JPS6344650A - Silver halide photographic sensitive material permitting rapid processing - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of reducing fog, without destroying photosensitive effect by incorporating a specific spectral sensitizing dye to an emulsion having a high silver chloride content, and a specific nitrogen contg. heterocyclic compd. to the titled material as a fog controlling agent, respectively. CONSTITUTION:The titled material contains a silver halide particle contg. >=80mol silver chloride, at least one kind of the spectral sensitizing dye shown by formula I, and at least one kind of the compd. shown by formula II in at least one layer of the silver halide emulsion layer. In formula I, X1-X4 are each hydrogen or halogen atom, alkyl, alkoxy, aryl or hydroxyl group, R1 and R2 are each alkyl group, X<-> is counter anion, (n) is 0 or 1. In formula II, Z is an atomic group necessary for forming benzotriazole ring or 1,2,3,4- thiatriazole ring. Thus, the titled material which can be effected rapid processing, and has high sensitivity and less tendency for generating fog, and has excellent storage stability is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has a silver halide emulsion layer mainly composed of silver chloride and is capable of rapid processing. The present invention relates to a silver halide photographic material that forms good images even when processed rapidly.

[Conventional technology and its problems]

In the field of silver halide photographic light-sensitive materials, there has been a demand for shortening the development processing time, and therefore there is a demand for the development of light-sensitive materials that enable even more rapid processing.

It is known that a light-sensitive material using silver halide grains with a high silver chloride content can achieve rapid development processing.

In particular, it is known that under certain conditions, for example in the absence of silver bromide, a significantly high development rate is exhibited.

However, those using silver halide grains with a high silver chloride content are suitable for rapid processing, but have the problem of low sensitivity. This problem arises because silver chloride absorbs almost no visible light. For this reason, it is necessary to apply various sensitization methods, but if chemical sensitization is performed on grains with a high silver chloride content, fogging tends to occur and raw samples (
When raw samples (before exposure) are stored over time, fog increases;
It may also cause a decrease in sensitivity.

On the other hand, it is common practice to add an antifogging agent to a silver halide emulsion to prevent fogging. However, antifoggants generally cause changes in the low frequency range, so
For emulsions with a high silver chloride content that are naturally low in 1y degree, it is difficult to use antifoggants.

Therefore, when using an antifoggant, it is essential to apply an effective sensitization method to the emulsion, but if an antifoggant is used for an emulsion with a high silver chloride content, sensitization by this sensitization method is also effective. The fact is that it becomes smaller.

In particular, when tetrazaindene and mercapto compounds, which are conventionally known as fog inhibitors, are used, these fog inhibitors are easily adsorbed to silver halide grains, so even if the grains are sensitized with a sensitizing dye, the The sensitizing dye is desorbed and the sensitizing effect becomes t-membered. This tendency is particularly noticeable for emulsions with a high silver chloride content.

In order to solve this problem, it is necessary to develop a sensitizer that has an effective sensitizing effect on emulsions with a high silver chloride content and that does not lose its effect even with any fog suppressant, or All that is needed is to develop a fog suppressant that has an effective antifogging function for emulsions with a high silver chloride content and that does not have any adverse effects on any sensitizing effects. is extremely difficult.

Therefore, we have no choice but to find a sensitizer and a fog suppressant that can sufficiently achieve their respective functions without having a negative effect on each other. There are an extremely wide variety of anti-fogging agents for emulsions with high ratios, and an enormous variety of anti-fogging agents. It was extremely difficult to find a drug.

However, as a result of intensive research and repeated examinations, the present inventors found that a certain type of spectral sensitizing dye was used for emulsions with a high silver chloride content, and a certain type of nitrogen-containing complex dye was used as a flash suppressor. It has been found that when a ring compound is used, effective sensitization can be achieved and effective fog suppression can be achieved without impairing this sensitizing effect.

(Structure and operation of the invention) That is, the problem with the prior art described above is that in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers: a) Silver halide grains containing 80 mol% or more of silver chloride b) Containing at least one spectral sensitizing dye represented by general formula CI) and at least one compound represented by C)-V formula (II) This problem is solved by a silver halide photographic material characterized by the following.

General formula (1) In the formula, χl+

R1 and Rz each represent an alkyl group.

X- represents a counter anion.

n represents O or 1.

General formula (II) (wherein, Z is a benzotriazole ring or 1,2°3.4
-Represents the atomic group necessary to form the thiatriadules ring. ) As a result of the silver halide photographic material of the present invention having the above structure, it is suitable for rapid processing, has high sensitivity and low fog, and even when raw samples before exposure are stored over time, there is no increase in fog or decrease in sensitivity. is suppressed, and therefore has good stability over time.

Although the spectral sensitizing dye of the above-mentioned ship type (I) is extremely effective as a sensitizer, when used in emulsions with a high silver chloride content, fog tends to increase, especially when stored over time. However, the above general formula (I
By using it in combination with the compound I), this fogging problem can be solved. Moreover, the compound of general formula (II) does not have a sensitizing effect.

On the other hand, the compound of general formula (n) above is a type of nitrogen-containing heterocyclic compound, but if the nitrogen-containing heterocyclic compound is added at the time when it shows a fog-inhibiting effect, the sensitivity may decrease, and the fog-inhibiting effect immediately after application may decrease. However, among nitrogen-containing heterocyclic compounds, it has problems such as being ineffective when stored over time and tending to reduce sensitivity especially for emulsions with a high silver chloride content. (2) has a strong effect on suppressing fog over time (and does not impair the sensitizing effect of the sensitizing dye of general formula (I) on emulsions with a high silver chloride content, so it is possible to improve the sensitivity of such emulsions. It is possible to effectively achieve this goal.

In this way, the sensitizing dye of general formula (1) and the compound of general formula C11) have a rare mutual relationship in which they each compensate for their shortcomings and do not adversely affect the advantages of the other. It was surprising that a sensitizing dye and a fog inhibitor exist that have such a mutual relationship.

In a preferred embodiment of the present invention, gold-sulfur sensitization may be used in combination. Although gold-sulfur sensitization is preferable for increasing sensitivity, it has the problem of significantly increasing fogging, particularly over time.

However, in the present invention, such an increase in fog is suppressed, and gold-sulfur sensitization can be preferably used. Gold-sulfur sensitization is particularly effective for rapid processing.

The following system, p, .

·tsu Next, the configuration of the present invention will be described in more detail.

In the present invention, the silver halide grains containing 80 mol% or more of silver chloride, the spectral sensitizing dye represented by the general formula CI), and the compound represented by the -i formula (I[) are contained in the halogenated grains. This is a silver emulsion layer (hereinafter, such an emulsion layer will be appropriately referred to as the "silver halide emulsion layer of the present invention"), but the light-sensitive material of the present invention may be embodied in a structure having one silver halide emulsion layer. When the layer contains the above-mentioned compounds, etc.

Furthermore, when the light-sensitive material of the present invention is embodied in a structure having a plurality of silver halide emulsion layers, the above-mentioned ? At least one of the M layers may be the silver halide emulsion layer of the present invention. Preferably, this structure of the present invention is applied to the front window emulsion layer, which is generally formed as the lowest layer (the layer closest to the support), and this is used as the silver halide emulsion layer of the present invention. good.

In the case of having a plurality of silver halide emulsion layers, it is natural that there may be an emulsion layer that does not have the structure of the silver halide emulsion layer of the present invention.

Next, the general formula CI used in the silver halide emulsion layer of the present invention]
The spectral sensitizing dye represented by is explained below.

In the spectral sensitizing dye of general formula (1) used in the present invention, each of X, X, X3 and x4 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a hydroxyl group. Specifically, the halogen atom includes, for example, a chlorine atom, and the alkyl group includes, for example, a methyl group and an ethyl group having 1 to 6 carbon atoms. As the alkoxy group, for example, the number of carbon atoms is 1 to
Examples of 6 include a methoxy group and a nidoxy group.

Preferably at least one chlorine atom is present, particularly preferably two chlorine atoms.

R1 and R2 each represent an alkyl group, and this alkyl group includes those having substituents. Preferably R+
, Rz is an unsubstituted alkyl group, or an alkyl group substituted with a carboxyl group or a sulfo group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a carbon This is the case of a sulfoalkyl group or a carboxyalkyl group having 1 to 4 atoms.

R+ and Rz may be the same or different, but preferably one is an alkyl group having 1 to 4 carbon atoms and substituted with a carboxyl group.

Xe represents a counter anion. Examples include, but are not limited to, halogen ions (Bre, 1e, etc.).

n represents O or 1.

The spectral sensitizing dye represented by -C[I] is a known compound, for example, as described in the specifications of British Patent No. 660,408, US Pat. No. 3,149,105, or JP-A No. 5
Publication No. 0-4127 or "The Cyanine Dice and Related Compounder" by Hemer (
Interscience Publishers, New York, 1969) (FlM, Hamer, TheC
yanine Dyes and Re1ated C
pounds”Interscience Public
ishers, New York 1969) No. 3
It can be easily synthesized by referring to Items 2 to 76.

Specific examples of the spectral sensitizing dye represented by general formula (I) used in the present invention are shown in Table 1 below, but the compounds that can be used in the present invention are not limited thereto.

(f″ In the above table-1, NEt is C,l(.

-N-czus.

C,115 The amount of the spectral enhancement dye used in the present invention is preferably 5 x 10-b to 5 x 10-'' mol/AgX
It is a mole. More preferably, lXl0-' to 1x10
-3 mol/AgX mol. Most preferably lXl0
-' to 9X10-' mol/AgX mol.

For example, methods well known in the art can be used to add the above-mentioned spectral enhancing dye to the emulsion in the practice of the present invention.

For example, these sensitizing dyes can be dispersed directly in the emulsion or dissolved in aqueous or water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents). However, in some cases they can be diluted with water and added to the emulsion in the form of a solution. It is also advantageous to use ultrasonic vibrations for this dissolution. The above-mentioned spectral sensitizing dye can be obtained by dissolving the sensitizing dye in a volatile organic solvent and dispersing the solution in a hydrophilic colloid, as described in U.S. Pat. No. 3,469.987. A method of adding the pigment to an emulsion is also used, as described in Japanese Patent Publication No. 46-24185 (1985), in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion. In addition, the above-mentioned spectral enhancement dye can be added to the emulsion in the form of a dispersion by an acid dissolution dispersion method.
, 342,605, 2.996,287, 3,425,835, etc. can also be used.

Further, the spectral enhancement dye represented by the general formula [I] may be used alone or in combination of two or more. When using two or more types, they may be added simultaneously or separately. When adding them separately, the order, time and interval can be arbitrarily determined depending on the purpose. Furthermore, there is no hindrance to the use in combination with sensitizing dyes other than those represented by the general formula CI).

The timing of addition of the above-mentioned spectral enhancing dye to be contained in the halogenated emulsion layer of the present invention is arbitrarily selected during the preparation process of the silver halide photographic emulsion. For example, it is generally added between the end of the first ripening and the end of the second ripening. The sensitizing dye can also be added in portions during the above-mentioned addition period.

The silver halide emulsion used to constitute the silver halide emulsion layer of the present invention may be any of silver chlorobromide, silver iodochloride, and silver chloroiodobromide silver chloride, but silver chloride contains 80 mol of silver halide emulsion. % or more of high chloride silver halide emulsion. Preferably, the silver chloride content is 95 to 100%. Silver iodide may be contained, but its content is preferably 1 mol % or less, more preferably 0.5 mol % or less, and most preferably no silver iodide. The silver bromide content is preferably 5 mol% or less, and may be 0 mol%.

In the present invention, silver halide grains having a silver chloride composition of 80 mol% or more are contained in a weight percentage of 80% or more of all the silver halide grains in the silver halide emulsion layer containing the silver halide grains. It is preferably 100%, and more preferably 100%. Further, the average silver chloride content of the emulsion layer containing such silver halide grains is preferably 80 mol% or more, more preferably 85 mol% or more.

Here, the silver halide grains contained in the silver halide emulsion layer preferably contain 80 mol% or more of silver chloride on average means that the molar ratio of silver chloride in the entire emulsion layer is 80 mol% or more. This does not preclude the possibility that some compositions may deviate from this, or that substances outside this molar ratio (for example, pure silver bromide) may be contained.

When the light-sensitive material of the present invention is embodied in a structure having a plurality of silver halide emulsion layers, it may have an emulsion layer having a structure other than the silver halide emulsion layer of the present invention as described above. Regarding the other 1, it is not necessarily necessary to have a high chloride silver halide composition. However, the average silver chloride content of all the emulsion layers constituting the light-sensitive material is 80 mol%.
or more, and more preferably all emulsion layers contain silver halide grains containing 80 mol % or more of silver chloride, especially the average of all layers, and more preferably, the average of all layers contains 95 mol % or more of silver halide grains. % or more is preferred.

The key of the present invention is the silver halide used in the photographic material, i.e., the silver halide grains used in the silver halide emulsion layer of the present invention and other emulsion layers formed as necessary.
The grain size of the silver halide grains (hereinafter referred to as "silver halide grains used in the present invention") is determined by the length of the side in the case of cubic silver halide grains, and the grain size of grains with shapes other than cubes such as spherical shapes. In this case, the length of one side when converted to a cube having the same volume is taken as the particle size, and the average particle size f is the particle size ri of each particle, the number n of particles having the particle size ri, and Σn.

When expressed as
It is less than μm.

The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse, but a monodisperse emulsion is more preferable. Here, monodisperse refers to an emulsion in which the coefficient of variation in the grain size distribution of silver halide grains contained in the emulsion is 22% or less, preferably 15% or less.

The coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Note that the particle size can be measured by various methods commonly used in the technical field for the above purpose. A representative method is Loveland's "Particle Size Analysis Method", a, s.

T. M., Symposium on Light Microscopy, 1955, pp. 94-122, or Chapter 2 of ``Theory of the Photographic Process'' by Mies and James, 3rd edition, Macmillan Publishing Co., Ltd. (1966). has been done.

The silver halide emulsion of the present invention (refers to the emulsion constituting the silver halide emulsion layer of the present invention and the emulsion constituting other emulsion layers formed as necessary).

The same applies below) The silver halide grains used in the acid method,
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or the particles may be grown from seed particles (
It may be allowed to grow after that. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and anti-ion ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and anti-silver ions may be generated by sequentially and simultaneously adding them while controlling p)l and pAg in the mixing pot.

By this method, monodisperse silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

Any equipment known in the photographic industry can be used as the silver halide emulsion manufacturing equipment.
In particular, methods such as introducing a silver salt aqueous solution and a halide salt aqueous solution through a nozzle immersed in a hydrophilic colloid solution in a mixing pot, a method of continuously changing the concentration of an additive solution, and a method of external filtration are used. Hz can be preferably used by applying a method of removing excess soluble salts and water from the hydrophilic colloid solution and preventing an increase in the interparticle distance.

The silver halide emulsion of the present invention is manufactured by controlling the grain size, grain shape, grain size distribution, and grain growth rate of the silver halide grains by using a halide 1ffl't8 agent as necessary. be able to.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (complex salts containing) and iron salts (complex salts containing) to contain these metal elements inside the particles and/or on the particle surfaces, and By placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. When removing the salts, please refer to Research Disclosure +- (Re5earch
Disclosure) No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the grain interior and the surface layer. There may be.

Silver halide grains of high chloride silver halide emulsions are easily obtained in cubic shapes, but cubic, octahedral, and tetradecahedral shapes prepared by the presence of various compounds during grain formation are also available. It may have a regular crystal shape, such as a crystal shape, or it may have an irregular crystal shape, such as a spherical or plate shape. In these particles, +100) plane and (111
) Any surface ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. Preferably, cubic particles are used in the present invention.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion layer of the present invention preferably contains a gold sensitizer. Examples of the gold compounds that can be used include (but are not limited to) chloroauric acid, sodium chloroaurate, and gold potassium thiosulfate. The concentration is X10-' moles of gold compound, preferably from 2X10-6 to lX10-' moles. More preferably 2.6X10-' to 4X10-' and most preferably 2.6X10-6 to 9X10-' moles.

The gold compound may be added at any stage of the silver halide emulsion production process, but preferably between the completion of silver halide formation and the completion of chemical aggravation. Further, after chemical ripening, compounds known as antifoggants or stabilizers in the photographic industry may be added before coating the silver halide emulsion. That is, it may be carried out at a time point at which a sensitizing effect is generally caused by the gold aggravating agent, or at a time point other than that time point.

Further, it is preferable that the silver halide emulsion layer of the present invention contains a sulfur aggravating agent. Examples of sulfur aggravating agents that can be used include (but are not limited to) sodium thiosulfate, thiourea derivatives (eg, diphenylthiourea, allylthiourea), and the like. The sulfur aggravating agent may be added in an amount that aggravates silver halide, and there is no particular limitation on it, but as a guide, in the case of sodium thiosulfate, it is preferably lXl0-' to 1 mol of silver halide.
lXl0-', more preferably 2X? O-'~8X1
It can be contained in an amount of 0-b mol.

"The lower margin of the general formula (II) used in the silver halide emulsion layer of the present invention.
) will be explained.

-a In formula (II), Z represents an atomic group necessary to form a benzotriazole ring or a 1,2,3,4-thiatriazole ring.

Among the compounds represented by the above-mentioned formula CII) used in the present invention, preferred are the compounds represented by the following general formula (Ila
) (Ilb).

General formula (Ila) General formula [:[[b] R1 and R1□ in general formula (II a) represent a hydrogen atom, a halogen atom, a nitro group, an aliphatic group, and an aromatic group.

-i formula (RI3 in II bl represents a hydrogen atom, a nitro group, a cyano group, an amino group, a mercapto group, an aliphatic group, an aromatic group, a heterocyclic group, and a -0 OR1a group. Here, RI4 is an aliphatic and aromatic groups.

Specific examples of compounds represented by the general formula ('[[a) and general formula (Ilb)] are shown below, but the present invention is not limited thereto.

a-6 Ijb-15-amino-1,2,3,4-thiatriazole nb-25-phenyl-1,2,3,4-thiatriazole nb-35-(P-aminophenyl)-1,2° 3.4
-Thiatriazole 11b-45-Nitro 1.2,3.4-Thiatriazole 11b-55-(P-carboxyphenylamino)1.
2.3.4-thiatriazole rIb-65-(3,5-dicarboxyphenylamino)l, 2.3.4-thiatriazole nb-75-(1-naphthylamino)1,2゜3.4-
Thiatriazole 11b-85-(1-cyclohexyl>1.2°3.4
-Thiatriazole 11b-95-(2-thienyl>1.2,3.4-thiatriazole 11b-105-(1-imidazolyl>1.2,3
゜4-Thiatriazole Ub-115-(4-thiazolyl) 1,2,3゜4-Thiatriazole The compound represented by the above general formula CI [a) is, for example, Draft (Berichte der Deuts)
chen Chemischen Ge5elis
draft) 20°23H1887), Journal of Organic Chemistry (J, Org,
Chem, ) 39.2469 (1965), USP
, 2824001, and Berchte (Beil,) 2
6 58.26-43.26-41 It can be synthesized according to the methods described in these documents.

The compound represented by the above general formula (Ilb) is, for example, published in the Journal of Organic Chemistry (J, O
rg, Chem,) 24,441,1054.175
0 (1957), same magazine 26, 1644.5221 (19
61), 27.3214 (1962) and Journal of the American Chemical Society-4
5,2541 (1923), same magazine 47.1916 (19
25), 48.2383 (1926), 49
．． 2745 (1927), same magazine 52, 1928 (19
30) It can be synthesized according to the methods described in these documents.

In order to incorporate the compound represented by the general formula (II) (hereinafter appropriately referred to as the "compound of the present invention" or compound CI+) into the silver halide emulsion layer, water or a compound optionally miscible with water is required. It may be added after being dissolved in an organic solvent (for example, methanol, ethanol, etc.). Compound (il) may be used alone or in combination with other compounds represented by the general formula (I[), or other stabilizers other than the compound represented by the -C formula C11), or capri inhibitors. May be used.

Various stabilizers and fog suppressants that can be used in combination will be described later.

Compound (n) is preferably added after the formation of silver halide grains. The timing of addition is before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation and before the start of chemical ripening, during chemical ripening, at the end of chemical ripening, and after the end of chemical μm formation. It may be applied at any time up to the time of application.

Preferably, it is added during chemical ripening, at the end of chemical ripening, or after the end of chemical ripening and before the time of coating.

The entire amount may be added at one time, or may be added in multiple portions.

It can be added directly to the silver halide emulsion or silver halide emulsion coating solution, or it can be added to the coating solution for the adjacent non-photosensitive hydrophilic colloid layer, and it can be added to the main layer by diffusion during multilayer coating. It may be contained in the silver halide emulsion layer according to the invention.

There is no particular restriction on the amount added, but it is usually lXl0-' mol to lXl0-1' mol per mol of silver halide.
It is preferably added in a range of 1X10-' mol to 1X10-2 mol.

Some of the compounds (n) of the present invention are compounds known in the art as stabilizers or antifoggants.

For example, British Patent No. 1,273,030,
No. 9936, JP 60-27010, JP 51-
No. 102639, JP-A-53-22416, JP-A-5
It is described in JP-A No. 5-59463, JP-A-55-79436, JP-A-59-232342, and the like.

2-・Hereafter, when the photosensitive material of the present invention is applied to a color photographic window optical material, an aromatic primary amine developer (for example, p-phenylenediamine derivative or A dye-forming coupler that forms a dye by performing a coupling reaction with an oxidized product of (aminophenol derivatives, etc.) can be used.

The coupler may be contained in each emulsion layer constituting the light-sensitive material, but as described above, the yellow coupler is preferably contained in the silver halide emulsion layer of the present invention. Examples of yellow couplers that can be used in the present invention include US Pat. Nos. 2,186.849 and 2,322,02
No. 7, No. 2,728,658, No. 2.875.0
No. 57, No. 3.265.506, No. 3.277.
No. 155, No. 3,408.194, No. 3,415
, No. 652, No. 3.447,928, No. 3.66
No. 4,841, No. 3,770°V, No. 446 in T building, No. 3,778.277, No. 3,849
．． No. 140, No. 3,894,875, British Patent No. 7
No. 78,089, No. 808, 276, No. 875.
No. 476, No. 1,402,511, No. 1,421
．． Specifications of No. 126 and No. 1,513,832, as well as Japanese Patent Publication No. 13576/1976 and Japanese Patent Publication No. 29432/1983
No. 48-66834, No. 49-10736, No. 49-122335, No. 50-28834, No. 50
-132926, 50-138832, 51-
No. 3631, No. 51-17438, No. 51-2603
No. 8, No. 51-26039, No. 51-50734,
No. 51-53825, No. 51-75521, No. 51
No. -89728, No. 51-102636, No. 51-1
No. 07137, No. 51-117031, No. 51-12
No. 2439, No. 51-143319, No. 53-952
No. 9, No. 53-82332, No. 53-135625, No. 53-145619, No. 54-23528, No. 54-48541, No. 54-65035, No. 54-
Examples include those described in No. 133329 and No. 55-598.

For example, as a white magenta coupler, U.S. Patent No. 1.96
9.479, 2.213.986, 2.2
No. 94,909, No. 2,338,677, No. 2,
No. 340,763, No. 2,343,703, No. 2
．． No. 359,332, No. 2,411°951, No. 2,435.550, No. 2,592,303, No. 2,600,788, No. 2,618,641,
2,619.419, 2,673.801, 2.691,659, 2.803.554
No. 2,829,975, No. 2,866, 70
No. 6, No. 2.881.167, No. 2.895.8
No. 26, No. 3.062.653, No. 3,127,
No. 269, No. 3,214.437, No. 3,253
, No. 924, No. 3,311,476, No. 3,41
9.391, 3.486.894, 3.5
No. 19.429, No. 3,558,318, No. 3,
No. 617,291, No. 3,684,514, No. 3
．． 705,896, 3,725,067, 3,888,680, British Patent No. 720,284, 737,700, 813.866, 892.886 No. 918.128, No. 1,0
No. 19,117, No. 1,042,832, No. 1.
047.612, 1.398, 828 and 1,398.979, West German Patent Publication No. 81
No. 4,996, Belgian Patent No. 1,070,030, Belgian Patent No. 724,427, Japanese Unexamined Patent Publication No. 46-60479, Japanese Patent Application Publication No. 49-29639, No. 49-111631, Belgian Patent No. 49
-129538, 50-13041, 50-1
No. 16471, No. 50-159336, No. 51-32
No. 32, No. 51-3233, No. 51-10935,
No. 51-16924, No. 51-20826, No. 51
-26541, 51-30228, 51-36
No. 938, No. 51-37230, No. 51-37646
No. 51-39039, No. 51-44927, No. 51-104344, No. 51-105820, No. 5
No. 1-108842, No. 51-112341, No. 51
-112342, 51-112343, 51-
No. 112344, No. 51-117032, No. 51-1
No. 26831, No. 52-31738, No. 53-912
No. 2, No. 53-35122, No. 53-75930,
No. 53-86214, No. 53-25835, No. 53
There are those described in publications such as No. 123129 and No. 54-56429.

As a cyan coupler, for example, U.S. Pat.
．． No. 410, No. 2,356,475, No. 2,36
No. 2.598, No. 2,367.531, No. 2.3
No. 69.929, No. 2.423,730, No. 2.
No. 474.293, No. 2,476.008, No. 2
, 498,466, 2.545,687, 2,728,660, 2,772.162, 2,895°826, 2,976.146 ,
No. 3,002,836, No. 3,419,390, No. 3,446,622, No. 3,476, 563
No. 3,737,316, No. 3,758.30
No. 8, No. 3,839,044, British Patent No. 478.
No. 991, No. 945, 542, No. 1,084,4
No. 80, No. 1.377.233, No. 1.388.
024 and 1.543,040, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, 50-112038, 50-117422, No. 50-130441, 5
No. 1-6551, No. 51-37647, No. 51-52
No. 828, No. 51-108841, No. 53-1096
No. 30, No. 54-48237, No. 54-66129, No. 54-131931, and No. 5'5-32071.

Couplers that form coupling products having a maximum spectral absorption wavelength in the wavelength range from 700 nm to 850 nm include Japanese Patent Publication No. 52-24849 and Japanese Patent Application Laid-open No. 53-12583.
Examples include those described in the following publications: No. 6, No. 53-129036, No. 55-21094, No. 55-21095, and No. 55-21096.

The above coupler is contained in a silver halide emulsion using a high boiling point organic solvent and a dispersion aid.

The silver halide photographic material of the present invention may contain fog during its manufacturing process, storage or development, such as tetrazaindenes, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, etc. Chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), and mercapto Pyrimidines, mercaptotriazines, thioketo compounds such as oxacyrithione, as well as benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. Many compounds known as antifoggants or stabilizers can be added.

There are no particular restrictions on the hydrophilic colloid for forming the hydrophilic colloid layer constituting the silver halide photographic light-sensitive material of the present invention. Gelatin and various other materials can be used. In addition to gelatin, colloidal albumin, agar, gum arabic, dextran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26%, polyacrylamide,
imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol vinylcyanoacetate copolymers, polyvinyl alcohol-polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated acylated proteins with vinyl groups. Polyvinylpyridine, a polymer obtained by polymerization with a monomer having
polyvinylamine, polyamine ethyl meccrylate,
Polyethyleneimine etc. can also be used.

Appropriate hardeners can be used, such as one or a combination of organic hardeners such as vinyl sulfone, acryloyl, and ethyleneimine, or inorganic hardeners such as chromium alum and potassium alum. can be used.

The photosensitive material of the present invention may contain a surfactant for purposes such as coating aid, antistatic, emulsifying and dispersing to improve slipperiness, and preventing adhesion.

Examples of surfactants include saponin, dodecylbenzenesulfonic acid sodium salt, sodium sulfosuccinate, and JP-A Nos. 49-46733 and 49-10722.
No. 50-16525 can be used.

Further, as ultraviolet absorbers, for example, penpridoazole compounds, thiazolidone compounds, acrylonitriles compounds, benzophenone compounds, etc. may be used, and other antistatic agents, fluorescent whitening agents, and antioxidants may be used as necessary. , stain inhibitors, etc. can be used.

In order to specifically obtain the photographic material of the present invention, a silver halide emulsion layer may be formed on a support after containing photographic additives in a silver halide emulsion. It can be coated via a subbing layer, intermediate layer, etc.

The supports used at this time include paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, etc., or two or more types of supports, such as a laminate of paper and polyolefin (polyethylene, polypropylene, etc.). A laminate of substrates, etc. is used. This support is then subjected to various general surface improvement treatments to improve its adhesion to the silver halide emulsion, such as surface treatment such as electron impact treatment, or subbing treatment to provide a subbing layer. The silver halide photographic emulsion is coated on this support and dried by a commonly known coating method such as dip coating, roller coating, bead coating, curtain flow coating, etc., and then dried.

When the present invention is applied to a color photographic material, the material can be developed by ordinary color development processing.

Useful color developing agents for color development include aromatic primary amine compounds such as N,N-diethyl-p-phenylenediamine, N-ethyl-N-hydroxyethylparaphenylenediamine, 4-(N-ethyl- N-hydroxyethyl)amino-2-methylaniline, Ru(N-ethyl-N-β-methanesulfonamidoethyl)amino-
2-Methylaniline, 4-(N,N-diethyl)amino-2-methylaniline, 4-(N-ethyl-N-methoxyethyl)amino-2-methylaniline and their sulfur salts, hydrochlorides, and sulfites , p-toluenesulfonate, and the like.

In particular, the rapid color developing solution can contain various photographic developing additives in addition to the color developing agent and the N,N-dialkylhydroxylamine salt as a preservative.

Examples include alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metaborate, and tribasic potassium phosphate, sodium phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, A pH buffering agent such as potassium bicarbonate, an organic solvent such as methanol, ethylene glycol triethanolamine, etc. can be appropriately selected and used.

The color developer may contain benzyl alcohol as a color development improver, but it is preferable that it does not.

It may also contain a small amount. That is, the amount of benzyl alcohol contained in the color developer is preferably O to 5-, more preferably O to 3-, per 11 color developer.

In addition to the above-mentioned N,N-dialkylhydroxylamine, it is particularly preferable to use a sulfite salt such as sodium sulfite or potassium sulfite in combination in the color developer in order to improve the storage stability of the color developer. The sulfite is preferably used in an amount of 0.05 g to 12 g, more preferably 0.1 g to 0.3 g, per color developer 1e.

Further, it is desirable that the content of water-soluble bromide as a development inhibitor in the invention developer i is small.Bromide may be contained in a very small amount, but it is most preferable that bromide is not contained at all.

The effect is remarkable when the concentration of the color developer is about 0.005 mol or more, and especially when the concentration is about 0.01 mol or more, N
, N-dialkylhydroxylamine salts are extremely effective in suppressing fog caused by rapid processing.

Note that rapid processing generally refers to color development processing time of 90 seconds or less. The temperature of the color developer is 20℃~50'
C, preferably 30°C to 40°C.

In the rapid processing method, after forming a dye image by color development, it is necessary to remove undeveloped silver halide and developed image silver by a bleach-fixing process.

The bleach-fixing time is preferably within 90 seconds, more preferably within 60 seconds.

Preferred developed silver bleaching agents include polyvalent metal salts of organic acids, such as ferric salts of organic acids. Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylene glycol bis(aminoethyl ether)tetraacetic acid, diaminopropanoltetraacetic acid,
There are iron salts such as N-(2-hydroxyethyl)ethylenediaminetriacetic acid, ethyliminodipropionic acid, cyclohexanediaminetetraacetic acid, and ethylenediaminetetraacetic acid. Further, polycarboxylic acid iron salts shown in JP-A-49-107737, such as iron salts of oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, tartaric acid, citric acid, salicylic acid, etc., may also be used. As the polyvalent metal, in addition to the above-mentioned ferric salts, cupric salts and cobalt salts may be used. Further, depending on the purpose, inorganic polyvalent metal salts such as ferric chloride and ferric sulfate may be used. In addition, as a fixing agent, conventionally known thiosulfates, thiocyanates, etc., and water-soluble alkalis such as potassium bromide, ammonium bromide, sodium iodide, etc. described in JP-A-48-101934, etc. Metal salts or ammonium bromides or iodides may also be included.

Further, in combination with color development and bleach-fixing, various treatments such as pre-hardening, neutralization, water washing, and stabilization can also be performed.

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

Example 1 A silver halide emulsion consisting of silver chlorobromide grains having an average grain size of 0.6 μm and uniformly containing 3 mol % of silver bromide was prepared by a simultaneous mixing method. This emulsion contains 3.5 ml of sodium thiosulfate.
X10-b mol 1 mol AgX was added, and 1 minute after the addition, gold chloride M2.7X10-' mol 1 mol AgX was added to perform chemical ripening. Next, the emulsion was divided and further Table 1
A spectral sensitizing dye (enhancing dye of the present invention or comparative sensitizing dye) (3×10 −4 mol/above) LtAgX shown in FIG. These spectrally sensitized emulsions were further divided and
As shown in Table 1, some of the nitrogen-containing heterocyclic compounds of the present invention shown in Table 1 or 1 mol of AgX were added to give blue sensitivity. A silver chlorobromide emulsion was prepared.

The samples shown in Table 1 were prepared by coating each blue-sensitive silver chlorobromide emulsion in the layer structure shown below.

The preparation of the sample was as follows.

Polyethylene on one side of a paper support of 170 g/=
On the other side of a support laminated with polyethylene containing 11% by weight of anatase titanium dioxide, corona discharge was applied to the titanium dioxide-containing polyethylene side, and the following layers were sequentially coated. Incidentally, the amount added is expressed per unit resistance unless otherwise specified.

Layer 1: 1.2 g of gelatin, 0.28 g (in terms of silver, the same applies hereinafter) of the above blue-sensitive silver chlorobromide emulsion, 0.50 g
0.78 g of yellow coupler (Y-1), 0.35 g dissolved in dinonyl fuculate (hereinafter abbreviated as DNP)
A layer containing image stabilizer 5TB-1 and 0.04 g of color stain inhibitor)-IQ-1 as described below.

WJ2...0.7g gelatin, 15mg anti-irradiation dye (AI-1), Long's (A
I-2) and 0.05 in which 0.05 g of HQ-1 was dissolved.
g of di-2-ethylhexyl phthalate (hereinafter referred to as DOP)
).

3...1.25g gelatin, 0.29g green-sensitive silver chlorobromide emulsion (Note 2, AgBr 1.2 mol%, average particle size 0.4011 m) dissolved in 0.308 DOP 0.45g Mazenk coupler (M-1), 0.0
8 g of light stabilizer 5TB - 2,0,15 g of light stabilizer 5
Layer containing TB-3 and 0.01 g HQ-1.

Layer 4...1.2g gelatin, 0.08H HQ-
0.35 g of D in which 1.0.4 g of ultraviolet absorber (UV-1) and 0.2 g of ultraviolet absorber (UV-2) are dissolved.
Intermediate layer containing OP.

Layer 5: Dissolved in 1.4 g of gelatin, 0.20 g of red-sensitive silver chlorobromide emulsion (Note-2, 3 mol% AgBr, average particle size 0.65.17 m), 0.20 g of DOP Did 0
, 25 g of cyan coupler (C-1), 0.25 g of cyan coupler (C-2), O, 15 g of 5TI3-
1 and 0.01 g of HQ-1.

Layer 6...1.0g gelatin and 0.208 DOP
Dissolved in L 0.30 g (D U v -1 and 0.0
5g (7) Layer containing polyhinylpyrrolidone.

Layer 7: A layer containing 0.5 g of gelatin.

As a hardening agent, 2,4-dichloro-6-hydroxy-
5-) Sodium riazine was added to the above layer, and a reactant of (tetrakisvinylsulfonylmethyl)methane and sodium taurate in a 4:1 molar ratio was added to layer 4 immediately before coating.

C+Jzs(n) rlI.

rI I I Q -1 V-1 Csll + + (t) v-2 I-I I-2 TB-1 TB-2 TB-3 0CIIHI? Comparative compound (comparative sensitizing dye) Ratio-A Ratio-B (comparative fog suppressant) H (Note-1) Green-sensitive silver chlorobromide emulsion containing sodium thiosulfate at 3.5% per mole of silver halide
Chemical sensitization was carried out by adding 10-' mole of X to green sensitizing dye (
Optical sensitization was performed using GSD-1). 4-hydroxy-6-methyl-1,3,3a as stabilizer.

The amount of 7-chitrazaindene compound was 1.2 g per mole of silver halide.

(Note-2) Red-sensitive silver chlorobromide emulsion containing sodium thiosulfate at 3.5% per mole of silver halide.
Chemical sensitization was carried out by adding 10-3 mol of X to red sensitizing dye (
Optical sensitization was performed using R3D-1).

4-hydroxy-6-methyl-1,3゜3 as a stabilizer
1.2 g of a, 7-chitrazaindene compound was added per mole of silver halide.

(CL) 2SO3e The obtained sample was exposed stepwise to intense white light and then processed according to the processing steps shown below.

In addition, some of the obtained samples were stored for 6 days at 50° C. and 72° relative 80% before being exposed, and then exposed stepwise to strong white light and then processed according to the processing steps shown below.

Processing process> Color development 35°C 45 seconds Bleach-fixing 35°C 50 seconds Washing 30-34°C 90 seconds Drying 50-70°C 60 seconds The compositions of the color developing solution and bleach-fixing solution used are as follows ( per Il).

(Color developer) Pure water 800ml N-N diethylhydroxylamine 6ml Potassium chloride 2.0g Potassium sulfite
0.2 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5 g sodium tetrapolyphosphate 2 g potassium carbonate
30 g triethanolamine
Add 8.3 g of pure water to adjust the pH to 11 and adjust the pH to 10.08.

(Bleach-fix solution) Pure water 800mj! Iron(III) ammonium ethylenediaminetetraacetate
65 g 2-sodium ethylenediaminetetraacetic acid g Ammonium thiosulfate 85 g Sodium bisulfite 10 g Sodium metabisulfite 2 g Sodium chloride
10 g hydroxylamine sulfate
Add 2g of pure water to 11 and adjust pH to 11 with dilute sulfuric acid.
Adjust to 6.2.

The density of the sample obtained by the development process was measured using monochromatic blue light, and the sensitivity was determined from the obtained characteristic curve.The unexposed sample was then developed by extending the color development time to 100 seconds, and the fog density was measured. I did it.

The results obtained are shown in Table-1.

The following can be seen from Table 1.

In sample fish 1 to Tao 6, the spectral sensitizing dye with two benzothiazole nuclei shows high sensitivity to AgC1, but the fog is high, and the desensitization and fog increase over time are significant (benzoselenazole Comparison of sample NIIL1 using a sensitizing dye having a nucleus and samples History 2 to Kan 6 using a sensitizing dye having a benzothiazole nucleus).

Samples 7 to 19 use a spectral sensitizing dye containing two benzothiazole nuclei, and a compound is added to suppress fog desensitization and fog desensitization over time.
Dye No. 1 (comparative sensitizing dye containing a benzothiazole nucleus) shows an overall improvement trend compared to LTL-6 even when the compound of the present invention is added, and in particular, although the desensitization over time becomes slightly smaller, desensitization and fogging The upper limit of the increase and fogging over time still occurs.

However, with compounds other than the present invention, the desensitization before storage is very large, and the desensitization with respect to stability over time is the same as that of the present invention, but there is no fog-inhibiting effect, and the fog-inhibiting effect is the same as that of the present invention, but the desensitization is There is no compound that has a greater effect than the compound of the present invention, such as a large value.

- Even in samples Nos. 12 to 19 using the spectral sensitizing dyes of Rikiki's invention, the fogging sensitivity of the samples other than the compounds of the present invention changed before and after storage. However, samples 13 to 15 and fish 17 using the sensitizing dye of the present invention and the compound of the present invention
It can be seen that samples No. 1 to 19 have the original sensitivity obtained by sensitizing with the spectral enhancement dye before storage, but have low fogging, and the effect is maintained even after storage over time. These effects were inconceivable from the effects obtained when the sensitizing dye of the present invention or the compound of the present invention was used alone.

Example-2 Spectral sensitizing dye shown in Table-2 (however, the amount added is the same as Example-1)
(same as ) and compound (however, the amount of compound added is 5.0X1
The same procedure as in Example 1 was carried out except that 0-' mol (1 mol AgX) was used, and the results shown in Table 2 were obtained.

From Table 2, by using samples in which the spectral enhancing dye of the present invention and the compound of the general formula (n b), which is the nitrogen-containing heterocyclic compound of the present invention, were added in different amounts from the Examples, It can be seen that the same effect as -1 can be obtained.

--I: ゛ ゛ ゛ ゛ ゛ 以 き き き き き き き き 工 工 工 工 工 工
Toru Takatsuki Procedural Amendment 1, Indication of the case 1989 Patent IQfj% 189927 No. 2, Name of the invention Rapidly processable silver halide photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent applicant Address: 191 Tokyo 1-5 Sakura-cho, Miyakohino-shi, amended vs. Tomei J18, ``Detailed Description of the Invention'' column.

6. Contents of amendment The detailed description of the invention is amended as follows.

(2) General formula [1] on page 10, line 6, is corrected as follows.

(3) Delete "The concentration of the color developer...is extremely high." from line 6 to line 10 on page 37.

(4) Page 48 ratio -^ is corrected as below.

(5) Page 48E is corrected as follows.

1l (6) Page 50, R5D-1, is corrected as follows.

(7) Between PJ% 31st line 8th line and 15th line, 1 promobenzimiguzole, ... thioketo compound, and 1 is corrected as below.

1 Bromobenzimigol M, 7 M/) lyazoles, etc.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains: a) 80 mol% or more of silver chloride; Silver halide grains containing b) at least one spectral sensitizing dye represented by general formula [I], and c) at least one compound represented by general formula [II] material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X_1, X_2, X_3 and X_4 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and a hydroxyl group, respectively. R_1 and R_2 each represent an alkyl group. X represents a counter anion. n represents 0 or 1. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z is a benzotriazole ring or 1, 2, 3, 4
-Represents the atomic group necessary to form a thiadriazole ring. )