3,419.
No. 391, No. 3,476.560, No. 3,476.5
No. 63, No. 3.481,741, No. 3,519,4
29th, No. 3,583,971, No. 3,622.3
28@, No. 3,684,514, No. 4,004,92
No. 9, No. 4,070,191, No. 4,138,258
M, 4,138.264M, 4,163,670, 4,292,400@, 4.369,248, etc. can be used.

As a DIR coupler, for example, British Patent No. 953.4
No. 54, U.S. Patent No. 3,227,554, U.S. Patent No. 3,61
5.506, 3,617,291, 3,70
No. 1,783, 3.933,500@, 4,09
No. 5,984, No. 4,149,886, No. 4,28
No. 6,054, No. 4,359,521, Japanese Unexamined Patent Publication No. 1983-
No. 90932, No. 56-116029, No. 57-15
No. 1944, etc., and U.S. Pat. No. 4,24
No. 8,962, 4,409.323@, JP-A-57-
No. 154234, No. 58-162949, No. 5B-2
No. 05150, No. 59-195643, No. 59-20
No. 6834, No. 59-206836, No. 59-210
Timing D described in No. 440, No. 60-7429, etc.
IR couplers can be preferably used.

Examples of DIR compounds include those described in US Pat. No. 3,632.
No. 345, No. 3,928,041, No. 3,938
, No. 996, No. 3.958,993, No. 3,961
, No. 959, No. 4,046,574, No. 4,052
, No. 213, No. 4,171,223, No. 4,171,
223, JP-A-52-65433, JP-A No. 52-1303
274, No. 51-128335, etc. can be preferably used.

As a colorless coupler, I! U.S. Patent No. 2,998,314@, British Patent No. 1,284,649, West German Patent No. 1,168,76 for adjustment, color turbidity, and capri prevention.
A so-called Weiss coupler described in No. 9 can be used.

Dye-forming couplers, colored couplers, DIR couplers, and DTP that do not need to be adsorbed onto the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among optical brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. The oil-in-water emulsion dispersion method can be applied to a method of dispersing hydrophobic additives such as couplers, and usually a high boiling point organic solvent with a boiling point of about 150'C or higher is mixed with a low boiling point and/or water-soluble organic solvent as necessary. It was dissolved using a solvent and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant and a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jit mixer, and ultrasonic device. After that, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

In the present invention, the ratio of the high boiling point organic solvent and the low boiling point organic solvent according to the present invention is i:0.1 to 1:50, more preferably 1:
The ratio is preferably 1 to 1:20.

Anionic surfactants and nonionic surfactants are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point organic solvent alone or in combination with a high boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. , cationic surfactants can be used.

Between the emulsion layers of the light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers, the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

As the color antifogging agent, hydroquinone derivatives, amine phenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. are preferable, and specific examples thereof are described in U.S. Patent Nos. 2 and 3.
No. 60,290, No. 2,336,327, No. 2.40
No. 3,721, No. 2,418,613, No. 2,67
5,314@, 2,701,197@, 2,704
, No. 713, No. 2,728,659, No. 2,732,
No. 300, 2,735,765@, 3.700.4
No. 53, JP 50-92988@, JP 50-9298
No. 9, No. 50-93928, No. 50-110337, No. 50-156431, No. 52-146235, No. 55-95948, No. 59-5247, Special Publication No. 1973
1. Image stabilizers for preventing deterioration of dye images can be used in light-sensitive materials using the silver halide emulsion of the present invention, as disclosed in No. 23813 and the like.

Image stabilizers include, for example, hydroquinone derivatives, gallic derivatives, phenol derivatives and their bis forms, hydroxycoumarans and their spiro forms, hydroxychroman and their spiro forms, piperidine derivatives, aromatic amine compounds, benzodioxane derivatives, and penzo derivatives. Dioxole derivatives, compounds containing 1,113 carbon atoms, dioether compounds, etc. are preferred. As a specific example, British Patent No. 1,41
No. 0,846, JP-A-4.9-134326@, 52
-35633, 52-147434, 52-1
No. 50630, No. 54-145530, No. 55-63
No. 21, No. 55-21004, No. 55-124141
Month, No. 59-3432, No. 59-5246, No. 59
-10539, Special Publication No. 48-31 [i25, No. 49
-20973, 49-20974, 5o-23
No. 813, No. 52-27534, U.S. Patent No. 2,36
No. 0,290, No. 2,418,613, No. 2,675
, No. 314, No. 2,701.197, No. 2,704,
No. 713, No. 2,710,801, No. 2,728.6
59@, fffJ2,732,300, 2,735
, No. 765, No. 2.1116.028, No. 3,06
No. 9,262, 3,336.135@, 3,43
No. 2,300, No. 3,457,079, No. 3,573
, No. 050, No. 3,574,627, No. 3,698,
No. 909, 3. i'o.

, No. 455, No. 3,764,337, No. 3,935,
No. 016, No. 3.982,944, No. 4,013,7
No. 01, No. 4,113,495, No. 4,120,72
No. 3, No. 4,155,765, No. 4,159,910
No. 4,254,216, No. 4,268,593, No. 4,279.990, No. 4,332,886,
4,360,589 Jl! , 4,430.425, and 4,452,884.

A known method can be used to develop the photosensitive material of the present invention. The processing moisture level used is between 18°C and 50°C, and depending on the purpose, any of black and white photographic processing, lithographic visual processing, or color photographic processing to form a dye image can be applied.

Black and white photographic processing uses dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), ascorbic acid, etc. alone or in combination as developing agents. It can be used as

The developing solution may contain other known preservatives, alkaline agents, pl-
It contains a 111 buffering agent, a fog suppressant, etc., and may also contain a solubilizing agent, a toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, etc. as necessary.

The photographic emulsion of the present invention can be subjected to a "lith type" development process. "Lith-type" processing refers to the processing of high-contrast photosensitive materials for plate making to obtain line drawings or halftone dot images, and usually uses dihydroxybenzenes as a developing agent.

The present invention can also be applied to so-called developer-containing type photosensitive materials in which a developing agent is contained in the photosensitive material and processed in an alkaline bath.

Next, when forming a dye image, an alkaline aqueous solution containing a color developing agent is used. As the color developing agent, a known primary aromatic amine developer such as phenylene diamines can be used.

Color developers also contain pl-(buffers, halogen salts, and organic antifoggants, water softeners, etc. such as alkali metal sulfites, carbonates, borates, and phosphates,
It may contain preservatives, organic solvents such as benzyl alcohol and ethylene glycol, and development accelerators such as polyethylene glycol, quaternary ammonium salts and amines.

Processing after color development is usually a bleaching process.

The bleaching solution may be applied simultaneously with the fixing process or separately. As bleaching agents, compounds of polyvalent metals such as iron (■), cobalt (■), chromium (■), copper (II>), persulfates, and the like are used.

For example, ferrocyanide, dichromate, iron, an organic complex salt of cobalt, ethylenediaminetetraacetic acid, nitrilotriacetic acid, persulfate, permanganate, etc. can be used.

The photosensitive material of the present invention does not slow down its bleaching (desilvering) speed even when processed with a bleaching agent with a weak bleaching blade, such as persulfate, so that it can be bleached without causing any pollution. Become.

In the case of a bleaching solution with a weak bleaching blade, a compound known as a bleaching accelerator can be added to the solution.

Hereinafter, the present invention will be explained in more detail based on Examples.

Example-1 High sensitivity X containing 2.0 mol% silver iodide and the rest consisting of silver bromide
After chemically ripening the linear silver iodobromide emulsion to the highest sensitivity using gold and sulfur sensitization, 1.00 of 4-hydroxy-6-methyl-1°3.3a,7-titrazaindene was added per mole of silver halide. was added to stop the ripening.

Next, the emulsion was divided into 11 equal parts, each of the compounds according to the present invention was added as shown in Table 1 below, and after sufficient adsorption, an appropriate amount of saponin as a coating aid and an appropriate amount of formalin as a hardening agent were added. An emulsion was prepared.

The obtained emulsion was uniformly coated on a subbed polyester base so that the silver density was 3 (+/112), and then dried to prepare a sample according to the present invention.

The photographic material prepared as above was left at room temperature for 3 days as a fresh sample, and the photographic material was prepared as a fresh sample at a temperature of 65°C and a humidity of 50°C.
% for 3 days, and forced deterioration aging samples that were left for 3 days at a temperature of 50° C. and a humidity of 80%.

After this, X-ray exposure was performed using a screen containing calcium tungstate (CaWo4) as a phosphor, and then development was performed at 35°C for 30 seconds with the following processing solution [A] to fix it, and then washed with water and dried. Sensitivity was measured.

Processing liquid [A] (Developer for black and white photographic materials) 1-phenyl-3-pyrazolidone 1.50 human 0 quinone
30 (15-nitroindazole 0.25Q potassium bromide
5. OQ anhydrous sodium sulfite
55 Q Potassium hydroxide 3
0 g boric acid
10Q glutaraldehyde (25%)
5a Add water to bring the total volume to 11.

The results obtained are shown in Table 1 below.

However, the fog value is the value obtained by subtracting the base density, the sensitivity value is expressed as a relative sensitivity from the sensitivity at the fog value + 0.5 position, with the comparison sample set as 100, and gamma is the linear portion on the characteristic curve. It is shown by the slope of .

As is clear from Table 1 above, the sample No. according to the present invention
, 2 to 11, the occurrence of fog and deterioration of gamma were suppressed despite the harsh storage conditions, and the stability under film storage was improved.

Example 2 A silver iodobromide emulsion containing 7 mol % of silver iodide and having an average grain size of 1.2 μm was chemically ripened with gold and sulfur sensitizers to the highest sensitivity, and then 4-hydroxy-6-methyl-1° 3.3a, 7-
The chemical ripening was stopped by adding 1.0 ml of citrazaindene per mole of silver halide.

Next, an appropriate amount of 5,5'-diphenyl-9-ethyl-3,3'-di-γ-sulfopropyloxacarbocyanine sodium salt was added as a green-sensitive sensitizing dye to prepare a green-sensitive silver halide emulsion.

Then, per mole of silver halide, 1-(2,4,6-trichlorophenyl)-3 was added as magenta coupler.
-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone, 80 g, as a colored magenta coupler, 1-(2,4,6-triclophenyl)-4-<1-naphthylazo ) -3-
(2-chloro-5-octadecenylsuccinimidoanilino)-5-golazolone was weighed at 2.50, mixed with tricresyl phosphate 120 (1, and 2401111 ethyl acetate) and dissolved by heating. Then 5 g of sodium triisopropylnaphthalene sulfonate and 7.5 g of sodium triisopropylnaphthalene sulfonate
% gelatin aqueous solution 5 g0 LI1 After adding the compounds according to the present invention to the solution and allowing sufficient adsorption, add 2-hydroxy- as a gelatin hardener.
An appropriate amount of sodium 4,6-cyclotriazine was uniformly added to prepare a silver halide emulsion.

This emulsion is mixed with 3. A sample was prepared by uniformly coating and drying the coating onto a triacetate film that had been undercoated to an amount of Oa/m''.

The obtained film sample was subjected to a forced deterioration test similar to that in Example 1, and then wedge exposed in a conventional manner and color developed according to the following color processing steps.

The color sensitometry results obtained from the obtained pieces are shown in Table 2 below.

The fog in the table is the value after subtracting the base concentration, and the sensitivity is the blank sample No. 12 after 3 days of natural study.
) is expressed as 100. or,
Gamma is expressed by the slope of the straight line.

Processing process [Processing temperature 38℃] Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
6 minutes 30 seconds. Washing with water Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer J 4-amino-3-methyl-N=ethyl-N-(β-hydroxyethyl>-aniline nitrate 4.75!J
Anhydrous sodium sulfite 4.259 Hydroxylamine 1/2 nitrate 2.0 0 Anhydrous potassium carbonate 37.5 Q Sodium bromide 1.3 g NitriO triacetic acid 3
Sodium salt (monohydrate) 2.5 0 Potassium hydroxide 1.0g Add water to make 1 (1).

[N white liquor] Ethylenediaminetetraacetate iron ammonium salt ioo, o gethylenediaminetetraacetate 8!2 Ammonium salt 10. OQ ammonium bromide 150. OQ wood vinegar @
Add water to io and o 1
Adjust to pl-16.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.00 Anhydrous sodium sulfite 8.6q Sodium metasulfite 2.3g Add water to adjust to 1Ω,
Adjust to 16.0 using acetic acid.

[Stabilizing liquid Copolmarin <37% aqueous solution] 1. s J
Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5 J water to make 1 q.

The following margin * [Comparative PTM represents 1-phenyl-5-mercaptotetrazole. Table 2 above shows that even in photosensitive materials containing color formers, the fog suppressant of the present invention has excellent stability during film storage.

Example 3 A multilayer color negative photosensitive material was prepared by sequentially coating the following layers from the 1st layer to the 13th layer on a transparent cellulose triacetate film.

1st layer: antihalation layer 0.3Q/I forged gelatin aqueous solution containing black colloidal silver
It was applied so that it became 2.

2nd layer: Intermediate layer An aqueous gelatin solution was coated to a dry film thickness of 1.0 μm.

3rd layer: Red-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6μ, silver iodobromide emulsion containing 4 mol% silver iodide, average grain size 0.3μ, iodide emulsion) silver 4 mol%
A silver iodobromide emulsion containing (mixed in a ratio of 2:1) was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3,3'-di( anhydrous 5,5'-dichloro-9-
Ethyl-3,3′-di(3-sulfobutyl)thiacarbocyanine hydroxide: and anhydrous 2-[2-((
5-chloro-3-ethyl-2(3H)-benzothiazocyan)methyl)-1-butenyl-5-chloro-3-(4
-sulfobutyl)benzoxacilium was added.

Next, 4-hydroxy-6-methyl-1,3゜3a,7-
Citrazaindene per mole of silver halide 1.00
A red-sensitive low-sensitivity emulsion was prepared by adding it.

Then, per mole of silver halide, 1-hydroxy-N-[4-(2,4-di-t-amylphenoxy)ethyl] 59(] was used as the cyan coupler.

Additionally, 5 g of dodecyl gallate o was added, tricresyl phosphate 65 o and ethyl acetate 1361110-
A 7.5% aqueous gelatin solution containing 5Ω of sodium triisopropylnaphthalene sulfonate was prepared by heating and dissolving a mixture of
A red-sensitive low-sensitivity emulsion was prepared by adding the dispersion emulsified and dispersed in a colloid mill to 0 rnl, and the amount of coated silver was 2.
It was applied so that the ratio was 0(]/l112.

4th layer: red-sensitive high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide) is chemically sensitized with gold and sulfur sensitizers, and further red Anhydrous 9-ethyl-3,3'-di(3-sulfopropyl>-4°5.4',5'-dibenzothiacarbocyanine hydroxide) as a sensitizing dye; anhydrous 5,5'-dichloro-9
-ethyl-3,3'-di(3-sulfobutyl)thiacarbocyanine hydroxide; and anhydrous 2-[2-((
5-chloro-3-ethyl-2(3H)-penzothiazoliden)methyl)-1-butenyl-5-chloro-3-(4
-sulfobutyl)benzoxacilium was added.

Next, 4-hydroxy-6-methyl-1,3゜3a,7-
1.0 g of citrazaindene and 1-phenyl-5-mercaptotetrazole were added per mole of silver halide.

Furthermore, per mole of silver halide, as a cyan coupler,
1-hydroxy-N-[4-(2,4-di-t-amylphenoxy)butyl]-2 naphthamide 17g1 dodecyl gallate 0. A 1.5% aqueous gelatin solution 301 containing 1.5 g of sodium triisopropylnaphthalene sulfonate was prepared by adding 5Q and heating and dissolving a mixture of tricresyl phosphate 200 and ethyl acetate 60I1112.
1 and a dispersion emulsified and dispersed in a colloid mill to prepare a red-sensitive high-sensitivity emulsion, and coated silver it 2. O
It was applied so that it was a/m2.

5th layer: Intermediate layer Same as 21st 61st if: Green-sensitive low-sensitivity silver halide emulsion layer After chemically sensitizing the same emulsion as the 3rd layer, anhydrous 5,5'-dichloro- 9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'
-di<3-sulfobutyl)oxacarbocyanine human [J oxide; and anhydrous 9-ethyl-3,3'-di(
3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide is added, followed by 4-hydroxy-6-methyl 1,3°3a,7-chitrazaindene at a rate of 1 per mole of silver halide. A green-sensitive, low-sensitivity emulsion was prepared by adding .0 (]).

Furthermore, per mole of silver halide, magenta coupler and
100 g of (3-(2,4-di-t-amylphJnoxy)acetamide)-5-pyrazolone, 1-(2,4゜6-trichlorophenyl)-4-(1-nanotyl azo) as a colored magenta coupler. -3-(2-chloro-
5-octadecenyl succinimide anilino)-5-pyrazolone 2.50, and dodecyl gallate 0. sg was added, a mixture of tricresylphosphny I-120Q and 240 ml of ethyl acetate was heated and dissolved, and the dispersion was added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate and emulsified and dispersed in a colloid mill. A green-sensitive high-sensitivity emulsion was prepared and coated with silver m 1,5 a
/ra''.

7th layer: green-sensitive, high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide) is chemically sensitized with gold and sulfuric acid sensitizers, and further Anhydrous 5,5'-dichloro-9-ethyl-3,3 as a green-sensitive sensitizing dye
'-di(3-sulfobutyl)oxacarbocyanine with droxide; anhydrous 5,5'-diphenyl-9-edyl-3'3'-di(3-sulfobutyl)oxacarbocyanine hydroxide; J5 and anhydrous 9-L-til -3゜3'
-di(3-sulfopropyl)-5,6゜5',6'
--Add dibenzoyl 1-nacarbocyanine hydroxide, then add 4-hydroxy-
6-Methyl-1,3,3a,7-chitrazaindene 1.
0Q and 10.0 mg of 1-phenyl-5-mercap 1-te 1-razole were added to prepare a green-sensitive and highly sensitive silver 1-genide emulsion.

Furthermore, go (2,4,6-trichlorophenyl)-3-(3
-(2,4-di[-amylphenoxy)acetamide)-5-pyrazolone 80g 1 as colored magenta coupler 1-(2,4,6-trichlorophenyl)-4
-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone 2.5 g, 2.5-di-t-octylhydroquinone 1
．． Add 50 and add tricresyl phosphate 12
A mixture of 00 and 240 ml of ethyl acetate was dissolved by heating, added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and the dispersion was emulsified and dispersed in a colloid mill to prepare a green-sensitive high-sensitivity emulsion. It was applied in an amount of 1.8 g/m'.

8th layer: Intermediate layer Same as 2nd layer 9th layer: Yellow filter 2. Yellow filter in gelatin aqueous solution in which colloidal silver is dispersed.
5-di-t-octylhydroquinone 3Q and di-2-ethylhexyltstarate 1.517 to ethyl acetate 101
A dispersion of gelatin dissolved at 11t and dispersed in an aqueous gelatin solution containing 0.30 g/m of sodium triisopropylnaphthalene sulfonate was added;
2.5-di-t-octylhydroquinone 0,10o/
It was applied so that the thickness was m.

10th layer: blue-sensitive, low-sensitivity halogen raw emulsion layer silver iodobromide emulsion (average grain size 0.6μ, containing 6 mol% silver iodide)
was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3,3'-di(3-
sulfopropyl) thiacyanine hydroxide was added.

Next, 1 g of 6-methyl-1,3,3a,7-te-1-razaindene was added per mole of silver halide, and the emulsion was divided into compounds according to the present invention and PTM for comparison as shown in Table 3 below. (1-phenyl-5-mercaptotetrazole) was added to prepare a blue-sensitive, low-sensitivity silver halide emulsion.

Then, for each emulsion, α-pivaloyl-α-(1
-benzyl-2-phenyl-3゜5-dioxo-1,2
,4-1-lyasilydin-4-yl)-2'-chloro0-
5'-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide 120Q, α-(3-[α-
(2,4-di-t-amylphenoxy)butylamitoco)benzoyl-2'-methoxyacetanilide 50(]
A mixture of 120 g of dibutyl phthalate and 300 ral of ethyl acetate was heated and dissolved, added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and the dispersion emulsified in a colloid mill was added to obtain a blue-sensitive, low-sensitivity halogen. A silver oxide emulsion was prepared, and the amount of coated silver was 0.
It was coated at a rate of 7 a/m2.

11th layer: Blue-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide)
was chemically sensitized with a gold and sulfur layer sensitizer, and anhydrous 5,5'-dimethoxy-3,3'-di(3-
sulfopropyl) thiacyanine hydroxide was added.

Next, the emulsion was divided and PTMs of the compound according to the present invention and the comparative compound were respectively added as shown in Table 3 below to prepare a blue-sensitive, high-sensitivity silver halide emulsion.

These emulsions were then treated with α-pivaloyl-α-(
1-benzyl-2-phenyl-3゜5-dioxo-1,
2,4-triacylidin-4-yl)-2'-chloro-
Add 80 g of 5'-'α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide (], heat and dissolve a mixture of 80 g of dibutyl phthalate and 240 J of ethyl acetate, and add to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate. A blue-sensitive, high-sensitivity silver halide emulsion was prepared by adding the dispersion emulsified and dispersed in a colloid mill, and coated to give a coating silver of 1 k 0.9 o/m 2 .

12th layer: Intermediate layer di-2-ethylhexyl phthalate 20.2-[3-cyano-3-(n-dodecylaminocarbonyl)alicyan]-1-ethylpyrrolidine 2g and ethyl acetate 2ml
A dispersion prepared by dispersing in an aqueous gelatin solution containing 0.6 g of sodium triisopropylnaphthalene sulfonate was added, and this was applied so that the gelatin concentration was 1.0 Ω/l.

Thirteenth layer: A gelatin aqueous solution containing 4 g of gelatin and 0.2 g of 1,2-bisvinylsulfonylethane per Wi-retention layer 1001e was coated in an amount of 1.3 a/ra of gelatin.

The obtained sample was subjected to the same forced deterioration test treatment as in Example 2, then wedge exposed in the usual manner, and then subjected to the same treatment as in Example 2 to obtain a color image.

The optical density of a yellow image from this sample was measured through a blue filter to evaluate the fog suppressing effect.

The fog value in the table is the value obtained by subtracting the mask density from the minimum density, and the sensitivity is shown as a relative sensitivity expressed as 1oo of that of the natural device of the comparison sample (sample No. 0.19).

It can also be seen from Table 3 that the samples of the present invention cause less fogging during storage and can provide a fog suppressing effect with less desensitization.

Table 3 shows that samples Nos. 23 to 29 according to the present invention have excellent storage stability over time even in the case of multilayer color photosensitive materials.

Example 4 In this example, the desilvering rate of yellow colloidal silver was investigated. Using the sample obtained in Example 3, the bleaching treatment time was varied and the yellow color density was measured.

The bleaching solution used had the following composition.

Wet white liquid phase formed sodium persulfate 55a Sodium dihydrogen phosphate 15 g Sodium chloride
25 g sodium tetrapolyphosphate Add 1 g water to make a total volume of 1 (l).

The processing steps were exactly the same as those shown in Example 2 above, except that the bleaching solution was changed.

From Table 4 in the margin below, it can be seen that the compounds of the present invention have less desilvering inhibition by stable silver salts exhibited by compounds having an antifogging effect, and compared to PTM (comparison), which is a conventionally known compound, yellow colloidal silver This shows that the yellow color density is low because it is bleached in a short time.

4. [Effects of the Invention] As is clear from the above examples, according to the present invention, the halogenated resin does not cause fogging, decrease in sensitivity, or decrease in gamma even under severe storage conditions. A silver photographic light-sensitive material can be obtained, and in the case of a color light-sensitive material, a color light-sensitive material with good desilvering and bleaching properties can be provided.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment (self-interest) August 9, 1986

Claims (1)

[Scope of Claims] At least one compound represented by the following general formula [I]
A silver halide photographic material characterized by containing seeds. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Y in the formula is a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ represents (R^1 R^2 each represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, R^1 and R^
There is no case where 2 is a hydrogen atom at the same time. R^3 and R^4 represent an alkyl group, cycloalkyl group, aryl group or amino group, and R^5 represents an alkyl group or an aryl group). X^1 and X^2 each represent a hydrogen atom, an alkyl group, an aryl group, or a group in which X^1 and X^2 combine with each other to form a benzene ring. ]