JPS62275247A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain the photographic characteristics of a very high contrasty and a negative gradation having >10 of gamma value by processing the silver halide photographic sensitive material in the presence of a specific compd. CONSTITUTION:The silver halide photographic sensitive material is processed in the presence of the compd. shown by formula I. In formula I, Ar is aryl group, and concretely, phenyl group or naphthyl group which may be substd. The substituent is exemplified by alkyl group, aryl group, halogen atom or a combination thereof. The nitrogen contg. heterocyclic ring residue shown by R is concretely exemplified by pyridyl, pyrazinyl, primidyl group, etc., which may be substd. or the combination thereof. The concrete example of the compd. shown by formula I is those shown by formula I-1.

Description

Detailed Description of the Invention (8) Industrial Application Field The present invention relates to a method for developing a silver halide photographic light-sensitive material, and in particular provides an extremely high-contrast negative image, a highly sensitive negative image, and a good halftone image quality. It relates to photographic materials.

(8) Prior Art The addition of hydrazine compounds to silver halide photographic emulsions and developing solutions is described in US Pat. No. 3,730,727 (developing solution combining ascorbic acid and hydrazine);
3,227,552 (Using hydrazine as an auxiliary developer to obtain a direct positive color image), 3
, 386,831 (contains β-monophenyl hydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials), 2.419,975, and l-1e.
Written by eS [The rheory of Photography]
phic Processj 3rd edition (1966) 28
It is known for pages such as 1 page.

Among these, US Pat. No. 2,419,975 in particular discloses that a high-contrast negative image can be obtained by adding a hydrazine compound.

That is, a hydrazine compound is added to a silver chlorobromide emulsion, and 12
．． It is stated that when developed with a developer having a high pH of 8, extremely high-contrast photographic characteristics with a gamma (γ) of over 10 can be obtained.

However, strong alkaline developers with a DH close to 13 are easily oxidized in the air, are unstable, and cannot withstand long-term storage or use. The ultra-high contrast photographic characteristics with a gamma value exceeding 10 are extremely useful for photographic reproduction of continuous-tone images using dot images (dot images) useful in printing plate making, and reproduction of line drawings, whether negative or positive images. Useful.

Conventionally, for this purpose, a silver chlorobromide emulsion with a silver chloride content exceeding 50 mol%, preferably 75 mol% is used, and the effective concentration of sulfite ions is kept extremely low (usually 0.1 mol%). A method of developing with a hydroquinone developer (mol/i or less) was commonly used (lith development).

However, in this method, due to the low sulfite ion content in the developer, the developer is extremely unstable and cannot be stored for more than 3 days.

Furthermore, since all of these methods require the use of silver chlorobromide emulsions with relatively high silver chloride content, high sensitivity cannot be obtained.

Therefore, there has been a strong demand for using a highly sensitive emulsion and a stable developer to obtain ultra-high contrast photographic characteristics useful for reproducing halftone images and line drawings.

To this end, U.S. Pat.
No. 269.929, No. 4,272,614, No. 4,
No. 323, No. 643, etc., disclose silver halide photographic materials that use a stable developer to provide extremely high-contrast negative photographic properties, but the acylhydrazine compounds used in these materials have several drawbacks. It has been found that there is.

That is, these hydrazines are known to generate nitrogen gas during the development process, and this gas may collect in the film to form bubbles, which may damage photographic images.

Therefore, there has been a desire for a compound which can reduce the generation of bubbles and at the same time reduce the cost of producing a sensitive material, and which can provide extremely sharp photographic characteristics even when added in a small amount. Also, if development is continued using these hydrazines, countless circular fogs (sand fogs) will appear in the unexposed areas.
pepper fog> was likely to occur, significantly impairing image quality.

In addition, conventional hydrazines are required in large amounts for sensitization and high contrast, and when particularly high sensitivity is required in terms of the performance of the photosensitive material, other sensitization techniques [e.g. chemical Increasing sensitization: increasing particle size; US Patent No. 4
However, when these sensitization techniques are used in combination,
Generally, sensitization and enhancement blurring may occur over time during storage.

Furthermore, when development is performed using conventional hydrazines,
So-called uneven development is likely to occur due to uneven stirring of the developer. This development unevenness is noticeable in automatic processor processing, and if the development processing is strengthened to eliminate this phenomenon, the above-mentioned sand fog phenomenon occurs, which is a drawback.

Therefore, there has been a desire for a compound that does not have the problems of stability over time, uneven development, or sand fog as described above, is effective when added in a very small amount, and is easy to synthesize.

(C) Purpose of the Invention The purpose of the present invention is, firstly, to develop a gamma film using a stable developer.
It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of obtaining photographic characteristics of extremely high contrast negative gradation with a value exceeding 10.

A second object of the present invention is to provide a negative-working silver halide photographic material containing hydrazines that can provide good image quality without problems with uneven development or sand fog.

A third object of the present invention is to provide a negative-working silver halide photograph containing hydrazines that can provide the desired photographic characteristics of extremely high contrast negative gradation with a small amount of addition without adversely affecting photographic performance. The purpose of the present invention is to provide photosensitive materials.

A fourth object of the present invention is to improve the processing stability (e.g., no development unevenness, sand fog, etc.) by adding hydrazines, which can provide photographic properties such as rapid sharp contrast, to the processing solution. An object of the present invention is to provide a method for developing a silver oxide photographic material with high contrast.

(D>Construction of the Invention The various aspects of the present invention were achieved by developing a silver halide photographic material in the presence of a compound represented by the following general formula (1).

General formula (1) %Formula% [In the formula, Ar represents an aryl group, and R represents a nitrogen-containing heterocyclic residue.

R1 and R2 are hydrogen atoms or +C+-Ro (wherein, Ro
represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group, and n represents an integer of 1 or 2. ). ) In the general formula (I>), the aryl group represented by Ar is specifically a phenyl group or a naphthyl group that may have a substituent, and examples of the substituent include alkyl group, aryl group, halogen atom, alkoxy group, aryloxy group, alkenyl group, substituted amino group, acylamino group, sulfonamide group,
Examples include an alkylidene amino group, a thiourea group, a thioamide group, a petro IMM, or a combination thereof.

In the general formula (I>), the nitrogen-containing heterocyclic residue represented by R is specifically a pyridyl group which may have a substituent, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a quinolyl group, An isoquinol group, a phthalazinyl group 1, a naphthyridinyl group, a quinoxalinyl group, a quinazonilyl group, a cinnolinyl group, or a pteridinyl group, and examples of substituents include an alkyl group, an aryl group, a halogen atom, a substituted amino group, a cyano group, Examples include an acylamino group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a combination thereof.

Ar or R in the general formula (I>) may incorporate a ballast group commonly used in immobile photographic additives such as couplers.

The ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, and the like.

In the general formula (1), among the groups represented by Ro, the alkyl group and alkenyl group preferably have 30 or less carbon atoms, and necessarily include a halogen atom, a cyan group, an alkoxy group, and an aryl group. It may have a substituent such as an oxy group, an aryl group, or a substituted amine group.

In the general formula (1), among the groups represented by Ro, the aryl group is a phenyl group or a naphthyl group which may have a substituent, and examples of the substituent include an alkyl group,
Examples include an aryl group, a halogen atom, an alkoxy group, an aryloxy group, or a combination thereof.

Among the groups represented by Ro in general formula (I), the alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

In the general formula (1), among the groups represented by Ro, the aryloxy group is preferably a monocyclic group, and is a halogen atom, an alkyl group, etc. It may be replaced.

Specific examples of the compound represented by general formula (1) are shown below.

However, the present invention is not limited to the following compounds.

(Margin below) 3゜ 4゜ 6゜ 8゜ 10° 11° 14° 15° mouth 17° 21° 22゜ 23° 25° 26° 27° 28° 29° 30° The compounds of the present invention can be synthesized by various methods.

For example, the corresponding hydrazine compound (Ar-NHNHz
) and a nitrogen-containing heterocyclic carboxylic acid with dicyclohexylcarbodiimide in an appropriate solvent such as acetonitrile or dioxane, or instead of the nitrogen-containing heterocyclic carboxylic acid, a nitrogen-containing heterocyclic carboxylic acid ester is reacted with toluene, benzene, ethanol, etc. It can be easily obtained by reacting in an appropriate solvent.

Alternatively, a method in which a diazonium salt and α-pyridoin are reacted in acetone-water can be used.

The method for synthesizing the compound of the present invention will be explained below using specific examples.

Synthesis Example 1 Synthesis of Exemplified Compound 1: 2.14 g (0.01 mol) of α-pyridoin was mixed with 85 rdl of acetone and 10 ml of water, and 2.2 g of 4-methylbenzenediazonium sulfate was added to the mixture while stirring at room temperature. (0
A solution prepared by dissolving .

The mixture was then neutralized with an aqueous M/2-sodium hydrogen carbonate solution and treated with activated carbon. The filtrate was concentrated under reduced pressure on a water bath, cooled with water, and crystallized by filtration. This crystal is purified by column chromatography to obtain the desired crystal 1.
I got a 9. The melting point was 152.5-'153.0'c.

Synthesis Example 2> Synthesis of Exemplified Compound 7: P-1-lylhydrazine hydrochloride 1.58g (0,01
mol) and 2.19 g of nicotinic acid phenyl ester (0,
01X1.1 mol) and triethylamine 1.06'j
(0.01xl, 05 mol) was mixed with toluene',=Oml, heated under reflux for 10 hours, water was added, extracted with ethyl acetate, washed with water, and dried over sodium sulfate. The extract was distilled off under reduced pressure on a water bath, and the residue was purified by column chromatography to obtain 1.36 g of the desired crystals. Melting point is 124
．． The temperature ranged from 5 to 125.5°C.

Synthesis Example 3> Synthesis of Exemplified Compound 22: p-methoxyphenylhydrazine hydrochloride 0.87 g (0
,005 mol) and quinoline-2-carboxylic acid 0°87y
(0,005 mol) and triethylamine 0.513 (0
,005 mol) was mixed with 20 ml of acetonitrile, and while stirring at room temperature, 1 mol of dicyclohexylcarbodiimide was mixed with 20 ml of acetonitrile.
．． A solution of 039 (0,005 mol) in 15 d of acetonitrile was added over about 3 minutes.

After stirring at the same temperature for 4 hours, the precipitate was filtered off, the filtrate was distilled off under reduced pressure on a water bath, and the residue was purified by column chromatography to obtain 0.74 q of the desired crystals. Melting point is 154.0~
It was 155.0'C.

Synthesis Example 4> Synthesis of Exemplified Compound 27: 1.14 V (0,005 mol) of 1-(P-tolyl)-2-(3,-pyridinecarboxy)hydrazide and 0.51 g (0,005 mol) of triethylamine. ) was dissolved in 20 ml of dioxane, and while stirring while cooling with ice water, a solution of 0.54 g (0,005 mol) of hechloroethyl carbonate dissolved in 10 ml of dioxane was added over about 5 minutes, and then at the same temperature for 30 minutes. After stirring, the mixture was further stirred at room temperature for 4 hours. After that, the plate product was filtered off, the filtrate was dried under reduced pressure on a water bath, and the residue was purified with column chroma 1 to obtain target product 1J.

'H-NMR (CDCj 3/TMS): δ=1°2
6(t, 3H1-CHz CH3) :2.35 (
S, 3 to 1, - 〇up λ-): 4.26 (Q,
2 To1, - C top'IzCH3) Near, 15
7.38 (m, 51-(arom) :8.2 (
m, 1 Harom>: 8.78 (brs
, 1 Harom.

1H1-Ndan):9.10(s,'J l-1-1ar
o.

In the light-sensitive material of the present invention, the compound represented by general formula (1) is preferably contained in the surface latent image type silver halide emulsion layer. It may also be included in the colloid layer.

Such layers include a subbing layer, an intermediate layer, a filter layer, a protective layer,
The layer may have any function, such as an antihalation layer, as long as it does not prevent the compound represented by formula (1) from diffusing into the silver halide grains.

The content of the compound of the invention in the layer varies depending on the properties of the silver halide emulsion used, the chemical structure of the compound and the development conditions, so that the appropriate content may vary over a wide range, but the surface latent image A range of about 1.times.10@-8 to 1.times.10@-2 moles per mole of silver in the type silver halide emulsion is practically useful.

When mixed in the developer with the hydrazine compound represented by the general formula (1) used in the present invention,
10-1 mol/di is suitable, more preferably 5X1
0″~5X10-”/’! A range of is particularly preferred.

The silver halide used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide, etc. can be used. However, when silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is preferably in the range of 5 mol % or less.

There are no particular limitations on the form, crystal habit, size, etc. of the silver halide grains, but grains with a diameter of 0.7 microns or less are preferred.

Silver halide emulsions are made of gold compounds such as chlorauric acid salts and gold trichloride, salts of noble metals such as rhodium and iridium, sulfur compounds that react with silver salts to form silver sulfide, stannous salts, etc. Sensitivity can be increased by using reducing substances such as amines without making the particles coarser.

Further, iron compounds such as salts of noble metals such as rhodium and iridium, and blush salts may be present during physical ripening or nucleation of silver halide grains.

In particular, the addition of rhodium salts or complex salts is preferable because it further promotes the effect of the present invention of achieving ultra-high contrast photographic characteristics in a short development time.

In the present invention, a surface latent image type silver halide emulsion refers to an emulsion comprising silver halide grains having surface sensitivity higher than internal sensitivity, and this emulsion is preferably described in US Pat. No. 4,224,
It has a difference between surface sensitivity and internal sensitivity as specified in the specification of No. 401.

It is desirable that the silver halide emulsion be monodisperse, particularly an emulsion having the monodispersity defined in the above-mentioned US Pat. No. 4,224,401.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes,
and hemioxonol dyes.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a pigment belonging to complex merocyanine pigments.

These sensitizing dyes may be used alone or in combination.

Combinations of sensitizing dyes are often used, especially for the purpose of hypersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a photosensitizing effect or a substance that does not substantially absorb visible light and exhibits strong sensitization.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, 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, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. - As gelatin, in addition to lime-treated gelatin, acid-treated gelatin and [3ul 1. Soc, Sci, Phot, Ja
Enzyme-treated gelatin as described in Pan N (116, P2O (1966)) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or stabilizing the photographic performance.

That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles. : Mercaptopyrimidines, mercaptotriazines, thioketo compounds; Azaindenes: Many compounds conventionally known as antifoggants or stabilizers can be added.

Among these, particularly preferred are benzotriazoles (e.g., 5-methylbenzotriazoles) and nitroindazoles (e.g., 5-nitroindazole).
It is.

These compounds may be included in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.

For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-
Methylol compounds, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-6-hydroxy-s-
triazine, etc.), etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be contained for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, non-ionic materials such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenylsuccinic acid polyglycerides, etc.), fatty acid esters of polyalcohols, alkyl esters of sugars, etc. surfactants: alkyl carboxylates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, etc., containing carboxy groups, sulfo groups, phospho groups, sulfur ester groups, phosphate ester groups, Anionic surfactants containing acidic groups; amphoteric surfactants such as amino Ml, aminoalkyl sulfonic acids, aminoalkyl sulfur 1 or phosphoric acid esters; aliphatic or aromatic quaternary@ammonium salts, pyridinium, imidazolium, etc. Cationic surfactants such as heterocyclic quaternary ammonium salts can be used.

In the photographic light-sensitive material used in the present invention, in the photographic emulsion layer and other hydrophilic colloid layers, for the purpose of improving dimensional stability, etc.
It may contain a decomposed product of a water-insoluble or poorly soluble synthetic polymer.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α
, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and the like can be used.

In order to obtain super (i2r tone) photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use the conventional Lith developer or the U.S. Pat.
, 419,975, it is not necessary to use a highly alkaline developer with a pH close to 13, and a stable developer can be used. Sufficient amount of sulfite ion as (especially 0.15 mol/f1
(above)) can be used, and the pH
Negative images with sufficient ultra-high contrast can be obtained by using a developing solution of 9.5 or higher, particularly 10.5 to 12.3.

There are no particular limitations on the developing agents used in the method of the present invention, including dihydroxybenzenes, 3-pyrazolidones,
Amine phenols and the like can be used alone or in combination.

The developer also contains alkali metal sulfites, carbonates,
pH buffering agents such as borates and phosphates; development inhibitors and antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles); can be included.

In addition, if necessary, water softeners, solubilizing agents, toning agents, development accelerators, surfactants, antifoaming agents, hardeners, and film silver stain preventive agents (for example, 2-mercaptobenzimidazole sulfonic acids) It may also include.

Specific examples of these additives are described in Research Disclosure No. 176, No. 17643, and the like.

As the fixer, one having a commonly used composition can be used.

As a fixing agent, in addition to thiosulfate and thiocyanate,
Organic sulfur compounds known to be effective as fixing agents can be used.

Further, the fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

In the present invention, a method may be adopted in which a developing agent is incorporated into the photosensitive material and the material is processed with an alkaline activator solution.

(JP 57-129436@, JP 57-129433
No. 57-'I29434, No. 57-129435
(see, e.g., U.S. Pat. No. 4,323,643).

The treatment temperature is usually chosen between 18°C and 50'C, but it may also be lower than 18°C or above 50'C.

It is preferable to use an automatic processor for photographic processing.

In the present invention, even if the total processing time from when the photosensitive material is placed in an automatic processor to when it comes out is set to 60 seconds to 120 seconds, sufficient photographic characteristics with ultra-high contrast and negative gradation can be obtained.

(E) Example <Example 1> Average particle size 0.97% AC]Br, 3% AgI.
A silver iodobromide emulsion consisting of 25 μm cubic crystals was prepared by a double jet method, washed with water and redissolved in a conventional manner, and then subjected to chemical sensitization and color sensitization using sodium thiosulfate.

This silver iodobromide emulsion was coated onto a polyester film at an amount of 1 m/m and 3.79 m/m of silver.

After wet exposure was applied to the film sample prepared in this way, 1f! of the exemplary compound of the present invention or the comparative compound was added to a developer having the composition shown below. 1 mmol was added per sample, and development was performed at 20'C for 1 to 5 minutes.

Developer solution> Hydroquinone 30 74-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.39 Sodium sulfite 75 gEDTA-2
Na 1.09 Tripotassium phosphate 809 Potassium bromide
2.0gNaOH13!7 5-methylbenztriazole 0.3L31-
Diethylamine-2,3-dihydroxypropane 179 Add water and ρF with 1ρ potassium hydroxide
Tune in to 111.5.

Comparative compound (A> the law of nature Comparative compound (B) Comparative compound (C) The results are shown in Table 1.

(The following is a blank space) As is clear from Table 1, the compounds of the present invention have photographic properties with high contrast, and no increase in fog occurs even after long-term development.

<Example 2> Next, the silver iodobromide emulsion obtained in Example 1 was divided into 9 parts, and then compound 12.18.22 of general formula (I) of the present invention was divided into 9 parts.
and comparative compound (D) in the amounts shown in Table 2,
3.7 silver per 1'rrt on polyester film
It was applied so that it became g.

After applying wet exposure to the film sample prepared in this way, using a developer having the composition shown in Example 1,
Development was performed at 20'C for 1 to 5 minutes.

Comparative compound (D> The results are shown in Table 2.

As is clear from Table 2, the compound of the present invention had high contrast photographic properties even after 20'C1 minute development.

It can be seen that even if the process is completed and the phenomenon is carried out for a long time, there is no increase in fog or it is very small.

Furthermore, when looking at the unexposed areas of each sample after development, no sand fog was observed in the new compound of the present invention.

Claims (1)

[Claims] (1) A silver halide photographic light-sensitive material is expressed by the following general formula (I):
An image forming method characterized by developing in the presence of a compound represented by: General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Ar represents an aryl group, and R represents a nitrogen-containing heterocyclic residue. R_1 and R_2 are hydrogen atoms or ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_0 represents an alkyl group, alkenyl group, aryl group, alkoxy group, or aryloxy group, and n represents an integer of 1 or 2. ). ]