JPS6147944A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably form a high-contrast image with a photosensitive material by incorporating a specified amt. of silver chloride, a specified amt. of rhodium salt, and a hydrazine compd. in an emulsion layer. CONSTITUTION:The emulsion layer contains silver halide contg. 50-80mol% silver chloride, the water-soluble rhodium salt, such as rhodium trichloride, in an amt. of 10<-8>-10<-5>mol per mol of silver halide, and the hydrazine compd. represented by formula I, R1 being aryl, and R2 being H, phenyl, or alkyl; such as 1-formyl-2-[4-{2-(2,4-di-t-benzylphenoxy)butyramide}phenyl]hydrazine. The photosensitive material having the emulsion layer contg. said silver halide, said rhodium salt, and this hydrazine compd. can form a high-contrast image small in fog, and improved in stability.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the invention (industrial application field) The present invention relates to a silver halide photographic material that provides high-contrast images, and more specifically, a high-contrast technology ( This is related to improvements to malfunctions that occur in equipment.

(Prior Art) In recent years, in the field of printing photolithography, printed matter has become increasingly colored and complex. For this reason, demands for improved and stable quality of silver halide photographic materials for printing, which are intermediate media for printing, are increasing year by year. Conventionally, general 110 silver-genide photographic light-sensitive materials for printing (hereinafter referred to as printing light-sensitive materials) have been given so-called 1-lith development processing suitability in order to achieve high quality. developing"
It is well known to those skilled in the art that it is mechanically impossible to contain a large amount of sulfite ion, which is a preservative, in the developing solution for lζ, and that the stability of the developing solution is extremely poor. It is a fact that

In addition, as a technique for obtaining high-contrast images using a hydrazine compound,
No. 21, No. 53-20922, No. 53-49429, No. 53-66731, No. 53-66732, No. 5
No. 3-77616, No. 53-84714, No. 53-1
No. 37133, No. 54-37732, No. 54-406
No. 29, No. 55-52050, No. 55-90940, No. 56-67843, etc. are disclosed. In the processing methods in these series of image forming methods using hydrazine compounds, the pH value of the developer containing the hydrazine compound or the pH value of the developer for processing photographic materials containing the hydrazine compound is at a relatively high level. In order to obtain a good image, it is necessary to have the following conditions, and this has five disadvantages: it reduces the useful life of the developer.

On the other hand, in JP-A-56-106244, a high-contrast image is formed at a relatively low pH (it~11.5) by containing a hydrazine compound and a development-promoting amount of an amine compound during image formation. A technology that can be used has been disclosed.

High-contrast image forming methods using these hydrazine compounds can produce very high-contrast images, but
This method has a serious disadvantage in that when the degree of fatigue of the developer increases, significant capri occurs. Furthermore, even when the degree of fatigue of the developer is not so great, black dots like black sesame seeds (hereinafter referred to as PF 5 (abbreviation for Peraper Fog)) may appear between the halftone dots in unexposed areas, for example, when shooting with a contact screen. ), which can cause malfunctions that can be a serious drawback in terms of product value.In the above-mentioned JP-A-53-16623 and JP-A-53-20921, the occurrence of fog including PF was observed. This is suppressed by incorporating Bensito IJ azole, a widely known inhibitor, into the /X silver halide photographic emulsion, but the effect is not sufficient and, moreover, the contrast may be impaired. It is hard to say that it is a perfected technology. Furthermore, when the technique disclosed in JP-A No. 56-106244 is used, /) the composition of the silver halide grains contains 60 mol% or more of silver bromide, the stability of the silver halide photographic light-sensitive material over time; There are five problems with poor performance. Needless to say, this silver halide photographic material having poor stability over time is a serious drawback in use. Therefore, there is a technical challenge to develop a silver halide photographic light-sensitive material that has excellent stability over time without impairing high contrast while suppressing the fog containing PF, which is a drawback of high contrast technology using hydrazine compounds. .

(Object of the Invention) The first object of the present invention is to provide a silver halide photographic material that can stably form a high-contrast image using a hydrazine compound. A second object of the present invention is to provide a high-contrast silver halide photographic material 'f containing PF and free from capri occurrence. The third object is to provide a silver halide photographic material with excellent stability over time.

(2) Structure of the Invention The object of the present invention can be achieved by the following structure of the present invention. containing 50 mol% or more and less than 80 mol% of silver chloride, and having 10-8 to 10-' mol of water-soluble rhodium salt present per 1 mol of silver halide during the preparation of silver halide;
A silver halide photographic photosensitive material comprising at least one silver halide emulsion layer containing at least one hydrazine compound represented by the following general formula (1).

General formula (1) %Formula% [In the formula, R1 represents an aryl group that may have a substituent, and 2 represents a hydrogen atom, or a phenyl group that may have a substituent or a carbon number of 1- 3 represents an alkyl group. ] (Specific explanation of the structure of the invention) Hereinafter, the structure Iζ of the present invention will be specifically explained in detail.

The silver halide used in the present invention is silver chloride.
It is silver chlorobromide or silver chloroiodobromide contained in a range of 0 mol % or more and less than 80 mol %. Silver chloride content is 50 mol%
If the amount is less, the stability of the silver halide photographic material over time will be poor. On the other hand, if the amount is more than 80 mol %, the occurrence of PF-containing fog on the film after development is significant.

The silver halide grain size is not particularly limited, but it is preferable that the average grain size is smaller than 0.5 μm, and 90% or more of the total grains fall within ±40% of the average grain size, so-called. Monodisperse particles are preferred.

The crystal habit of silver halide grains may be cubic, tetradecahedral, octahedral, etc.
Tapunt a particles disclosed in No. 525 may also be used.

The silver halide grains in the present invention may be prepared by a single jet method such as a forward mixing method or a back mixing method, or by a simultaneous mixing method; b.a double jet method. More preferred is a simultaneous mixing method. Further, any method such as an ammonia method, a neutral method, an acid method, or an irregular ammonia method disclosed in Japanese Patent Publication No. 58-3232 may be used. More preferred is an acidic method or a neutral method.

The water-soluble rhodium salt used in the present invention includes:
Examples include rhodium dioxide, rhodium trichloride, ammonium hexachlororhodate, etc., but preferred is a halogeno complex compound of trivalent rhodium, such as hexachlororhodic acid (III) acid or a salt thereof.

The amount of the water-soluble rhodium salt used in the present invention is preferably in the range of 10@-8 to tcr' mole per mole of silver halide contained in the silver halide emulsion layer of the present invention. The amount of water-soluble rhodium salt added is 10-1 per mole of silver halide.
When the amount is less than 8 moles, the effect is not sufficiently exhibited, and when it exceeds 10@-5 moles, a desensitizing effect and a softening effect are exhibited, making it impossible to put it to practical use.

In the present invention, the water-soluble rhodium salt is present at the time of IJ of the silver halide emulsion of the silver halide emulsion layer of the invention, but the time of preparation is not the process of emulsification and physical ripening.
It may be added at any time in step 1 (ii) by any method.However, the preferred time for addition is during emulsification.
More particularly preferred is a method in which a water-soluble rhodium salt is added to a halide solution. This is because, in order to maximize the effect of rhodium, rhodium atoms must be uniformly distributed from the interior to the surface of silver halide grains, and for this reason, it is preferable to add rhodium atoms to the halide solution.

The aryl group represented by R1 in general formula (11) of the present invention is preferably a 5-phenyl nucleus whose electron-withdrawing property derived from Hammett's sigma value is smaller than +0.30. Hammett's sigma The value can be determined relatively easily from literature, etc. An unsubstituted phenyl group is considered as one of the preferable groups. Furthermore, as a preferable substituent for 1ζ or an aryl group.

hao/7′ group (e.g. fluoro group, chloro2TT),
-alkyl group (e.g. methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group,
n-hexyl M, n-octyl group, tert-octyl group, n-decyl group, n-dodecyl group), alkoxy group, acylamino group (e.g. acetylamino group, propanoylamino group, benzoylamino group) is obtained by 2μ .

Particularly preferred are those having a ballast group for photographic additives.

Ballast groups generally contain 8 or more carbon atoms,
For example, when the m-tert-pentylphenoxy group is substituted with butylamide or the like, it effectively works to suppress the diffusivity in the film layer after coating the emulsion.

R2 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 general formula (1) of the present invention
) Examples of the hydrazine compounds shown in ) are listed below, but the present invention is not limited to the following examples.

+1)-3 C3H1l-t J The compound represented by the general formula (1) can generally be synthesized by a reaction between hydrazines and formic acid, or a reaction between hydrazines and an acyl halide.

The compound represented by the general formula (1) is used in an amount of IX10-' mol to 1X10-' mol per mol of silver halide, particularly preferably 5X10-' mol to 1X10-' mol.
It is in the molar range.

In order to add the hydrazine compound represented by the general formula (1) into the emulsion, an exaggerated method of adding additives in a photographic emulsion can be used. For example, a water-soluble compound is made into an aqueous solution with an excessive concentration, and is water-insoluble or ai+￥! The compound F can be used by dissolving it in a suitable organic solvent that is miscible with water and adding it 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. Chemical sensitization includes sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof, and preferably chemical sensitization is performed using sulfur sensitization alone. As the sulfur sensitizer, in addition to the sulfur compounds found in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used, and these are described in U.S. Pat. ,574,944
The silver halide photographic emulsions of the present invention described in Japanese Patent Publication No. 2,410,689, λ72 Kame No. 668, and Japanese Patent Publication No. 59-11892 each impart photosensitivity in a desired photosensitive wavelength range. can do.

Here, optical sensitization may be performed using one or more types of sensitizing dyes. Various sensitizing dyes can be used, but optical sensitizing dyes advantageously used in the present invention include cyanines, carbocyanines, merocyanines, trinuclear or sclerotia. Examples include merocyanines, trinuclear or sclerotial cyanines, styryls, holopolar cyanines, hemicyanines, oxonols and hemioxonols. Part of the structure contains basic groups such as thiazoline and thiazole, or rhodanine, thiohydantoin, oxazolidinedione, barbituric acid,
Those containing a nucleus such as thiobarbylic acid or pyrazolone are preferable, and such a nucleus can be substituted with alkyl, hydroxyalkylhalogen, phenyl, cyano, or alkoxy, and these optical sensitizing dyes can be substituted with a carbocyclic or heterocyclic ring. May be condensed.

The silver halide emulsion of the present invention includes stabilizers such as tetrazaindenes, antifouling agents such as triazoles and tetrazoles, covering power improvers, and irradiation inhibitors such as oxanol dyes.
It is possible to add dialkylaminobenzylidene dyes, polymer latexes as wetting agents, and other additives used in general photographic emulsions, such as spreading agents and hardening agents.

As the support for the silver halide photographic material of the present invention, commonly used supports such as polyester base, TAC base, baryta paper, laminated paper, glass plate, etc. are used.

As the developer used for developing the silver halide photographic material of the present invention, either a developer used for general silver halide photographic materials or a lithium developer can be used. The developing agents of these developers include dihydroquinobenzenes such as hydroquinone, chlorohydroquinone, and catechol, 1-phenyl-3-pyrazolidone,
1-phenyl-4,4-dimethyl-3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3
3-pyrazolidones such as -pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and also N-methyl-p-aminophenol, N-(4-hydroxyphenyl) Examples include para-aminophenols such as glycine, β-notanesulfonamide ester, ethylaminotoluidine, p-phenylenediamines such as N,N-diethyl-p-7 22-diamine, and ascorbic wLs. It is used as an aqueous solution containing one or more such developing agents.

In addition, the developer may contain preservatives such as sodium sulfite, potassium heliumite, formaldehyde sodium bisulfite, hydroxylamine, ethylene urea, and inorganic salts such as sodium bromide, potassium bromide, potassium iodide, etc. development inhibitor, 1-phenyl-5-mercaptotetrazole,
1a1 or higher organic inhibitors such as 5-nitropentzimidazole, 5-nitropenttriazole, 5-nitrointasole, 5-methyl-benztriazole, 4-thiazoline-2-thione, etc., sodium hydroxide, potassium hydroxide alkaline agents such as jetanolamine, triethanolamine, 3-diethylamino-1-propanol, 2-methylamino-1-ethanol, 3-diethylamino-1,2-propanediol, diinpropylamine, 5-amino- 1-pentanol, 6-amino-1-
Alkanolamines that have a development accelerating effect such as hexanol and -ol, buffering agents that have a buffering effect in developing solutions such as sodium carbonate, sodium phosphate, aqueous carbonate solution, and aqueous phosphoric acid solution, sodium sulfate, sodium acetate, and sodium citrate. salts such as, sodium ethylenediaminetetraacetate, sodium nitrotriacetate, water softeners with chelating effects such as sodium hydroxydiaminetriacetate, developer hardeners such as glutaraldehyde, diethylene glycol, dimethylformaldehyde, ethyl alcohol, benzyl. Solvents for developing agents and organic inhibitors such as alcohol, methylimidacillin, methylimidazole,
A development v4 stabilizer such as polyethylene glycol, dodecylpyridinium bromide, etc. can be added.

There are no particular restrictions on the pH of the developer, but a range of pH 9 to 13 is ideal.

An example of the composition of a preferred developer for developing the silver halide photographic material of the present invention is as follows. Hydroquinone 20-607/l and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.1-21/l or 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.1/l as developing agents. 1~2jl/! 1. Sodium sulfite 10-200/1 or potassium sulfite 10-2001/1 as a developer preservative. bromide as a development inhibitor for inorganic salts) IJium and potassium bromide 1-101
/ / l, alkanolamines with development accelerating effect 1-50! 1//, as an organic inhibitor e.g. 5-
Methylbenztriazole 0.05-21/it or 5-nitroindazole 0.01-21//l, buffering agent such as sodium carbonate 1-50 f//l or phosphoric acid aqueous solution (1 mol/l) 10-800 me
/l, adding ethylenediamine 4 vinegar 5!2 sodium salt 0.1-10, p/J as a chelating agent.

p using a suitable alkaline agent (e.g. potassium hydroxide)
This is a developer with H adjusted to 11.0 to 115.

The silver halide photographic light-sensitive material of the invention is developed with the above-mentioned developer, and then undergoes the processes of fixing, washing with water, and drying to fix the image. At this time, there are no particular restrictions on the development temperature and development time in the development process, but the development temperature is preferably in the range of 20 to 45°C and the development time is in the range of 15 seconds to 200 seconds.

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

Silver chlorobromide emulsions /161 to /I65 were prepared using the following solutions A, B, and C. The amounts of sodium chloride and potassium bromide used in solution C are shown in Table 1 together with the silver halide grain composition of the prepared emulsion.

[Solution A]

Ossein gelatin 17.9 Polyisopropylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution
5- Distilled water
1280cc [Solution B] Silver nitrate 1701 Distilled water 410d [Solution C] Chloride) IJum Table 1 Amounts listed Potassium Bromide Table 1 Amounts listed Ossein Gelatin III Trichloride Oxium trihydrate Table 1 Amounts listed Polyisopropylene-polyethylene Oxydisuccinic acid ester sodium salt 10%
Ethanol-soluble M, 31rLI! Table 1 Umbrella hc13.3H2060μI is reduced to 1 mole of silver halide 128 x 1 (r' mole).

Solution [3] and solution C were added to solution A by a simultaneous mixing method. Table 2 shows the insulating temperature at the time of addition, solution B and solution C.
The addition time is 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 in all cases. After the addition of solution n and solution C, Ostwald ripening was performed for 10 minutes at the insulated temperature, followed by desalting and washing with water in a conventional manner, and then 600 ml of an aqueous solution of ossein gelatin (containing 3M ossein gelatin) was added. The mixture was dispersed by stirring at 55° C. for 30 minutes to obtain emulsions 161 to 20.

Observation using an electron microscope revealed that these emulsions were monodisperse emulsions with an average grain size of 0.22 to 0.27 μm, and more than 90% of all grains had an average grain size of ±0.1 μm.Table 2 Emulsion pg Conditions during production: Next, 15 μm of sodium thiosulfate was added per mole of silver chlorobromide to this emulsion, and chemical ripening was performed at 60° for 0.60 minutes. Next, this emulsion was added to 6-methyl-4-hydroxy-1,
3,3a,7-chitrazaindene was added in an amount of IJ'/Ag x 1 mol. Anhydro-5゜51-dichloro-9-ethyl-3,31-bis(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt 1 as a sensitizing dye
k 200 R9/kg x 1 mole, and polyethylene glycol was added at 250 IP/Ag x 1 mole.

Next, the hydrazine compound 1-formyl-
z-(4-(z-(z,4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine at 1.01/
1 mol of AgX was added, and for samples No. 21-/1623, 5-methylbenzotriazole Y0, which is a capri inhibitor described in Example 1ζ of JP-A-53-16623, was added.
．． 5.9/Ag x 1 mol was added. after that.

Polyethylene glycol 2501117/Ag
1 mole, ethyl acrylate latex polymer 2 i
/ m'.

Gelatin 2-5. ji'/77, AgX grains were coated with saponin solution as a spreading agent on a polyethylene terephthalate base so that the silver content was 3.51/d.This emulsion layer was coated with saponin solution to give a gelatin content of 1.5&/rrX. It was protected by a hardening overcoat layer to which mucochloric acid was added as solution and hardening agent.

The thus obtained sample '& was exposed to white light for 1 second under a light wedge using an 8-1 sensitometer (manufactured by Konishi Roku Photo Industries), developed with a developer for 30 seconds at 38°C, and then The fixing, washing and drying procedures shown in Table 3 were carried out, and the properties shown in Table 4 were measured.

Table 3 Composition of developer (Developer 1j) Hydroquinone 34, fl
-phenyl-4,4-dimethyl-3-pyrazolidone
0.23 & ethylenediaminetetraacetic acid disodium salt g 3-diethylamino-1,2-propanediol

151!5-Methylbenzotriazole 0.4
gNaz803761 NaBr
31NaC61,31 1 mol/l phosphoric acid solution 400 pH 11
, 51 rubbing Iζ water removal with necessary NaOH 11!
shall be.

Table 4 *1 Sensitivity at concentration 25, expressed as relative sensitivity with Sample 5 as 100.

*2 On the photographic characteristic curve, ◎, 0. Indicated by Δ and X.

Normally, the O level is essential for printing photosensitive materials. *3 Black sesame-like black dots ( That is, PF) is 1
The occurrence was observed using a 0x magnifying glass. 0,0. Mu,
Δx, ×.

The occurrence worsens in the order of xx and xxx. A value of O is desirable in terms of quality, but a value of X or less is at a level that cannot be put to practical use at all.

*4 As a substitute test for the storage stability of the sample over time, the sample was
After adjusting the humidity to 5° C. and 50% RH, it was sealed in a photographic barrier packaging material and heat-treated at 50° C. for 30 days.

After that, it was exposed and developed. The methods for evaluating sensitivity and PF occurrence are as described above.

*5 Fog is expressed as capri density when developed at 38°C for 30 seconds.

From Table 4, it can be seen that in the silver halide photographic material having a /S silver halide emulsion layer containing a hydrazine compound,
When the silver chloride content of the silver halide emulsion and the amount of water-soluble rhodium salt present during the preparation of the silver halide emulsion are within the range of the present invention, high contrast, PF generation, and stability over time (sensitivity) (3) Effects of the Invention The silver halide photographic light-sensitive material according to the present invention can stably form high-contrast images, and does not cause fogging including PF. , and excellent stability over time.

Claims (1)

[Scope of Claims] Contains 50 mol% or more and less than 80 mol% of silver chloride, and contains 10^-^8 to 10^-^5 mol of water-soluble rhodium salt per mol of silver halide during preparation of silver halide. make it exist,
A silver halide photographic material comprising at least one silver halide emulsion layer containing at least one hydrazine compound represented by the following general formula (1). General formula (1) R_1NHNHCOR_2 [In the formula, R_1 represents an aryl group that may have a substituent, and R_2 is a hydrogen atom, or a phenyl group or an alkyl group having 1 to 3 carbon atoms, each of which may have a substituent. represents a group. ]