JPH0416938A - Picture forming method - Google Patents

Abstract

PURPOSE:To obtain the photographic characteristics of extremely high contrast negative gradation with gamma value exceeding 10 by developing a silver halide photographic sensitive material in the presence of a specific compd. CONSTITUTION:The silver halide photographic sensitive material is developed in the presence of the compd. expressed by formula I. In the formula Ar1, Ar2 denote a bivalent arom. group; R1 to R4 denote a hydrogen atom, alkyl group, aryl group or heterocyclic group. R1 and R2, R3 and R4 may combine to form a cyclic structure. L denotes a bivalent combination group; n denotes 0 or 1. The photographic characteristics of the extremely high contrast negative gradation with the gamma value exceeding 10 are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) 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.

(B) Prior Art Adding a hydrazine compound to a silver halide photographic emulsion or developer is described in US Pat. No. 730゜727 (developer containing a combination of ascorbic acid and hydrazine)
, No. 3,227,552 (using hydrazine as an auxiliary developer to directly obtain a positive color image), No. 3,386,831 (using aliphatic carbon as a stabilizer for silver halide sensitive materials) 2,419.975, and Mee
The Theuy of Photog ``ap
hic ProcessJ 3rd edition (1966) 281
It is known for pages etc.

Among these, especially U.S. Patent Box 2. 419. 975
No. 1, it is disclosed that high-contrast negative images 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, a strong alkaline developer having a pH close to 13 is easily oxidized in the air, is unstable, and cannot withstand long-term storage or use. The ultra-high contrast photographic characteristics with a gamma value exceeding 10 are useful for photographic reproduction of continuous-tone images using halftone images (+]ot images), which are useful for printing plate making, or reproduction of line drawings, whether negative or positive images. extremely 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 A method of developing with a hydroquinone developer (mol/1 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 contents, 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. 243. No. 739,
4,269.929, 4. 272゜614,
No. 4,323.643 and other publications disclose silver halide photographic materials that use a stable developer to provide extremely high-contrast negative photographic properties, but there are several acylhydrazine compounds used in these materials. It has been found that it has some drawbacks.

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. Further, if development is continued using these hydrazines, numerous circular fogs (sand fog; pepper log) are likely to occur in unexposed areas, which significantly impairs 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 Box 4
, 272.606 and 4,241.164)], but when these sensitization techniques are used in combination,
Generally, sensitization and enhancement blur 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 during automatic processing, and if the development processing is strengthened to eliminate this phenomenon, the above-mentioned sand fogging phenomenon occurs, which is a drawback.

Therefore, there has been a desire for a compound that is effective when added in a very small amount, without the problems of stability over time, uneven development, or sand fog as mentioned above, and that is easy to synthesize.

(C) Object of the Invention The first object of the present invention is to provide a silver halide photographic light-sensitive material that can obtain photographic properties with extremely high negative gradations exceeding comma or 10 using a stable developer. It is to provide.

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 decagenide 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. An object of the present invention is to provide photographic materials.

The fourth purpose of the present invention is to improve processing stability (e.g. development unevenness,
/) To provide a method for developing a silver halide photographic light-sensitive material in high contrast by adding a hydrazine to a developing processing solution, which can quickly give photographic properties such as no sand fog, etc., and high contrast. That's true.

(D) Structure 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 (I).

(Margin below) General formula [l] (L),.

[In the formula, Ar, , Ar2 represent a divalent aromatic group, and R1, R2, R3, R4 are a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group.

Further, R1 and R2, and R3 and R4 may be connected to each other to form a cyclic structure.

L represents a divalent linking group, and n represents 0 or 1. ] In the general formula [I], the divalent aromatic group represented by ArI and Ar2 is specifically a phenylene group or a naphthylene group which may have a substituent, and the substituent Examples of groups include alkyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, alkenyl groups, amino groups, acylamino groups, sulfonamide groups, hydroxyl groups, alkylidene amino groups, thiourea groups, thioamide groups, hetero Examples include a ring group, a combination thereof, and the like.

In the general formula [I], the alkyl group among the groups represented by R1, R2, R3, and R4 is preferably an alkyl group having 30 or less carbon atoms, such as a halogen atom, a hydroxyl group, a cyano group, or a carboxyl group. It may have a substituent such as a group, an alkoxy group, an aryloxy group, a sulfo group, an allyl group, or a substituted amino group.

In the general formula [■], among the groups represented by R1, R2, R3 and R4, the aryl group is a phenyl group or a naphthyl group which may have a substituent.

Examples of preferred substituents include an alkyl group, an aryl group, a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkenyl group, an amino group, an acylamino group, a sulfonamide group, an alkylidene amino group, a heterocyclic group, or
Examples include combinations of these.

In the general formula [IF, among the groups represented by R1, R2, R3, and R4, the heterocyclic group represents a monocyclic or bicyclic heterocyclic ring, even if the ring has a substituent. good.

In the general formula (I), L represents a divalent linking group, and specifically represents a linking group shown in the following general formula (IF), (m) or (IV).

General formula (II) R5R6 -N-(-L, -)N General formula (III) 0+L, ÷0 General formula (IV) C-+L, 10 General formula (II), (I[) and (IV) In, the divalent linking group represented by Ll means an atom or atomic group containing at least one of C, N, and 5SOO, specifically,
For example, alkylene group, alkenylene group, alkynylene group, arylene group, -08--NH--N= -CO-
-802 (these groups may have a substituent),
etc. alone or in combination.

In general formula (II), R5 and R6 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R5 and R8 may be connected to each other to form a cyclic structure.

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

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

(The following is a blank space) The compound of general formula (I) of the present invention can be easily synthesized by a method known to those skilled in the art, as shown in the following synthesis example.

Hereinafter, the method for synthesizing the compound of the present invention will be explained by giving specific examples.

(Left below) Synthesis Example 1 Synthesis of Exemplary Compound (7) (Synthesis Scheme) (B) 22.5 g of P-nitrophenylhydrazine and 75 ml of diethyl oxalate are mixed and heated on a water bath for 7 hours. After cooling, the precipitated crystals are collected by filtration and washed several times with ethanol to obtain compound (A).

Yield: 30.1g Melting point 178-179℃ Compound (
Dissolve 7.7 g of B) in 500 ml of dioxane, add 14.3 g of compound (A), and heat on a water bath for 2.5 hours. After cooling, the precipitated crystals are collected by filtration and washed with ethanol to obtain compound (C).

Yield: 15.6g Melting point 152°C (decomposition) 15.5g of compound (C) was dissolved in 10100O of methanol,
Catalytic reduction was performed over a Pd-C catalyst to obtain compound (D).

Yield, 9.3g Melting point 163°C (decomposition) Compound (D
) in 1500 ml of dioxane, 3.7 g of triethylamine was added, and while stirring at room temperature, 5.8 g of phenyl chlorocarbonate was dissolved in 100 ml of dioxane.
Add the solution dissolved in the solution dropwise. After stirring for 30 minutes, the precipitated triethylamine hydrochloride was filtered off, the solvent was distilled off under reduced pressure, ethanol was added, and the precipitate was collected by filtration. The crystals are washed with ethanol to obtain compound (E).

Yield: 10.5 g Melting point: 214° C. (decomposition) 5.3 g of compound (E) and 1.2 g of compound (F) are refluxed in 100 ml of dioxane for 3 hours. Filter the precipitated crystals,
Exemplary compound (7) was obtained by washing with ethanol.

Yield: 4.5 g Melting point: 213°C (decomposition) - 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 be contained in a hydrophilic colloid layer adjacent to a surface latent image type silver halide emulsion layer.

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

The content of the compound of the present 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 can vary over a wide range; A range of about 1.times.10@-6 to 1.times.10@-2 moles per mole of silver in the type silver halide emulsion is practically useful.

When the hydrazine compound represented by the general formula (I) used in the present invention is mixed into the developer, 10-4
~10-1 mol/I! is suitable, more preferably 5
A range of X10-' to 5X10-2/l 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 morphology, crystal habit, size distribution, etc. of the silver halide grains, but grain sizes 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, salts of noble metals such as rhodium and iridium, and iron compounds such as red blood salts may be present during physical ripening or nucleation of silver halide grains.

In particular, the addition of a rhodium salt or a complex salt thereof 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 emulsion used in the present invention may be spectrally sensitized with methine dyes or others.

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 supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

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, carboxydimethyl cellulose, and cellulose sulfate; sugar derivatives such as sodium alginate and starch derivatives. , polyvinyl alcohol, partial acetal of polyhinyl 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, polyvinylimitazole, and the like.

As gelatin, in addition to lime-treated ceratin, 1. Acid-treated gelatin or Butt 1. Soc, Sci, Pho
t, Japan, NCL 16, P2O (1966
) Enzyme-treated gelatin as described in ) may also be used,
Furthermore, gelatin hydrolysates and enzymatically decomposed products can 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 for stabilizing photographic performance.

That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chloropenzimitazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles,
Mercaptotetrazoles, mercaptopyrimidines,
Many compounds conventionally known as antifoggants or stabilizers can be added, such as mercaptotriazines, thioketo compounds; asaindenes;

Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazole) and nitroindazoles (eg, 5-nitroindazole).

These compounds may be included in the treatment liquid.

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

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-5-) riazine), 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 polyhydric alcohols, alkyl esters of sugars, etc. acidic surfactants, alkyl carboxylates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, etc., such as carboxyl groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing diamino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, amphoteric surfactants, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternaries such as pyridinium, imidazolium, etc. Cationic surfactants such as ammonium salts can also be used.

In the photographic light-sensitive material used in the present invention, for the purpose of improving dimensional stability, the photographic emulsion layer and other hydrophilic colloid layers are added.
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,
Polymers containing combinations of α,β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. as monomer components can be used.

In order to obtain ultra-high contrast photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use conventional Lith developer or U.S. Pat.
It is not necessary to use a highly alkaline developer with a pH close to 13 as described in No. 9.975, and a stable developer can be used.

That is, in the silver halide photographic light-sensitive material of the present invention, a developer containing a sufficient amount of sulfite ions as a preservative (particularly 0.15 mol/I or more) can be used, and the developer has a pH of 9.
By using a developing solution with a molecular weight of 5 or more, particularly 10.5 to 12.3, a sufficiently ultra-high contrast negative image can be obtained.

There is no particular restriction on the developing agent that can be used in the method of the present invention, and examples include 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.

(Unexamined Japanese Patent Publication No. 57-129436, No. 57-129433
No. 57-129434, No. 57-129435, U.S. Pat. No. 4,323,643, etc.).

The processing temperature is usually selected between 18°C and 50°C,
The temperature may be lower than 18°C or higher than 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 0.2 containing 97% AgBr and 3% AgI
A silver iodobromide emulsion consisting of 5μ cubic crystals was prepared by the tuple jet method, washed with water and redissolved by a conventional method, and then
Chemical sensitization was performed using sodium thiosulfate.

After dividing this silver iodobromide emulsion into 13 parts, compounds (2), (3), (7), (13) of the general formula (I) of the present invention were prepared.
After adding Comparative Compounds (A) and (B) in the amounts shown in Table 1, the amount of silver was 3,
It was applied so that it weighed 7g.

After applying wedge exposure to the film sample prepared in this way, it was heated at 20°C using a developer having the composition shown below.
Developing was carried out for 1 to 5 minutes.

<Developer> Hydroquinone 30g 4-hydroxymethyl-4-methyl 1-phenyl-3-pyrazolidone 0.3g Sodium sulfite 75g EDTA・2Na
1.0g tripotassium phosphate
80g potassium bromide 2.0gN
13 g of aOH 0.3 g of 5-methylbenztriazole 17 g of 1-diethylamino-2,3 dihydroxypropane Add water and pip with 11 potassium hydroxide
Adjust to H11.5.

Comparative compound (A) Comparative compound (B) \. )l, Cll,. 1 The results are shown in Table 1.

As is clear from Table 1, the compound of the present invention is different from the comparative compound (
In A) and (B), it can be seen that the high-contrast photographic characteristics are the same even after processing for 1 minute at 20°C, and there is no increase in fog even after long-term development. .

Furthermore, the sensitivity change due to the change in development time was higher than that of the comparative compound (A).
, (B), which indicates that the stability against development is high.

In addition, looking at the unexposed areas of each sample after development, it was found that the samples to which comparative compounds (A) and (B) were added (Nα2~
In 5), obvious sand fog already occurred after 3 minutes of development time, whereas no sand fog was observed in the samples to which the compound of the present invention was added (Nα6 to 13).

(Margin below) <Example 2> Next, a part of the film sample obtained in Example 1 was heated at 40°C for 30 days, and then exposed and developed (
20° C. for 3 minutes) and compared with the sensitivity and fog values immediately after coating.

The results are shown in Table H.

<Table (hereinafter referred to as blank space) As is clear from Table (2), it can be seen that the compounds of the present invention exhibit extremely little change in sensitivity and increase in fog over time of storage.

<Example 3> Next, using another part of the film sample obtained in Example 1, a halftone dot quality test was conducted.

That is, using a 150 line gray contact screen,
After exposing each film sample to light via a sensimetry coarse exposure wedge, it was incubated at 38°C with the same developer as before.
Developed for 2 seconds and checked the dot quality.

The results are shown in Table ■.

The halftone dot quality is visually evaluated on a five-level scale, with 5 representing the best quality and 1 representing the worst quality. As a halftone original plate for plate making, 5.4 is practically usable, 3 is poor but barely usable, and 2.1 is of a quality that is practically unusable.

<Table ■> (Hereafter, blank) As is clear from Table ■, it can be seen that the compounds of the present invention exhibit good halftone dot quality.

Claims (1)

[Scope of Claims] 1) An image forming method characterized by developing a silver halide photographic light-sensitive material in the presence of a compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Ar and Ar_2 represent divalent aromatic groups, and R
_1, R_2, , R_3, and R_4 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, R_1 and R_2, R_3 and R_4 may be connected to each other to form a cyclic structure. L represents a divalent linking group, and n represents 0 or 1. ]