JPH063761A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the repression of a latent image and to improve sensitivity by incorporating a specified compd. into a silver halide emulsion layer and other hydrophilic colloid layers. CONSTITUTION:A compd. expressed by formula is incorporated into the silver halide emulsion layer and other hydrophilic colloid layers (preferably into adjacent layers) of the photosensitive material. In formula, R1-R4 denote respectively hydrogen atom, alkyl, alkenyl, aryl, hydroxy, mercapto, phosphono, amino, nitro, cyano, halogen atom, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl, or alkoxy groups. R1 and R2 may be connected with each other to form a ring structure. However, at least one of R1-R4 is an alkyl group or allyl group having a heteroring as a substituent. This compd. is easily synthesized by a well-known method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which latent image regression is prevented.

[0002]

2. Description of the Related Art In order to obtain an image by silver halide photography, there are two processes, a photographic exposure process for producing a latent image and a development processing process for converting the produced latent image into a silver image or a dye image. It is well known that two processes are required (eg Mess and James,
The Theory of the Photogr
apic Process). The formation of a latent image by photographic exposure is chemically a very slight change in silver halide crystals, and the latent image itself (see above) has an inherently unstable property. Therefore, the latent image is likely to be attenuated with the lapse of time from photographing exposure to development processing (the attenuation of the latent image is called latent image regression), which usually causes a disadvantage of lowering photographic sensitivity. The progress of latent image regression generally depends on the storage conditions of the exposed light-sensitive material. For example, it is recognized that the regression is remarkable in the high temperature storage and is small in the low temperature storage.

The simplest method of avoiding latent image regression is to carry out development immediately after photographing exposure, and the next simplest method is to cool the photographed light-sensitive material and store it at a low temperature until the development after photographing exposure. Is the way to do it. Although these methods are the easiest solutions from a chemical point of view, it is hard to say that they are preferable solutions considering the convenience of the user. In terms of actual conditions of use and usage, negative materials for photography and reversal materials are often left at room temperature for several months from exposure to development, and even positive materials for copying take several months. It may be left for a while.

[0004]

For the above reasons, it is desirable to make a special device during the production of a silver halide photographic light-sensitive material to obtain a light-sensitive material in which latent image regression is prevented.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a compound represented by the following general formula (I) is
It has been newly found that when it is contained in a silver halide emulsion layer and / or other hydrophilic colloid layer (preferably adjacent layers), it has an excellent latent image regression preventing ability. General formula (I)

[0006]

[Chemical 2]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atom, alkyl group, alkenyl group, aryl group, hydroxy group, mercapto group, phosphono group, amino group, nitro group, cyano group, halogen Represents an atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkoxy group, and R ₁ ,
R ₂ may combine to form a ring structure, provided that R ₁ and R
_At least one of ₂ , R ₃ and R ₄ represents an alkyl group having a heterocycle as a substituent or an allyl group. )

The general formula (I) will be described in detail. In the formula, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, an alkyl group,
It represents an alkenyl group, aryl group, hydroxy group, mercapto group, phosphono group, amino group, nitro group, cyano group, halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group or alkoxy group. However, at least one of R ₁ , R ₂ , R ₃ , and R ₄ represents an alkyl group having a heterocycle as a substituent or an allyl group. Alkyl group, aryl group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group,
The alkoxy group may further have a substituent, and as the substituent, the groups mentioned for R ₁ and R ₂ can be similarly mentioned. Further, R ₁ and R ₂ may be connected to each other to form a ring structure.

Preferred examples of R ₁ and R ₂ include a hydrogen atom, an alkyl group and an alkenyl group which may have a substituent having 1 to 12 carbon atoms, or a substituent which has 6 to 12 carbon atoms. Mention may be made of good aryl groups. R ₁ , R
_A preferable example is that the sum of carbon numbers of ₂ is 1 to 20. More preferred examples of R ₁ and R ₂ include R ₁
As a hydrogen atom, an allyl group, or an amino group (dimethylamino group, diethylamino group, etc.) or a heterocycle (morpholino group, N-methylpiperazinyl group, pyrrolidinyl group, piperidinyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, Pyridazinyl group, indolyl group, etc.) can be mentioned as an alkyl group having R ₂
Examples thereof include an alkyl group and an alkenyl group which may have a substituent having 1 to 5 carbon atoms, and an aryl group which may have a substituent having 6 to 12 carbon atoms. Specific examples of R ₁ include a hydrogen atom, an allyl group, a dimethylaminomethyl group, a morpholinomethyl group, an N-methylpiperazinylmethyl group and a pyrrolidinylmethyl group. Examples of R ₂ include a methyl group, an ethyl group, an allyl group, a phenyl group and a p-methoxyphenyl group.

Preferred examples of R ₃ and R ₄ include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent, and an alkenyl group. Specific examples thereof include a hydrogen atom, a methyl group, an allyl group, a morpholinomethyl group, an N-methylpiperazinylmethyl group and a pyrrolidinylmethyl group. As the alkyl group having a heterocycle as a substituent, an N-methyl-piperazinylmethyl group and an N-hydroxy-piperazinylmethyl group are particularly preferable. Specific examples of the compound represented by the general formula (I) include the following compounds, but are not limited thereto.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

The above compound can be easily synthesized by a well-known method. The reference documents below are listed below. Comprehensive
Heterocyclic Chemistry,
Volume 3, pages 40-56, pages 106-142, 1
79-191. The Journal of Am
erican Chemical Society,
Volume 67, 2197-2200 (194
5). The amount of the compound represented by the general formula (I) of the present invention to be added may be appropriately selected depending on the silver halide photographic emulsion to be used, so long as the effect of preventing latent image regression is exhibited. 10 ^{−5 to} 5 × per mol of silver halide
10 ⁻² mol is preferable, and 10 ⁻⁴ to 10 ⁻² mol is particularly preferable. In the present invention, the compound represented by formula (I) is contained in any one or more silver halide emulsions and / or hydrophilic colloid layers in the silver halide photographic light-sensitive material. That is, a silver halide emulsion layer or a hydrophilic colloid layer other than that (for example, a protective layer, an intermediate layer,
Filter layer) and the like by a known method. For example, it is dissolved in an aqueous solution or a suitable organic solvent miscible with water (for example, alcohols, ethers, glycols, ketones, esters, amides, etc. that do not adversely affect photographic properties) As an emulsion or in a hydrophilic colloid. It is also possible to use the well-known methods of adding water-insoluble couplers to emulsions in the form of dispersions. The addition timing is not particularly limited, and it may be added at any time from after physical ripening to immediately before coating, but it is most preferable to add just before coating.

Further, the compounds of the present invention represented by the general formula (I) have the excellent properties of preventing latent image regression and enhancing photographic sensitivity as apparent from the examples. . When used as a sensitizer, the same amount as described above can be used. The silver halide in the silver halide light-sensitive material used in the present invention is composed of silver chloride, silver chlorobromide, silver bromide, silver iodobromide or silver iodochlorobromide. The average particle size is not particularly limited. The silver halide emulsion of the present invention comprises P.
Chimie et Physiq by Glafkides
ue Photographique (Paul Mo
ntel, 1967), G.N. F. Photographic Emulsion Che by Duffin
mistry (published by The Focal Press, 1
966), V.I. L. Zelikman et al. Making and Coating Photog
radical Emulsion (The Focal
It can be prepared using the method described in Press, 1964, etc. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. .

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. Two or more kinds of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together. Further, as the silver halide solvent, ammonia, rhodan potassium or a thioether compound can be used. Silver halide grains are regular (reg, such as cubic, octahedral and tetradecahedral).
It may have an (ulular) crystallite, or a spherical shape,
It may have an irregular crystal form such as a plate shape, or may have a composite form of these crystal forms. It may consist of a mixture of particles of various crystal forms. The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase. As the binder or protective colloid for the silver halide emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl, imidazole and polyvinylpyrazole can be used. The silver halide emulsion of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; for example of oxazoline thione Thioketo compounds such as; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-
Methyl (1,3,3a, 7) tetrazaindenes) Pentaazaindenes, etc .; Many known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Can be added. For example, US Pat.
No. 4,474, No. 3,982,947, No. 4,02
Reference can be made to the description in the specification of No. 1,248 or Japanese Patent Publication No. 52-28660.

As the silver halide emulsion, a so-called unheated (primitive) emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized. For chemical sensitization, the above-mentioned Glafkides or Zelikm
An et al. or H. Frieser ed Die G
rundlagen der Photographi
schen Promise mit Silver
hellogeniden, (Akademische
The method described in Verlagesellschaft, 1968) can be used. That is, thiosulfates, thioureas, thiazoles, sulfur sensitization using active gelatin or compounds such as rhodanines, primary tin salts, amines, hydrazines, formamidinesulfinic acid,
It can be used alone or in combination with a reduction sensitization method using a silane compound or the like, a gold complex salt, a noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as platinum, iridium and palladium.

Further, the compound of the present invention can be used in combination with the above-mentioned known chemical sensitizer during the chemical ripening. In the silver halide emulsion of the present invention, in addition, a gelatin hardening agent, a surfactant, a spectral sensitizing dye, a development accelerator,
Any of the so-called photographic additives commonly used in the art, such as polymer latex, dye, color coupler, anti-fading agent, etc., can be used. For the preparation of these additives and silver halide emulsions, see Research Di
Reference may be made to the description of sclosure 176, 22-31 (December 1978). The present invention can be applied to negative and positive black and color photographic light-sensitive materials. The silver halide photographic light-sensitive material of the present invention has at least a layer selected from a surface protective layer, an intermediate layer, a filter layer, an undercoat layer, a packing layer, an image receiving layer and the like on the support, in addition to the silver halide emulsion layer. It has one layer.

As the support, a cellulose acetate film, a polyethylene terephthalate film, a polyolefin-coated paper or the like can be used. The composition of layers other than the silver halide emulsion layer of the present invention (for example, a binder,
(Gelatin hardening agent, surfactant, antistatic agent, ultraviolet absorber, mordant, polymer latex, slip agent, plasticizer, matting agent, adhesion improving agent, dye, etc.), silver halide emulsion layer and other layers The coating and drying methods, and the exposure and development methods of the silver halide light-sensitive material are not particularly limited, and include, for example, Research Disclosure described above.
Reference can be made to the description of Re 176, pages 22 to 31 (December 1978).

[0021]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Example-1 A gelatin emulsion of silver iodobromide containing 2.5 mol% of silver iodide was prepared. Then, sodium thiosulfate, sodium chloroaurate, and potassium thiocyanate were added, and the mixture was aged at 58 ° C. for 70 minutes to perform gold-sulfur sensitization. Next, the compound of the present invention and the compound for comparison were added to this emulsion as shown in Table 1 below, and further 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (stabilizer ),
Dodecylbenzene sodium sulfonate (application aid)
And 2,4-dichloro-6-hydroxy-s-triazine (hardener) were added, coated on a triacetyl cellulose film and dried to obtain Samples 1 to 9. Expose these samples through an optical wedge using a sensitometer,
It was developed with Kodak D-72 developer at 20 ° C. for 4 minutes, and fixed and washed with water by a usual method. When developed immediately after exposure, after exposure, at 35 ° C., relative humidity (RH) 7
Table 1 shows a comparison with the case where the film was stored after being stored in a 5% atmosphere for one week.

[0022]

[Table 1]

The photographic sensitivity is expressed by the reciprocal of the logarithm of the exposure amount required to obtain an optical density of fog + 0.2. In Table 1, the sensitivity of Sample 1 developed immediately after exposure is 100 and the other is relative. I expressed it. From the results in Table 1, it is possible to know the degree of sensitization and latent image regression in Samples 4 to 9 using the compound of the present invention by comparison with the samples using the control and comparative compounds. It is clear from Table 1 that addition of the compound of the present invention well prevents latent image regression.

Example 2 A gold-sulfur sensitized silver iodobromide emulsion having a monodisperse double structure sensitized with sodium thiosulfate, chloroauric acid and potassium thiocyanate (iodination: 6 mol%, average grain size: 0. Eight pieces of 6μ and a core-shell ratio of 1: 1) were prepared. The compounds shown in Table 2 were added to each, and yellow couplers (* 1 and *
2 used 1: 1), coupler dispersant (tricresyl phosphate), stabilizer (4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene), coating aid (sodium dodecylbenzene sulfonate), hardener (2,4-
Dichloro-6-hydroxy-s-triazine Na salt) was added and coated on a triacetylcellulose film support by a coextrusion method together with a gelatin protective layer and dried to prepare Sample 11.
~ 18 were obtained. These samples were exposed through an optical wedge using a sensitometer and subjected to the color development processing described below. When developed immediately after exposure and after exposure at 40 ° C. and 75% R.C.
H. Table 2 shows the results of the case where the film was developed after being stored in the atmosphere of 4 days. The relative sensitivity was set to 100 when the sample 11 was developed immediately after exposure as in Example 1.

[0025]

[Table 2]

As is apparent from Table 2, the addition of the compound of the present invention well prevents the regression of the latent image. * 1 Yellow coupler

[0027]

[Chemical 6]

* 2 Yellow coupler

[0029]

[Chemical 7]

(Color development processing) Color development 2 minutes 45 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The processing liquid composition used in each step is as follows. It was on the street.

[0031]

[0032]

[0033]

[0034]

Example-3 A sample similar to the sample A of Example 1 described in JP-A-4-142536 was prepared. In the third layer emulsion of Sample A, the compound No. of the present invention was added. 13 and No. 14 and No. Samples 22, 23, and 24 were prepared by adding 19 to each of 3.5 × 10 ⁻⁴ mol / mol Ag. For comparison, the sample without addition was used as Sample 21, and the comparative compound (A) was 3.5 × 1.
Sample 25 was prepared by adding 0 ⁻⁴ mol / mol Ag. The above light-sensitive material was exposed to blue, red, and green through an optical wedge, and immediately after the exposure and after storage at room temperature for 2 days, JP-A-4-1-1.
The same treatment as in Example 1 of 42536 was performed. The results are shown in Table 3. The sensitivity was expressed as a relative sensitivity with 100 being the value of the sample 21 processed immediately after exposure as in Example 1.

[0036]

[Table 3]

As can be seen from Table 3, the compounds of the present invention prevent latent image regression well. Example-4 In Example-3, the first emulsion added to the third layer emulsion of Sample A was used.
As a result of performing the same processing as in Example-3 except that the compound was added to the layer emulsion, the latent image regression was prevented by the addition of the compound of the present invention as in Example-3.

[0038]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material in which latent image regression is prevented and sensitivity is increased.

Claims (1)

[Claims] 1. A compound having at least one silver halide emulsion layer on a support, and in the silver halide emulsion layer and / or other hydrophilic colloid layer, a compound represented by the following formula (I): A silver halide photographic light-sensitive material containing at least one kind. General formula (I) (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atom, alkyl group, alkenyl group, aryl group, hydroxy group, mercapto group, phosphono group, amino group, nitro group, cyano group,
Halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group,
It represents an alkoxy group, and R ₁ and R ₂ may combine to form a ring structure, provided that at least one of R ₁ , R ₂ , R ₃ and R ₄ has a hetero ring as a substituent. Represents an alkyl group or an allyl group. )