JP2514316B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Purpose of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material that gives a high-contrast image, and more specifically, it occurs in the high-contrast technique using a hydrazine compound. It is related to improvement against failures.

(Prior Art) In recent years, in the field of printed photolithography, colorization and complexity of printed matter have been greatly advanced. Therefore, demands for improving quality and stabilizing quality of the silver halide photographic light-sensitive material for printing, which is an intermediate medium for printing, are increasing year by year. Conventionally, a general silver halide photographic light-sensitive material for printing (hereinafter referred to as a printing light-sensitive material) is so-called "lith development" in order to achieve high quality.
Processability is given. However, in "lith development", it is mechanically impossible to contain a large amount of sulfite ion as a preservative in the developing treatment solution, and it is very difficult for a person skilled in the art to have a very poor stability of the developing solution. It is a well-known fact among others.

Further, as a technique for obtaining a high-contrast image using a hydrazine compound, JP-A-53-16623, JP-A-53-20921, and JP-A-53-20922.
No. 53, No. 53-49429, No. 53-66731, No. 53-66732, No. 53
-77616, 53-84714, 53-137133, 54-37732
No. 54, No. 54-40629, No. 55-52050, No. 55-90940, No. 56
-67843 and the like are disclosed. In the processing method in the image forming method using a series of hydrazine compounds, the pH value of the developer containing the hydrazine compound or the pH value of the developer of the photographic material containing the hydrazine compound is at a relatively high level. Is necessary for obtaining a good image, and therefore there is a drawback that the effective life of the developer is shortened.

On the other hand, in JP-A-56-106244, by incorporating a hydrazine compound and a development-accelerating amount of an amino compound during image formation, a high-contrast image can be formed at a relatively low pH (11
~ 11.5) is disclosed.

A high-contrast image forming method using these hydrazine compounds can obtain a very high-contrast image, but has a serious drawback that significant fog is generated when the fatigue of the developer becomes large. . Furthermore, even when the fatigue of the developer is not so great, black dots such as black sesame (hereinafter referred to as PF (abbreviation of pepper fog) between the halftone dots in the case of a non-exposed area such as a shooting net using a contact screen. Occurrence of a) is observed, which may cause a failure that can be a serious drawback in commercial value. In the above-mentioned JP-A-53-16623 and JP-A-53-20921, benzotriazole, which is a well-known inhibitor for the generation of fog containing PF, is contained in a silver halide photographic emulsion. However, the effect is not sufficient, and the contrast may be impaired, so it is hard to say that this is a completed technology. Further, when the technique disclosed in JP-A-56-106244 is used, when the silver halide grain composition contains 60 mol% or more of silver bromide, the stability of the silver halide photographic light-sensitive material with time is It has the problem of being bad. It goes without saying that this silver halide photographic material having poor stability over time is a serious drawback in use. Therefore,
There is a technical problem to develop a silver halide photographic light-sensitive material which is excellent in stability over time, while suppressing the fog containing PF which is a drawback of the high-contrast technique using a hydrazine compound and not impairing the high-contrast property.

(Object of the Invention) A first object of the present invention is to provide a silver halide photographic light-sensitive material using a hydrazine compound and capable of stably forming a high contrast image. A second object of the present invention is to provide a high-contrast silver halide photographic light-sensitive material containing PF which does not cause fog. A third object is to provide a silver halide photographic light-sensitive material excellent in stability over time.

(2) Structure of the Invention The object of the present invention can be achieved by the following structures of the present invention. It contains 50 mol% or more and less than 80 mol% of silver chloride, and when the silver halide is prepared, a water-soluble rhodium salt is present in an amount of 10 ^-8 to 10 ^-5 mol per mol of the silver halide, and spectrally sensitized with a spectral sensitizing dye. At least one hydrazine compound represented by the following general formula (1), which contains the perceived silver halide.
A silver halide photographic light-sensitive material for a developer, containing an alkanolamine, which has at least one silver halide emulsion layer containing various kinds.

General formula (1) R ₁ NHNHCOR ₂ [In the formula, R ₁ represents an aryl group which may have a substituent, R ₂ represents a hydrogen atom, or a phenyl group which may have a substituent or the number of carbon atoms. It represents an alkyl group of 1 to 3. (Specific Description of Configuration of Invention) Hereinafter, the configuration of the present invention will be specifically described in detail.

The silver halide used in the present invention is silver chloride.
Silver chlorobromide or silver chloroiodobromide is contained in the range of 50 mol% or more and less than 80 mol%. When the content of silver chloride is less than 50 mol%, the stability of the silver halide photographic light-sensitive material over time is poor. On the other hand, when the content is more than 80 mol%, the fog containing PF is significantly generated in the film after the development processing.

The silver halide grain size is not particularly limited, but it is preferable that the average grain size is smaller than 0.5 μm.
It is preferable that 0% or more are so-called monodisperse particles in which the average particle diameter is within ± 40%. The crystal habit of the silver halide grains may be cubic, tetradecahedral, octahedral, etc.,
Further, tablet type particles disclosed in JP-A-58-108525 may be used.

The silver halide grains used in the present invention may be prepared by a single jet method such as a forward mixing method or a back mixing method, or a double jet method by a simultaneous mixing method. More preferred is the simultaneous mixing method. Further, any of the ammonia method, the neutral method, the acidic method and the irregular ammonia method disclosed in JP-B-58-3232 may be used. The acidic method or the neutral method is more preferable.

Examples of the water-soluble rhodium salt used in the present invention include rhodium dioxide, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a halogeno complex compound of trivalent rhodium such as hexachlororhodium (III) acid or a salt thereof. is there.

The addition amount of the water-soluble rhodium salt used in the present invention is preferably in the range of 10 ^-8 to 10 ^-5 mol per mol of silver halide contained in the silver halide emulsion layer of the present invention. If the amount of the water-soluble rhodium salt added is less than 10 ^-8 mol per mol of silver halide, the effect is not sufficiently exerted, and if it exceeds 10 ^-5 mol, desensitizing effect and softening It is effective and cannot be put to practical use.

In the present invention, the water-soluble rhodium salt is present at the time of preparing the silver halide emulsion of the silver halide emulsion layer of the present invention, and the term "preparation" refers to the process of emulsification and physical ripening, and at any time in this process. It may be added by any method. However, the preferable addition time is at the time of emulsification, and the particularly preferable method is a method in which a water-soluble rhodium salt is added to the halide solution. This is because in order to maximize the effect of rhodium, rhodium atoms must be uniformly distributed from the inside to the surface of the silver halide grain, and therefore it is preferable to add them to the halide solution.

In the general formula (1) of the present invention, the aryl group represented by R ₁ is particularly preferably a phenyl nucleus having an electron-withdrawing property derived from Hammett's sigma value of less than +0.30. The Hammett's sigma value can be obtained relatively easily from literature or the like. An unsubstituted phenyl group is considered as one of the preferable groups. Furthermore, as a preferable substituent for the aryl group, a halogen group (for example, fluoro group, chloro group), an alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group). Group, n-octyl group, tert-octyl group, n-decyl group, n-dodecyl group), alkoxy group,
Examples thereof include an acylamino group (eg, acetylamino group, propanoylamino group, benzoylamino group). or,
Particularly preferred are those having ballast groups for photographic additives. The ballast group generally contains 8 or more carbon atoms, and is effective for suppressing the diffusibility in the film layer after coating the emulsion, for example, in the state where the m-tert-pentylphenoxy group is replaced with butylamide or the like. To work.

R ₂ represents a hydrogen atom, a phenyl group which may have a substituent or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is particularly preferred. Particularly preferred examples of the hydrazine compound represented by the general formula (1) of the present invention are listed below.
The present invention is not limited to the following examples.

The compound represented by the general formula (1) can be generally synthesized by a reaction of hydrazines with formic acid or a reaction of hydrazines with an acyl halide.

The compound represented by the general formula (1) is used in the range of 1 × 10 ^-4 mol to 1 × 10 ^-1 mol, and particularly preferably 5 × 10 ^-4 mol to 1 × 10 ² mol per mol of silver halide. Is the range.

In order to add the hydrazine compound represented by the general formula (1) to the emulsion, a usual method for adding the additives in the photographic emulsion can be used. For example, the water-soluble compound can be used as an aqueous solution having an appropriate concentration, and the water-insoluble or sparingly soluble compound can be dissolved in an appropriate organic solvent miscible with water and added to the emulsion as a solution.

The silver halide photographic emulsion of the silver halide emulsion layer of the present invention can be chemically sensitized. The chemical sensitization includes sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof, but preferably, the chemical sensitization is performed by sulfur sensitization alone. As the sulfur sensitizer, in addition to the sulfur compound contained in gelatin, various sulfur compounds, such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used, and these are U.S. Pat.No. 1,574,944. ,same
2,410,689, 2,728,668, and JP-B-59-11892.

The silver halide photographic emulsion of the present invention can impart photosensitivity to a desired photosensitive wavelength range. Here, one or more sensitizing dyes may be used for optical sensitization. As the sensitizing dye, various ones can be used, and as the optical sensitizing dye that can be advantageously used in the present invention, cyanines, carbocyanines, merocyanines, trinuclear or tetranuclear merocyanines, trisensitized dyes can be used. Examples thereof include nuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols and hemioxonols.These optical sensitizing dyes are nitrogen-containing heterocyclic nuclei and are part of their structure. Is preferably a basic group such as thiazoline, thiazole or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, barbituric acid, thiobarbituric acid, pyrazolone, etc., and such a nucleus is alkyl, hydroxyalkylhalogen, phenyl, cyano. , Alkoxy substituted, and these optical sensitizing dyes are charcoal Ring or heterocyclic ring may be fused.

In the silver halide emulsion of the present invention, stabilizers such as tetrazaindenes, antifoggants such as triazoles, tetrazoles, covering power improvers,
It is possible to add, for example, an oxanol dye or a dialkylaminobenzylidene dye as an anti-irradiation agent, a polymer latex as a wetting agent, and other additives used in general photographic emulsions, for example, a spreader or a hardener. Is.

As the support of the silver halide photographic light-sensitive material of the present invention, those generally used such as polyester base, TAC base, baryta paper, laminated paper and glass plate can be used.

As the developer used for developing the silver halide photographic light-sensitive material of the present invention, both a developer and a lith developer which are used for general silver halide photographic light-sensitive materials can be used. As a developing agent for these developing solutions, hydroquinone, chlorohydroquinone, dihydroxybenzenes such as catechol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl- 4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-
Examples thereof include 3-pyrazolidones such as pyrazolidone, and N-methyl-p-aminophenol and N- (4
-Hydroxyphenyl) glycine, para-aminophenols, β-methanesulfonamide ester, ethylaminotoluidine, p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, and ascorbic acid. It is used as an aqueous solution containing one or more such developing agents. In addition, the developer may be used to develop sodium sulfite, potassium sulfite, sodium formaldehyde bisulfite, hydroxylamine, preservatives such as ethylene urea, and inorganic salts such as sodium bromide, potassium bromide and potassium iodide. Inhibitor, 1-phenyl-5
One or more organic inhibitors such as mercaptotetrazole, 5-nitrobenzimidazole, 5-nitrobenztriazole, 5-nitroindazole, 5-methyl-benztriazole, 4-thiazoline-2-thione, sodium hydroxide , An alkaline agent such as potassium hydroxide, diethanolamine, triethanolamine, 3-diethylamino-1-propanol, 2-methylamino-1-ethanol, 3-diethylamino-1,2-propanediol, diisopropylamine, 5-amino- Alkanolamines having a development promoting effect such as 1-pentanol and 6-amino-1-hexanol, a buffer agent having a buffer effect in a developing solution such as sodium carbonate, sodium phosphate, an aqueous solution of carbonic acid and an aqueous solution of phosphoric acid, and sulfuric acid. Sodium, sodium acetate, Salts such as sodium ene acid,
Water softener by chelating effect of ethylenediamine tetrasodium acetate, nitrilo triacetate, hydroxydiamine triacetate, etc., development hardener such as glutaraldehyde, developing agent such as diethylene glycol, dimethylformaldehyde, ethyl alcohol, benzyl alcohol Further, a solvent for an organic inhibitor, a development modifier such as methylimidazoline, methylimidazole, polyethylene glycol, dodecylpyridinium bromide and the like can be added.

The pH of the developing solution is not particularly limited, but a pH range of 9 to 13 is preferable.

An example of the composition of a developer suitable for developing the silver halide photographic light-sensitive material of the present invention is as follows. Hydroquinone as developing agent 20-60g / l and 1-phenyl-4
-Methyl-4-hydroxymethyl-3-pyrazolidone 0.
1-2 g / l or 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.1-2 g / l, sodium sulfite 10-200 g / l or potassium sulfite 10-200 g / l as a developer preservative, of an inorganic salt Sodium bromide or potassium bromide 1-10 as a development inhibitor
g / l, 1-50g of alkanolamines with development acceleration effect
/ l, as an organic inhibitor, for example, 5-methylbenztriazole 0.05-2 g / l or 5-nitroindazole 0.01-
2g / l, sodium carbonate 1-50g / l as buffer agent and phosphoric acid aqueous solution (1mol / l) 10-800ml / l, ethylenediamine tetraacetic acid disodium salt 0.1-10g / l as chelating agent
Add a suitable alkaline agent (eg potassium hydroxide)
Is a developer whose pH is adjusted to 11.0 to 12.5 using.

The silver halide photographic light-sensitive material of the present invention is developed with the above-mentioned developing solution, and then the image is fixed through the processes of fixing, washing with water and drying. At this time, the development temperature and the development time in the development process are not particularly limited, but the development temperature is preferably 20 to 45 ° C. and the development time is preferably 15 to 200 seconds.

(Examples) The present invention will be described in more detail with reference to examples below, but the invention is not limited thereto.

Silver chlorobromide emulsions No. 1 to No. 5 were prepared using solutions A, B and C shown below. The amounts of sodium chloride and potassium bromide used in Solution C are shown in Table 1 together with the composition of the prepared emulsion silver halide grains.

[Solution A]

Ocein gelatin 17 g Polyisopropylene-polyethyleneoxy disuccinate sodium salt 10% ethanol solution 5 ml Distilled water 1280 cc [Solution B] Silver nitrate 170 g Distilled water 410 ml [Solution C] Sodium chloride Table 1 Potassium bromide Table 1 Indicated amount Ocein gelatin 11 g Rhodium trichloride trihydrate Table 1 Indicated amount Polyisopropylene-polyethyleneoxydisuccinate sodium salt 10% ethanol solution 3 ml Distilled water 412 ml Solution B and solution C were added to solution A by the simultaneous mixing method. Insulation temperature and the solution B and solution C at the time of addition to Table 2
The addition time of was shown. At this time, the pAg in the system was controlled at the values shown in Table 2, and the pH was controlled at pH = 3. After the addition of Solution B and Solution C, Ostwald ripening was performed for 10 minutes at the heat-retaining temperature, followed by desalting and rinsing by a conventional method, and then an aqueous solution of ossein gelatin 60
0 ml (containing 30 g of ossein gelatin) was added and dispersed by stirring at 55 ° C. for 30 minutes to obtain emulsions No. 1 to No. 20. Observation by an electron microscope revealed that these emulsions are monodisperse emulsions having an average grain size of 0.22 to 0.27 μm and 90% or more of all grains have an average grain size of ± 0.1 μm.

Next, 15 mg of sodium thiosulfate was added to 1 mol of silver chlorobromide in this emulsion, and chemical ripening was performed at 60 ° C. for 60 minutes. This emulsion was then mixed with 6-methyl-4-hydroxy-1,3,3a, 7
-1 g / Ag x 1 mol of tetrazaindene was added. Anhydro-5,5'-dichloro-9-ethyl-3, a sensitizing dye,
200 mg / Ag × 1 mol of 3′-bis (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt and 250 mg / Ag × 1 mol of polyethylene glycol were added.

Next, 1.0 g / Ag of 1-formyl-2- [4- {2- (2,4-di-t-pentylphenoxy) butylamido} phenyl] hydrazine, which is a hydrazine compound, was added to each sample.
1 mol was added, and Samples No. 21 to No. 23 were the fog inhibitors described in Examples of JP-A-53-16623.
Methylbenzotriazole was added at 0.5 g / Ag × 1 mol. Thereafter, the polyethylene glycol 250 mg / Ag × 1 mole of ethyl acrylate latex polymer 2 g / m ^2, gelatin 2.5g / m ^2, Ag × polyethyleneterephthalate As particles become 3.5 g / m ² of silver amount converted to phthalate-based on The saponin solution was applied as a spreading agent. This emulsion layer contains 1.5 g of gelatin
It was protected by a saponin solution and a dura mater overcoat layer containing mucochloric acid as a hardener so that the amount became / m ² .

The sample thus obtained was exposed to white light for 1 second under an optical wedge with a KS-1 type sensitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.), and then developed with a developer shown in Table 3 below at 38 ° C. for 30 seconds. ,
After that, fixing, washing with water and drying were performed, and the characteristics shown in Table 4 were measured.

Table 3 Composition of developer (Developer 1) Hydroquinone 34 g 1-Phenyl-4,4-dimethyl-3-pyrazolidone 0.23 g Ethylenediaminetetraacetic acid disodium salt 1 g 3-Diethylamino-1,2-propanediol 15 g 5-Methylbenzotriazole 0.4 g Na ₂ SO ₃ 76 g NaBr 3 g NaCl 1.3 g 1 mol / l phosphoric acid solution 400 ml Add NaOH necessary to make pH 11.5, and make water 1.

 The results are shown in Table 4.

* 1 Sensitivity at a concentration of 2.5 and relative sensitivity with Sample 5 as 100.

* 2 Shown with ◎, ○, △ and × from the highest linear gamma of density 0.3 to 3.0 on the photographic characteristic curve. Generally, the level of ○ is indispensable as a printing material.

* 3 The black sesame-like black dots (that is, PF) generated between the halftone dots when shooting with a contact screen gray negative No. 2 manufactured by Dainippon Screen Mfg. Co., Ltd.
The occurrence situation was observed using a 10-fold loupe. ◎, ○, △.
The occurrence is worse in the order of △ ×, ×, ××, ×××. ◎ is desired in terms of quality, but below x is a level that cannot be put to practical use at all.

* 4 25 samples were used as a substitute test for storability of samples.
After adjusting the humidity to ℃ and 50% RH, seal it in a photographic barrier packaging and seal it at 50 ℃
And heat treated for 30 days. Then, it was exposed and developed. The method of evaluating the sensitivity and the PF generation rate is as described above.

* 5 Fog is the fog density at 38 ° C for 30 seconds.

From Table 4, in a silver halide photographic light-sensitive material having a silver halide emulsion layer containing a hydrazine compound, the silver chloride content of the silver halide emulsion and the water-soluble rhodium salt present at the time of preparation of the silver halide emulsion are It can be seen that when the amount is within the range of the present invention, the three factors of hardness, PF generation and stability over time (in sensitivity and PF generation) are both excellent.

(3) Effects of the Invention The silver halide photographic light-sensitive material according to the present invention is capable of stably forming a high-contrast image, and is excellent in fog generation including PF and stability over time.

Claims (1)

(57) [Claims] 1. A silver halide containing 50 mol% or more and less than 80 mol% and a water-soluble rhodium salt is present in an amount of 10 ^-8 to 10 ^-5 mol per 1 mol of silver halide when the silver halide is prepared, and the spectral increase is obtained. An alkanolamine containing at least one silver halide emulsion layer containing silver halide spectrally sensitized with a dye and containing at least one hydrazine compound represented by the following general formula (1). A silver halide photographic light-sensitive material for a developer, which contains a class. General formula (1) R ₁ NHNHCOR ₂ [In the formula, R ₁ represents an aryl group which may have a substituent,
R ₂ represents a hydrogen atom, or a phenyl group which may have a substituent or an alkyl group having 1 to 3 carbon atoms. ]