JPH03184039A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress the fogging generated in dot images by incorporating at least one kind of specific compds. into the above photosensitive material. CONSTITUTION:At least one kind of the compds. expressed by formula I are incorporated into the photosensitive material. In the formula I, R1 denotes a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkinyl group, aryl group, or heterocyclic group; R2 denotes an alkylene group or alkenylene group; R3 denotes a hydrogen atom or alkyl group; R denotes a hydrogen atom or block group; Ar denotes an arylene group or heterocyclic group; one of A1 and A2 denote a hydrogen atom and the other denotes a hydrogen atom, acyl group, sulfonyl group or oxaryl group. Ar denotes an arylene group and R1 denotes a hydrogen atom, alkenyl group, alkinyl group, aryl group or heterocyclic group when R denotes a hydrogen atom. Ar denotes a hyterocyclic group. Thus, the sand- and pin-like fogging of the dots is suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and particularly to a photographic material containing a compound capable of functioning as a novel nucleating agent.

[Background of the invention]

Nucleating agents are known to be used, for example, as contrast enhancing agents in silver halide photographic light-sensitive materials used in photolithography processes, and as fogging agents in direct positive-type silver halide photographic light-sensitive materials.

In the photoengraving process, a silver halide photographic material with high contrast photographic properties is generally used in the step of converting continuous tone density changes of an original into a set of halftone dots having an area proportional to this density. There is.

Adds sharp characteristics to images! Conventionally, hydrazine has been added to silver halide photographic materials as a contrast enhancer, as shown in Japanese Patent Application Laid-open No. 56-106244, U.S. Patent No. 4,686.167, and European Patent No. 333.435. In addition, silver halide grains that effectively exhibit the high contrast characteristics of this compound are used, and other photographic additives are appropriately combined to obtain the desired photographic light-sensitive material. Ta. Such silver halide photographic light-sensitive materials are certainly stable as light-sensitive materials, and high-contrast photographic images can be obtained even when processed with a developer capable of rapid processing.

However, when converting a continuous tone original into a halftone image, sand-like or bottle-like fog, or so-called black bins, may occur in the halftone dots, resulting in a problem in which the quality of the halftone image is impaired. . In order to solve this problem, conventional methods have been taken such as adding various stabilizers and inhibitors containing heteroatoms, but these are not necessarily effective. Ta.

Therefore, there is a need for a photosensitive material using an effective contrast enhancer that solves the above-mentioned problems.

On the other hand, one method for forming a positive image using a direct positive silver halide photographic light-sensitive material is to use an unfogged internal latent image type silver halide emulsion, and after image exposure, the image is exposed in the presence of a fogging agent. A method is known in which surface development is performed to obtain a positive image.

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2,592,250;
, 456.957, 2,497.875, 2,
588.982, British Patent No. 1,151.363, Japanese Patent Publication No. 43-29405, Japanese Patent Publication No. 47-9434, Japanese Patent Publication No. 47-9677, British Patent No. 47-32813, Japanese Patent Publication No. 4732
No. 814, No. 48-9727, No. 48-9717,
U.S. Patent No. 3,761,266, U.S. Patent No. 3,496.577
The main ones are JP-A No. 50-8524, JP-A No. 50-38525, etc.

Hydrazine compounds are known as useful fogging agents.

For example, U.S. Patent Nos. 2,563,785 and 2,588
．． Hydrazine compounds described in US Pat. No. 982, naphthylhydrazine sulfonic acid described in US Pat. No. 2,064,700, or sulfomethylhydrazines described in US Pat. No. 1,403,018 are used as fogging agents. . Further, Japanese Patent Publication No. 17184/1984 describes that a color positive image can be obtained using a hydrazide or hydrazone compound.

However, when these compounds are used, the induction period before development is initiated is long compared to the development of conventional latent silver, and the development is therefore considerably delayed.

Furthermore, when applied to a multilayer color photographic material, the prior art has problems such as non-uniformity of characteristics between the eyebrows and a low maximum density.

In addition, in order to maintain a favorable fogging effect and obtain good results, development has conventionally been carried out at a high pH value of 12 or higher, but this significantly accelerates the deterioration of the developing agent and
This is not at all desirable as it deteriorates the film properties of the photographic light-sensitive material.

Therefore, as for direct positive type silver halide photographic light-sensitive materials, a light-sensitive material using an advantageous fogging agent that solves the above-mentioned problems is desired.

[Purpose of the invention]

A first object of the present invention is to provide a silver halide photographic material that has high-contrast photographic properties and is capable of suppressing fog occurring in halftone images and exhibiting high-contrast photographic properties. It is in.

The second object of the present invention is to apply it to a direct positive type silver halide photographic light-sensitive material, to obtain a sufficiently high maximum density (D wax) even when developed with a low pH developer, and to be able to achieve a high maximum density (D wax) in a short period of time. It is an object of the present invention to provide a photographic light-sensitive material which can obtain good images with a high maximum density and a low minimum density even after fog development, and which can suppress an increase in the minimum density even after storage over time.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer, which contains at least one compound represented by the following general formula [I]. achieved.

General formula (I) In the formula, R1 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R1 is an alkylene group or an alkenylene group.
R3 is a hydrogen atom or an alkyl group, R is a hydrogen atom or a block group, Ar is an arylene group or a heterocyclic group, %A
I and A! One side represents a hydrogen atom, and the other side represents a hydrogen atom, an acyl group, a sulfonyl group, or an oxalyl group.

However, when R represents a hydrogen atom, Ar represents an arylene group, and R represents a hydrogen atom, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, or A'' represents a heterocyclic group.

General formula [I] will be explained in more detail.

R1 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl,
i-globil, butyl, t-butyl, hexyl, octyl, L-octyl, decyl, dodecyl, tetradecyl,
cyclohexylmethyl, benzyl, etc.), cycloalkyl groups (e.g. cyclohexyl, 4-chlorocyclohexyl, etc.), alkenyl groups (e.g. allyl, l-propenyl, l,3-butadienyl, 2-butenyl, 2-pentenyl, cinnamyl) ), alkynyl groups (e.g., propargyl, 2-butynyl, etc.), aryl groups (e.g., phenyl, pt-butylphenyl, naphthyl, etc.), heterocyclic groups (e.g., pyridyl, tetrazolyl, oxacylyl, benzosyl), oxacylyl, benzothiazolyl,
The heterocyclic group preferably does not contain a mercapto group.

R2 represents an alkylene group (eg, methylene, ethylene, trimethylene, methylmethylene, ethylmethylene, butylmethylene, hexylmethylene, decylmethylene, etc.) or an alkenylene group (eg, propenylene, butenylene, etc.).

R3 represents a hydrogen atom or an alkyl group (eg, methyl, ethyl, benzyl, etc.).

Ar is an arylene group (e.g., phenylene, naphthylene, etc.) or a heterocyclic group (e.g., pyridine, thiophene,
7-ran, etc.). The arylene group or heterocyclic group represented by Ar includes those having substituents such as alkyl, alkoxy, hydroxyl, halogen, amino, acylamino, sulfonamide, and ureido.

R is a hydrogen atom and an alkyl group as a blocking group (for example, methyl, ethyl, benzyl, methoxymethyl,
(trifluoromethyl, phenoxymethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl, etc.)
, aryl group (e.g., phenyl, chlorphenyl, etc.), heterocyclic group (e.g., pyridyl, thienyl, furyl, etc.), R4 and R1 are hydrogen atoms, alkyl group (e.g., methyl, ethyl, benzyl, etc.), Alkenyl group (e.g. allyl, butenyl, etc.), alkynyl t: (a
ll −+ l−r propargyl-butynyl, etc.),
Aryl groups (e.g., phenyl, naphthyl, etc.), heterocyclic groups (e.g., 2,2,6,6-titramethylbiveridinyl, N-ethyl-N'-ethylpyrazolidinyl, pyridyl, etc.) , represents a hydroxyl group, an alkoxy group (e.g., methoxy, ethoxy, etc.), an amino group (e.g., amino, methylamino, etc.), and R and R represent a ring (e.g., piperidino, morpholino, etc.) together with a nitrogen atom. may be formed.

R6 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl,
methoxymethyl, hydroxyethyl, etc.), alkenyl groups (e.g., allyl, butenyl, etc.), alkynyl groups (e.g., propargyl, butynyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), heterocyclic groups ( For example 2,2,6,6-titramethylpiperidinyl, N-
methylpiperidinyl, pyridyl, etc.).

One of A1 and A is a hydrogen atom, and the other is a hydrogen atom, an acyl group (e.g., acetyl, trinoloacetyl, etc.), a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an oxalyl group (e.g., ethoxalyl). It is most preferable that A and A2 are both hydrogen atoms.

Representative specific compounds represented by the above general formula [I] are shown below, and (specific compounds) (2) (3) (4) C, Hs (6) (9 ) (lO) (12) (13) (15) (I6) (17) (19) (21) (22) (23) (24) (25) (26) (27) (28) (29) ( 30) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) CH,0H CH,0H CH,OH (51) (52) (53) (54) (55) (56) (57) (59) (60) (61) (62) (63 ) (64) (65) (66) (67) (68) Next, a method for synthesizing the compound of the present invention will be described.

For example, compound (1) can be synthesized from the intermediate described in European Patent No. 330.109 according to the following synthetic method.

Compound (36) can be synthesized from the intermediate described in Japanese Patent Application No. 62-336565 according to the following synthesis method.

Other compounds can also be synthesized using similar synthetic methods.

Next, a preferred embodiment in which the silver halide photographic material of the present invention is applied to a light-sensitive material exhibiting photographic properties with high contrast will be described.

The silver halide photographic light-sensitive material capable of obtaining high-contrast images to which the present invention is applied includes the general formula [I
] At least one compound represented by formula (1) is contained as a substance that functions as a contrast enhancer, and the amount of the compound of general formula (1) contained in the photographic light-sensitive material is 5 x 10- per mole of silver halogenide
Preferably, it is 'mole-5×10-' mole.

In particular, it is preferably in the range of 5 X 1()-'mol-lXl0-''mol.

The silver halide photographic light-sensitive material of the present invention has a length of at least 1 m
It has a silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on each side of the support. This silver halide emulsion can be coated directly onto the support, or it can be coated via another layer, such as a hydrophilic colloid layer that does not contain the silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layer may be coated separately into silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer consisting of a hydrophilic colloid may be provided between each silver halide emulsion layer. Also, an intermediate layer may be provided between the /% silver halide emulsion layer and the protective layer.

That is, non-photosensitive hydrophilic colloid layers such as an intermediate layer, a protective layer, an antihalation layer, and a backing layer may be provided as necessary.

In order to incorporate the 42 compound represented by the general formula (1) into the silver halogenide photographic light-sensitive material of the present invention in order to function as a contrast enhancer, it is necessary to incorporate it into the hydrophilic colloid layer of the light-sensitive material. Preferably, it is particularly preferably contained in a hydrophilic colloid layer adjacent to the silver halide emulsion layer and/or the silver halide emulsion layer.

Next, the silver halide used in the silver halide photographic material of the present invention will be explained. Silver halide of any composition can be used. For example, silver chloride, silver chlorobromide,
There are silver chloroiodobromide, pure silver bromide, silver iodobromide, and silver chloroiodobromide. The average diameter of the silver halide particles is 0.05 to 0.
．． A thickness in the range of 5 μm is preferably used, and a thickness in the range of 0.10 to 0.40 μm is particularly preferred.

Although the grain size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted so that the monodispersity value defined below is in the range of 1 to 30, more preferably in the range of 5 to 20. .

Here, the degree of monodispersity is defined by the following formula.

That is, the degree of monodispersity is defined as a value obtained by dividing the standard deviation of particle diameter by the average particle diameter times 100. For convenience, the grain size of the silver halide grains is expressed by the principal dimension of cubic crystal grains, and other grains (octahedron, tetradecahedron, etc.) are calculated by the square root of the projected area.

When carrying out the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, the core part is silver chloride or silver iodobromide, and the shell part is silver halide grains. It is possible to use silver chlorobromide grains or silver chloroiodobromide grains in which the core portion is silver bromide, and the core portion is silver bromide and the shell portion is silver chloride. At this time,
Iodine can be contained in any layer, but iodine
It is preferably within mol%.

The silver halide grains used include cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron during the grain formation and/or growth process. Metal ions can be added using at least one selected from salts (including complex salts) to contain these metal elements inside the particles and/or on the particle surfaces, and the particles can be placed in an appropriate reducing atmosphere. By this, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Furthermore, silver halide can be sensitized with various chemical sensitizers. As the sensitizer, for example, activated gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, etc.),
Selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, silver tin chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2
-Aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroole-
Various noble metal sensitizers, such as sodium chloroparadite and the like, can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

When the present invention is applied to a light-sensitive material capable of obtaining a high-contrast image, it is preferable to use a light-sensitive material in which the silver halide grains are grains whose surface sensitivity is higher than that of the internal sensitivity, that is, silver halide grains which give a so-called negative image. Therefore, performance can be enhanced by treatment with the above chemical sensitizers.

In addition, the silver halide emulsion used is mercapto (l
-722-5-mercaptotetrazole, 2-mercaptobenzothiazole), benzotriazoles (5-
Stabilization or fog suppression can be performed using bromobenzotriazole, 5-methylbenzotriazole), benzimidazoles (6-nidropenzimidazole), and the like. Incidentally, a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardening agent, a development accelerator, etc. can also be added to the silver halide emulsion used in the present invention.

When the compound of general formula [I] according to the present invention is added to a hydrophilic colloid layer, gelatin is suitable as a binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used.

In carrying out the present invention, supports that can be used for light-sensitive materials for obtaining high-contrast images include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. can be mentioned. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

For example, the following developing agents are used to develop silver halide photographic materials that produce high-contrast images.

Representative examples of HO-(CI-[I], -OH type developing agents include hydroquinone, and others include catechol and pyrogallol.

Further, as the HO-(CH-CI(), -NH1 type developer, ortho- and para-aminophenol or aminopyrazolone are representative), N-methyl-p-aminophenol, N-β-hydroxyethyl -p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc. Heterocyclic type developers include l
-phenyl-3-pyrazolidone, l-phenyl-4,4
-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Examples include 3-pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.

Other books include The Theory of the Photographic Process, 4th edition (Tb8The
ory of the Photographic P
rocess, Fourth Edition) 29
pp. 1-334 and Journal of the American
Chemical Society (Journal of the
Awerican Che+m1cal 5ociet
y) The developer described in Vol. 73, 3100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. When used alone, hydroquinone is preferred; when used in combination, a combination of hydroquinone and 1-7 enyl-3-pyrazolidone, or a combination of hydroquinone and N-methyl-p-aminophenol is preferred.

Furthermore, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for development, the effects of the present invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as potassium bromide, organic development inhibitors such as benzotriazole, and ethylenediamine. Metal ion scavengers such as tetraacetic acid, methanol, ethanol, benzyl alcohol,
Development accelerators such as polyalkylene oxide, sodium alkylaryl sulfonates, surfactants such as natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, ions such as sodium sulfate, etc. It is optional to add a strength modifier or the like.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent.

Next, a preferred embodiment in which the light-sensitive material of the present invention is used as a direct positive type silver halide photographic material will be described.

In this case, the general formula [! The compound represented by ] can function as a fogging agent. Hereinafter, when the compound represented by the general formula [1] is used as a fogging agent, it is referred to as "the fogging agent of the present invention".

The fogging agent of the present invention is present in such a manner that at least one of them can be coupled to an internal latent image type silver halide emulsion, which is an emulsion that directly gives a positive image, during development processing after image exposure. Just force it. That is, after exposure of a photographic light-sensitive material having an internal latent image type silver halide emulsion, it may be incorporated into the light-sensitive material in such a form that it is developed in the presence of the fogging agent of the present invention.

In a preferred embodiment, at least one fogging agent of the present invention is added to a silver halide emulsion layer or a layer adjacent thereto (for example, a silver halide photosensitive layer, an intermediate layer, a filter layer,
protective layer, antihalation layer, etc.).

The amount of the fogging agent used in the present invention can vary widely depending on the characteristics of the silver halide emulsion used, the type of fogging agent, and the development conditions. The amount may be sufficient as long as it provides enough fogging action to obtain a positive image by subsequent development with a surface developer. It is desirable that the amount provides a sufficient maximum density (for example, 2.0 or more) after the development process.

In order to incorporate the fogging agent of the present invention into a silver halide emulsion, approximately 10-5 to 10-1 mol of a nuclear preservative should be added to 1 mol of silver halide at an appropriate time after ripening. It is preferable to

Silver halide developers that can be used in the development process in carrying out the present invention include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc. or a mixture thereof. These developers can also be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution.

In carrying out the present invention, the developing composition used for developing the direct positive type silver halide photographic light-sensitive material may further contain a specific anti-capri agent and a development inhibitor. Alternatively, it is also possible to optionally incorporate these compositions into the layers of silver halide photographic materials. usually,
Useful anti-capri agents include, for example, benzotriazoles, benzothiazoles such as 5-methylbenzothiazole; l-phenyl-5-mercaptotetrazoles, 5-methylbenzotriazole, etc., l-methyl-2-
Heterocyclic thiones such as tetrazoline-5-thione and the like include aromatic and aliphatic mercapto compounds.

When the present invention is applied to a direct positive type silver halide photographic light-sensitive material, the silver halide emulsion is an internal latent image type silver halide emulsion, that is, a latent image is mainly formed inside the silver halide grains, and a photosensitive nucleus is formed. It is an emulsion having silver halide grains having most of the silver halide grains inside the grains. The silver halide used to form this emulsion includes any silver halide, such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like.

Particularly preferably, the emulsion used in this case is obtained by exposing a portion of a sample coated with the emulsion to a transparent support to a light intensity scale for a defined period of time up to about 1 second, to obtain a substantially halogen-free emulsion. When developing for 4 minutes at 20°C using the following surface developer A, which does not contain a silver oxide solvent and develops only the surface image of the grains, another part of the same emulsion sample is similarly exposed and the inside of the grains is developed. 20 minutes with internal developer B below to develop an image of
It shows a maximum density not greater than 115, which is the maximum density obtained when developed for 4 minutes at °C. Preferably,
The maximum density obtained with surface developer A is not more than 1/10 of the maximum density obtained with internal developer.

Surface developer A Metol 2.56L-Ascorbic acid 10 g Sodium metaborate (tetrahydrate) 20 g Potassium bromide
Add 1g water
IQ internal camphor solution B Metol 2.0g subii!
E acid 7-da (anhydrous) 90, 0g Hydroquinone 8.0g Sodium carbonate hydrate 52.5g Potassium bromide
5.0g potassium iodide
Add 0.5g water
112 Also, internal latent image type silver halide emulsions include those prepared by various methods. For example, the conversion silver halide emulsion described in U.S. Pat. No. 2,592.250 or U.S. Pat. No. 3,206.
No. 316, No. 3,317.322, No. 3,367.7
No. 78, Japanese Patent Publication No. 43-29405, silver halide emulsions having internally chemically sensitized silver halide grains, or U.S. Pat.
Silver halide emulsions having silver halide grains containing polyvalent metal ions as described in No. 447,927 and No. 3,531゜291, or JP-A-50-852
Silver halide emulsions comprising grains having a laminated structure as described in No. 4, or silver halide emulsions containing silver iodide prepared by the ammonia method described in Japanese Patent Application No. 74062/1980. It is.

Furthermore, the internal latent image type silver halide emulsion used preferably contains 11 to 10 g of a compound having an azaindene ring and a nitrogen-containing heterocyclic compound having a mercapto group per mole of silver halide. Can give more stable results with lower minimum concentrations.

As the compound having an azaindene ring, 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene is preferable. Examples of the nitrogen-containing heterocyclic compound having a mercapto group include a pyrazole ring, a 1.2.4-) riazole ring, a 1.2.3-) riazole ring, a 1.3.4-thiadiazole ring, and a 1,2.3- Thiadiazole ring, 1.2.
4-thiadiazole ring, 1.2.5-thiadiazole ring, 1.2.3゜4-tetrazole ring, pyridazine ring, 1
．． 2.3-triazine ring, 1.2.4-) riazine ring,
1.3.5-triazine ring, a ring in which 2 to 3 of these rings are condensed, such as triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring, etc., and 7-talazinone ring, indazole ring, etc., and l-7enyl-5-mercaptotetrazole is preferable.

The silver halide photographic light-sensitive material of the present invention, particularly when applied to a positive-type light-sensitive material, can be a black-and-white photographic light-sensitive material, or
It may be a monochromatic color photograph or a multicolor color photographic light-sensitive material.

In the case of a full-color photosensitive material, it is preferable to have a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. In this case, a photographic image is usually obtained from a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler. A photosensitive material is formed.

In one preferred embodiment, the layer structure includes a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer in order from the side farthest from the support, and a non-photosensitive layer (yellow filter) is provided between the blue-sensitive layer and the green-sensitive layer. layer).

As the yellow coupler, known acylacetanilide couplers can be preferably used, and among these, benzoylacetanilide and pivaloylacetanilide compounds are preferred.

As the magenta coupler, 5-pyrazolone couplers, pyrazoloazole couplers, and acylacetonitrile couplers can be used.

As the cyan coupler, naphthol couplers and phenol couplers can also be preferably used.

In addition, the support may have a photosensitive silver halide emulsion layer as described above and a non-photosensitive layer serving as a yellow filter layer, as well as an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer. It is possible to provide a large number of various photographic constituent layers such as. As these coating methods, dip coating method, air doctor coating method, extrusion coating method, slide hopper coating method, curtain 70-coating method, etc. can be applied.

In the case of a direct positive silver halide photographic light-sensitive material, the support may be, for example, a polyethylene terephthalate film, undercoated if necessary, a polyethylene film, a polystyrene film, a polypropylene film, a cellulose acetate film, or a glass film. , baryta paper, polyethylene laminate paper, etc.

The support may be opaque or transparent,
It can be selected depending on the intended photosensitive material.

Depending on the purpose, various photographic additives such as wetting agents, film property improvers, and coating aids may be added to the silver halide emulsion of the photographic material. Furthermore, other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, A development speed regulator, matting agent, etc. may also be used.

It is also useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and besozophenone compounds to prevent fading of dye images due to short-wavelength actinic rays.

In the silver halide emulsion layer, gelatin or other suitable gelatin derivatives can be used as a protective colloid or binder depending on the purpose, and other hydrophilic binders (binders) can be used depending on the purpose. ) can be included. The above-mentioned photographic light-sensitive material can be added to photographic constituent layers such as an emulsion layer, an intermediate layer, a protective layer, a filter layer, and a backing layer, depending on the purpose. It is possible to contain agents, wetting agents, etc.

Additionally, each of the constituent layers can be hardened with any suitable hardener.

Furthermore, an As agent (antistaining agent) can be used in the photosensitive material.

〔Example〕

Examples of the present invention will be described below. Note that, as a matter of course, the present invention is not limited only to the following examples.

Example 1 An exemplary compound represented by general formula (1) and a comparative compound (the types of which are shown in Table 1 below) were added to the silver halide emulsion layer of a photographic light-sensitive material in the following manner to prepare a sample. was prepared.

(Preparation of silver halide photographic light-sensitive material) 100 μm thick with a 0.1 g undercoat layer on both sides.
A silver halide emulsion layer having the following formulation (1) was coated on one of the undercoating layers of the polyethylene terephthalate film so that the amount of gelatin was 1.5 g/s and the amount of silver was 3.3 g/s. Then, on top of that, a protective layer of the following formulation (2) is applied with a gelatin amount of 1. 0g/m", and on the other undercoat layer on the opposite side, apply a backing layer according to the following recipe (3) so that the amount of gelatin is 3.5 g/m". Further, a protective layer having the following formulation (4) was applied thereon so that the amount of gelatin was 1 g/l to obtain samples Nos. 1 to 13.

Prescription (1) [Silver halide emulsion layer composition] Gelatin
1.5g 7m” Silver chlorobromide (AgC
ff 60 mol%, AgBr 40 mol%, monodispersity=
12) 3.3g/la” anti-capri agent = 4-hydroxy-6-methyl-1,3,3a
, 7-chitrazaindene 0.30g/la”
Compounds of the present invention or comparative compounds according to Table 2: Surfactant: Saponin 0.1 gem" Latex polymer: Polyethyl acrylate Ig/X Sensitizing dye 2 Five types of the following structural formulas (a) to (d) Used together.

(a) Regular sensitizing dye 5-g/2 (b) Ortho sensitizing dye (b) (c) Panchromatic sensitizing dye long c1 (d) Infrared sensitizing dye 3 mg/m'' Development regulator: Nonyl Phenoxypolyethylene glycol 10mg/1 5-methylbenzotriazole 7B/as”Adenine 3 g/l Guanine
2-g/l uracil
21g/11-phenyl-5-mercaptotetrazole 31g/-2 Hydroquinone 100mg/m”l
-Phenyl-3-t' lasolitone 10 mg/Sono 2 formulation (2) [Emulsion protective layer composition] Gelatin 1.0 g/■3 Matting agent: Polymethyl methacrylate surfactant with an average particle size of 3.0 to 5.0 μl Nidodecylbensodium charge modifier: CsF+yCOON)IaaC12 1C11 Formulation stabilizer: 0.05g/m" Zensulfonic acid 0.01g/m"105g/m"100g/m"30mg/m" 5-g/-8 1- Phenyl-5-mercaptotetrazole 3mg/m" Hardening agent: formalin 0.03g 1m" formulation (3) [Backing layer composition] Gelatin 3.5g/s" Surfactant: Saponin 0.1g/m" hardening Film agent: Glyoxal O, 1g/m” prescription (4) [
Backing protective layer composition] Gelatin matting agent 1 g/Peng 2: Polymethyl methacrylate with an average particle size of 3.0 to 5.0 μm 0.5 g/Rinfu surfactant: Sodium p-dodecylbenzenesulfonate A 0.01 g /m"Development regulator: 0, O1g/a" 5-nitroindazole 0.012g/-2 5-methylbenzotriazole l-phenyl-5-mercaptotetrazole 0.005g/n+"Hardener: Formalin 0.03g /va'' The resulting sample was subjected to a halftone quality test using the method described below.

(Testing method for halftone dot quality) After attaching a part of the screen (150 lines/inch) with a halftone dot area of 50% to the step wedge, and placing the sample in close contact with this screen, the sample was exposed to a xenon light source for 5 seconds. , development processing was carried out under the following conditions in an automatic processing machine for rapid processing using the following developing solution and fixing solution, and the halftone dot quality of the sample was observed with a 100x magnifying glass, and those with high halftone dot quality were 5" rank, and the following five ranks: "4", "3", "2", and rlJ. Note that the ranks rlJ and "2" are at practically unfavorable levels.

Fog in the halftone dots is also evaluated in the same way, and the highest rank is "5" when there are no black pins in the halftone dots, and the rank is "5" depending on the degree of occurrence of black pins in the halftone dots. 4", "
The evaluation was performed by sequentially lowering the ranks to ``3'', ``2'', and rlJ. In addition, the black bins are also large in ranks rl+ and "2", which is at a practically unfavorable level.

(Developer formulation) (Set *A) Pure water (ion exchange water) 150 taQ
Ethylenediaminetetraacetic acid disodium salt diethylene glycol 50 Potassium sulfite (55%W
/V aqueous solution) 100 potassium carbonate
50 Hydroquinone 155
-Methylbenzotriazole 2001-phenyl-5-mercaptotetrazole 0 mg: Amount to convert 9H of working solution to 1004 Potassium hydroxide Potassium bromide (composition B) Pure water (ion exchange water) Diethylene glycol g Diethylamino-1,2-propane Diol 15 g Ethylenediaminetetraacetic acid disodium salt 5 mg Acetic acid (90% aqueous solution) 0.3■a 5-nitroindazole 110 vIg
Sodium 2-mercaptobenzimidazole-5-sulfonate 30 mzl-722-3
- Pyrazolidone 500 mg When using a developer, the above compositions A and B were dissolved in the order of 500 mff of water and used after finishing to lα.

(Fixer formulation) (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0 m (1 Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g sodium citrate 2
Water salt 2g acetic acid (90% w/w aqueous solution)
13.6 an (composition) Pure water (ion exchange water) 17 rxQ
a acid (50% w/w aqueous solution) 4.7 g
Aluminum sulfate (AQ!03 equivalent content is 8.1%w/
When using a 26.5 g fixer solution, dissolve the above composition A1, a B, in the order of 500 μa of water, finish it to 111, and use it. This fixer p
H was approximately 4.3.

(Development processing conditions) (Process) (Temperature) (Time) Development 38°C 30 seconds constant
Arrived at 28°C, washed at 20 degrees with sand and water, washed at room temperature for 20 seconds.As comparative compounds added to the silver halide emulsion layer in formulation (1), the following compounds (a) to (c) were used.

(a) (b) CC) (Test results) Table 1 shows sample Nos. 11 to 13 prepared using the sample No. 1"IO of the present invention and the above comparative compound, and the silver halide emulsion layer thereof. The added compounds and their added amounts are shown.The compounds of general formula (1) in Table 1 are as follows:
It is shown by the number of the above-mentioned exemplified compound.

Table 2 shows the results of the halftone quality test, ranked for each of the above samples.

As is clear from Table 2, in terms of halftone quality, sample Nos. 1-10 according to the present invention were all ranked "4".
As described above, comparative sample No. 1l-13 both showed a result of rank "3".

Considering that the ranks "l" and "2" are at a level that cannot be used in practical use, it is difficult to say that the halftone dot quality of sample No. 11=13 is good. On the other hand, samples No. 1-10 according to the present invention both have extremely high halftone dot quality and are good.

In addition, regarding the degree of occurrence of black pins, which is an index of Capri, samples No. 1-10 according to the present invention were all ranked "5".
Comparative sample No. 11"13 was rated "4" and showed an extremely good result with no fog, while comparative sample No. 11"13 was ranked "2" and was found to show results that were difficult to withstand in practical use. .

In addition, instead of compound 1 of sample No. 1, 28.32°6
The effects of the present invention were also observed for each sample using Sample No. 9.

Table-1 Table-2 Example 2 In Sample No. 3 and Sample No. 8 of Example 1, the monodispersity (uniform grain size; according to the above definition) of the silver halide grains was changed from 4 to 40. Samples Nos. 14 to 23 were created and tested.

Also, when preparing the particles, rhodium was added at 8 x 10-' mol/
1 mol of Ag and 3 x 10-' mol of iridium/
1 mol of A g was added according to a conventional method. The silver halide composition here is a silver chlorobromide grain composition containing 98 mol% of silver chloride, and instead of adding sensitizing dyes ((a) to (d)),
A desensitizing dye with the following structure was added.

Desensitizing dye (sum of anode potential and cathode potential of polarographic is positive) Furthermore, 501 g/l of the following filter dye was added to the protective layer, and 100+sg/m'' of the following ultraviolet absorbing dye was added.

The rest was the same as Sample No. 003 and Sample No. 008, and for example, the same exemplified compounds No. 36 and No. 36 were used as the compounds represented by formula (I). Monodispersity is
It can be adjusted by a conventional controlled double jet method by changing the pH potential at the time of particle charging and the supply amounts of Ag ions and halide ions.

Further, exposure and development treatments were carried out in substantially the same manner as in Example 1, and the photographic performance was evaluated. However, in this example, the prepared sample was exposed to light using an ultra-high pressure mercury lamp with an energy of 51 J.

The evaluation results are shown in Table-3. Sample Nos. 14 to 23 are
The halftone dot quality is 4.5 to 5, and the black pin is 4.5 to 5, both of which are good.The halftone dot quality is high and the fog is extremely low.Example 3 Using the following silver halide emulsion, sensitization Using only the above-mentioned ortho-sensitizing dye (b)-1 as the dye,
(CH) as a hardening agent in formulation (2).

= CH30zCHi)zO to 0. The same procedure as in Example 1 was carried out except that the compound of the present invention and the comparative compound listed in Table 4 were used.

(Preparation of silver halide emulsion) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using a simultaneous mixing method. During this mixing, IrC(2
, was added at a rate of 6 x 10-' moles per mole of silver.

The obtained emulsion was an emulsion consisting of cubic grains with an average grain size of 0.20 .mu.m. After washing and desalting this emulsion with water in a conventional manner, the pA at 40°C was determined using an aqueous potassium iodide solution.
g was adjusted to 8.80. Furthermore, during redispersion, the following compounds [
A mixture of [A], [B], and [C] was added.

Developer recipe Hydroquinone N-methyl-p-aminophenol 1/2 sulfate Sodium hydroxide 45.0g 0.8g 18.0g Potassium hydroxide 55.0g5-
Sulfosalicylic acid 45.0gboric acid
25 + 0g Potassium sulfite 110.0g Disodium ethylenediaminetetraacetate 1.0g Potassium bromide 6.0g 5-methylbenzotriazole 0.6g Butyljetanolamine 15.0g Add water
1a (pH-11,6) In addition, the obtained sample was subjected to the same dot quality test as in Example 1, and further measured with a Konica digital densitometer PDP-65, and the density of sample No. 29 was 3.0. The sensitivity at 1
The relative sensitivity is expressed as 00, and the gamma is expressed as the tangent between the densities 0.3 and 3.0.

The results obtained are shown in Table 4.

As is clear from Table 4, the samples according to the present invention have higher sensitivity, higher contrast, and better halftone dot quality and black spots (degree of occurrence of black spots) than in comparison.

Table-4 Example 4 (Preparation of emulsion A) A monodisperse silver bromide emulsion was prepared as follows.

An aqueous solution containing ossein gelatin was controlled at 70°C, and an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were simultaneously added to the solution by a controlled double jet method while stirring vigorously. An octahedral emulsion was obtained.

To this emulsion were added 5 mg of sodium thiosulfate and 6 mg of chloroauric acid (tetrahydrate) per mole of silver, and
Chemical ripening was performed by heating for minutes to obtain a silver bromide core emulsion. The core emulsion thus obtained was further grown by adding an aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (50:50 molar ratio) to form a monodispersed octahedral grain with an average grain size of 0.7μ. A core/shell silver chlorobromide emulsion was obtained. After washing with water and desalting, this emulsion contains:
1.3 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) were added and heated at 60° C. for 70 minutes to perform a chemical sensitization treatment to obtain an internal latent image type silver halide emulsion.

(Preparation of sample) On a paper support laminated on both sides with polyethylene,
A color photographic light-sensitive material having the following layer structure was prepared, and sample No.
32.

Sample No. 32 (Unless otherwise specified, the amount of each compound is expressed numerically as the amount coated. The unit is sg/da'. However, the emulsion is converted to silver. The structure of the compound will be described later.) 7th layer (protective layer) Gelatin 12.3 6th layer (UV absorption layer) Gelatin 5.4 Ultraviolet absorber (UV-1) 1.0 Ultraviolet absorber (UV
-2) 2.8 Solvent (S O-3) 1.2 5th layer (blue sensitive layer) Emulsion A (contains sensitizing dye BD-1) 5.0 Gelatin
13.5 yellow coupler (Y
C-1) 8.4 Image stabilizer (A O-3)
3.0 solvent (So-1)
5.2 Compound (a) 5 X 10-" mol 1 mol Ag 4th layer (yellow filter layer) Gelatin 4.2 Yellow colloidal silver 1.0 Ultraviolet absorber (UV-
1) 0.5 ultraviolet absorber (UV-2)
1.4 Color mixing prevention agent (AS-1)
0.4 solvent (So-3)
0.8 Third layer (green photosensitive layer) Emulsion A (contains sensitizing dye GD-1) 2.7 Gelatin
13.0 magenta coupler (M
C-1) 2.4 Image stabilizer (AO-1)
2.0 solvent (SO-4')
3.15 Compound (a) 5 x 1o-3 mol 1 mol Ag
2nd layer (color mixing prevention layer) Gelatin 7.5 Color mixing prevention agent (
A s -1) 0.55 solvent (S O-
2') 0.72 1st layer (red-sensitive layer) Emulsion A (contains sensitizing dyes RD-1 and RD-2) 4.0 Gelatin 13.8 Cyan coupler (CC-1) 2.1 Cyan coupler ( C
C-2) 2.1 Image stabilizer (A O-3) 2
．． 2 Solvent (So-1) 3.3 Compound (
a) 5XlO-'' mol 1 mol Ag Coating was carried out using 5A-1 and 5A-2 as coating aids and HA-2 as a hardening agent.

D-1 D-2 D-1 D-1 CC-1 MC- MC-1 Q O- S O-3 O-1 Hs H V-1 V CsH+ +(t) A-1 C,H.

Activ CH*C00CHtCHC4H* A-2 Na03S CHCOOCHz(CFzCFx)zH
CHzCOOCHz(CFzCFx)zH On the other hand, sample N
o, 32, the compound (a) in each layer is replaced with the following compound (
b) , (C) and the general formula (1) of the present invention shown in Table-5
Samples Nos. 33 to 39 were prepared in exactly the same manner except that the fogging agent was changed to the following.

The above compounds (a) to (c) used as comparison fogging agents
are the comparative compounds (,) to (c) used in Example 1 above.
is the same as

Each of the obtained samples was exposed to light using a sensitometer through an optical wedge, and processed through the processing steps shown below.

(Processing-1) Processing process Time Color development 2 minutes bleach fixing 40 seconds stability Drying 20 seconds 3 times 30 seconds <Color developer-1> Diethylenetriaminepentaacetic acid benzyl alcoholdiethylene glycol sulfite sodium bromide sulfuric acidhydroxylamine chloride Sodium 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline potassium carbonate fluorescent whitening M (4,4'-diaminostilbendisulfonic acid derivative) Add water and heat to 33° C 33°C 33°C 60-80°C 2,0g 12,8g 3,4g 2,0g 0,5g 2,6g 3,2g 4,25g 30,0g 10g Q pH
10.5 (pH was adjusted with potassium hydroxide and sulfuric acid.) <Target fixer formulation> Ammonium thiosulfate (54wt%) 1501IQ sodium sulfite 15g ethylenediaminetetraacetate iron (III) ammonium 55g sodium ethylenediaminetetraacetate (dihydrate) Add 4g glacial acetic acid 8.61g water to 112pH
5.4 (pH was adjusted with aqueous ammonia or hydrochloric acid) <Stable liquid> ■-Hydroxyethylidene-1.1 Diphosphonic acid (60%) 1.6t
Q Bismuth chloride 0.35g Polyvinylpyrrolidone 0, 25g
Ammonia water 2.5ml12Nitrilotriacetic acid trisodium 1.0g5-Chloro-2-methyl-4 intiazolin-3-one 50mg2-
Cutyl-4-isothiazolin-3-one 501
．． 1g optical brightener (4,4'-diaminostilbene type)
Add 1.0g water, if, H7.
5 (The pH was adjusted with potassium hydroxide or hydrochloric acid.) (Processing-2) The pH of the color developer was adjusted to 11.0, except for I (well, the same as Processing-1).

The obtained images were subjected to sensitometry at line 1.%, and the magenta images were subjected to maximum density D wax, maximum/J% concentration Table-5. 39) was found to give good positive images with a higher maximum concentration and a lower minimum concentration even in low pH processing compared to samples containing comparative compounds (sample Nos. 32 to 34) which are known capri agents. Ta.

Example 5 Sample No. 4 was prepared in exactly the same manner as in Example 4, except that the compound shown in Table 6 was used as a fogging agent.

40 to 47 were created.

These samples were exposed in the same manner as in Example 4 and processed in Process-■. The minimum density of the obtained magenta image is I) sin
shall be.

On the other hand, a raw sample (a sample before exposure and development) was stored for 3 days at a temperature of 50'O1 and a humidity of 80% RH for forced deterioration, and then exposed and processed in the same manner as described above. Let the minimum density of the magenta image at this time be (D win)'.

Table 6 shows the values of Dsin and (Dwin)'.

As is clear from Table 6, the samples containing the capricant of the present invention (Sample Nos. 43 to 47) were more effective over time than the samples containing the comparative compounds (Samples Nos. 40 to 42), which are known fogging agents. It can be seen that there is little increase in the minimum concentration even after storage, indicating that the raw sample has excellent stability over time.

Also, instead of compound 11 of sample No. 43, 13.3
The effect of the present invention was also observed for each sample using 4.68.

Table [Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material with high contrast, excellent halftone dot quality, little capri, and high sensitivity. Furthermore, by applying the present invention directly to positive silver halide photographic light-sensitive materials, a sufficiently high maximum density can be obtained even when developed with a low pH developer, and the maximum density can be achieved with a relatively short capri development. A good positive image with a large size and a small minimum density was obtained, and an image with a small increase in minimum density even after storage over time could be provided.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer, characterized in that it contains at least one compound represented by the following general formula [I]. Photographic material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. or an alkenylene group, R_3 is a hydrogen atom or an alkyl group, R is a hydrogen atom or a block group, Ar is an arylene group or a heterocyclic group, one of A_1 and A_2 is a hydrogen atom, and the other is a hydrogen atom or an acyl group. , represents a sulfonyl group or an oxalyl group. However, when R represents a hydrogen atom, Ar represents an arylene group, and R_1 represents a hydrogen atom, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, or Ar represents a heterocyclic group. ]