JPH06130580A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain photographic performance having no problem in long storage stability, superior in running stability, and high in contrast as high as a gamma of >=10 in negative gradation by developing the silver halide photosensitive material in the presence of a specified compound. CONSTITUTION:The silver halide photosensitive material is developed in the presence of the compound having a 1-phenyl-3-pyrazolidino group having the function of a developing agent represented by formula I in which Y is the 1-phenyl-3-pyrazolidino group; Z is 2 valence binding group, -SO2- or a group of formula II; A1 is H, alkyl, alkenyl, aralkyl, or acyl; each of A2 and A3 is, independently, H, acyl, or sulfonyl; Ar is an aromatic residual or heterocyclic aromatic residual group; and X is formyl, acyl, sulfonyl, alkoxyoxalyl, substituted oxamoyl. It is preferred that the grain diameter of silver halide grains is <=0.7mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material which gives an extremely hard and highly sensitive negative image and good halftone dot image quality.

[0002]

2. Description of the Related Art Obtaining a favorable negative image by adding a hydrazine compound to a silver halide photographic emulsion is disclosed in US Pat. No. 2,419,975. It is described in the patent specification that when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH of 12.8, extremely high photographic characteristics with a gamma of more than 10 can be obtained. ing. However, if the pH is 13
A strong alkaline developer close to that is liable to be air-oxidized and unstable, and cannot withstand long-term storage and use. Ultra-high contrast photographic characteristics with a gamma of more than 10 are useful for printing plate making, whether it is a negative image or a positive image.
It is extremely useful for photographic reproduction of continuous-tone images or reproduction of line drawings.

Thereafter, US Pat. No. 4,224,401
No. 4, Ibid. 168, 977, Ibid. 4, 243, 739
Nos. 4,272,614, 4,323,643 and the like disclose a silver halide photographic emulsion which gives a very hard negative photographic property by using a stable developing solution. It was found that the acylhydrazine derivative used in 1. had some drawbacks.

That is, it is known that these conventional hydrazines generate nitrogen gas during the developing process, and these gases collect in the film to form bubbles, which impair the photographic image. Further, these conventional hydrazines have unevenness in infectious development due to agglomeration, which causes characteristic fog called black spots, which is a serious problem in the photomechanical process.
This occurs with the passage of time of the light-sensitive material, especially with storage at high temperature and high humidity, or with the fatigue of the developer over time, and is particularly noticeable due to deterioration of the developer, decrease of sulfite ion as a preservative, and increase of pH. .

Great efforts have been made to improve this black spot. For example, JP-A-62-275247 and 63.
Such is the use of nitrogen-containing heterocyclic hydrazine compounds described in, for example, No. 8715. However, black spot improvement is often accompanied by a reduction in sensitivity and gamma.

On the other hand, British Patent No. 2,011,397B discloses a phenylacylhydrazine compound having a heterocyclic residue having a mercapto group as an adsorptive group in the molecule, and US Pat. No. 3,718,470 discloses it. Although sensitizing dyes having a hydrazine group in the molecular structure have been described, they all have drawbacks such as insufficient activity as a nucleating agent and high activity but insufficient storage stability. And improvements were desired.

For the purpose of solving these drawbacks, Japanese Patent Laid-Open No.
0-179734, 61-170733, Japanese Patent Application Nos. 60-206093, 60-19739 and 60.
-111936, JP-A-62-130361, JP-A-62-178246, and U.S. Pat. No. 4,686,16.
No. 7, etc., or hydrazine derivatives having a functional group, such as JP-A-62-270948 and JP-A-63-29751, have been proposed, but all of them deteriorate the developing solution (for example, pH, sodium sulfite, etc.). It's hard to say enough.

[0008]

SUMMARY OF THE INVENTION The first object of the present invention is to:
Another object of the present invention is to provide a silver halide photographic light-sensitive material in which variations in photographic characteristics due to changes in developer composition are small.

Secondly, an object of the present invention is to provide a negative type silver halide photographic light-sensitive material exhibiting super-high contrast photographic characteristics and having less black spots.

A third object of the present invention is to provide a silver halide photographic light-sensitive material containing hydrazines which is easy to synthesize and has excellent storage stability and which is stable with time.

[0011]

The present inventor has found that this object can be achieved by using a compound of Chemical formula 3 having a 1-phenyl-3-pyrazolidino group having a developing agent function in the molecule. It started.

[0012]

[Chemical 3]

[In the formula, Y represents a 1-phenyl-3-pyrazolidino group, Z is a divalent linking group, and —SO ₂ —
Represents A ₁ is a hydrogen atom, an alkyl group, an alkenyl group,
It represents an aralkyl group or an acyl group, and A ₂ and A ₃ may be the same or different and each represents a hydrogen atom, an acyl group or a sulfonyl group. Ar is an aromatic residue or a heteroaromatic residue, and X is a formyl group, an acyl group, a sulfonyl group, an alkoxyoxalyl group, or a substituted oxamoyl group. ]

Specific examples of the compound represented by Chemical formula 3 are shown below. However, the present invention is not limited to the following compounds.

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

[0027]

[Chemical 16]

[0028]

[Chemical 17]

[0029]

[Chemical 18] Next, a method for synthesizing the compound of the present invention will be described with reference to specific examples.

Synthesis Example 1 Synthesis of Exemplified Compound (Formula 4) A synthetic scheme is shown in Formula 19. Intermediate (C) is disclosed in
It was synthesized according to the synthetic method disclosed in No. 216545.

[0031]

[Chemical 19]

15.3 g of p-nitrophenylhydrazine
50 ml of diethyl oxalate were mixed and heated on a water bath for 5 hours. After cooling, the precipitated crystals were collected by filtration and washed with ethanol to obtain 20.9 g of compound (A). Melting point 178-
179 ° C. Next, 10.0 g of the compound (A) was added to ethanol 6
Dissolved in a mixed solvent of 0 ml and 40 ml of 1,4-dioxane,
Catalytic reduction was performed under a Pd-C solvent to obtain 8.1 g of the compound (B). Melting point 102 ° C (decomposition).

Next, 1.12 g of compound (B) was added to 10 ml of acetic acid.
The above compound (C) was added, and the mixture was reacted at 70 ° C. for 3 hours on a water bath. After cooling, ether was added, and the precipitated crystals were collected by filtration and washed with ethanol repeatedly to obtain compound (D) 1.
9 g was obtained. Melting point 146 [deg.] C (decomposition).

Next, 0.8 g of the compound (D) was added to methanol 1
It was suspended in 0 ml, 3-diethylaminopropylamine was added, and the mixture was heated under reflux for 30 minutes. After the reaction, the solvent was distilled off under reduced pressure, ethanol was added, and the precipitated crystal was collected by filtration. After washing with ethanol, 720 mg of the desired compound 4 was obtained. Melting point 24
5 ° C

Synthesis Example 2 Synthesis of Exemplified Compound (Formula 5) A synthetic scheme is shown in Formula 20.

[0036]

[Chemical 20]

Starting material (F) 0.9 was dissolved in methanol and catalytically reduced in a Pd-C solvent. After the reaction was completed, the insoluble material was filtered off, and the filtrate was concentrated under reduced pressure at low temperature to obtain crude crystals of compound (G). This was not purified, and subsequently dissolved in 10 ml of acetic acid, compound (C) was added, and the reaction was carried out at 70 ° C. for 3 hours on a water bath. (A crystallized substance was observed 30 minutes after the reaction.) After the reaction was completed, the crystallized substance was collected by filtration to give 2-
The crystals were washed with propanol to obtain crude crystals of compound (Chemical Formula 5).
This was recrystallized from acetic acid to obtain 760 mg of a purified product of (Chemical Formula 5). Melting point 241 [deg.] C.

In the light-sensitive material of the present invention, the compound represented by Chemical formula 3 is preferably contained in the surface latent image type silver halide emulsion layer, but it is hydrophilic adjacent to the surface latent image type silver halide emulsion layer. It may be contained in the colloid layer. Such a layer has any function, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer and an antihalation layer, as long as it does not prevent the compound represented by Chemical formula 3 from diffusing into silver halide grains. It may be a layer. Since the content of the compound of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content may vary over a wide range, but the surface latent image About 1 × 10 ⁻⁶ to 1 × 10 per mol of silver in the silver halide emulsion
A range of ^-2 mol is practically useful.

When the hydrazine compound represented by Chemical formula 3 used in the present invention is mixed in the developing solution, it is 10 ^-4.
10 ^-1 mol / l is suitable, and more preferably 5 x 1
The range of 0 ^{−4 to} 5 × 10 ⁻² / l is particularly preferable.

The silver halide used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, and silver chloride, silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide. Etc. can be used, but when silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is preferably 5 mol% or less. The form, crystal habit, size distribution, etc. of the silver halide grains are not particularly limited, but those having a grain size of 0.7 μm or less are preferable.

The silver halide emulsion is a sulfur compound or stannous compound which reacts with a gold compound such as chloroauric acid salt or gold trichloride, a salt of a noble metal such as rhodium or iridium, or a silver salt to form silver sulfide. The sensitivity can be increased with a reducing substance such as a salt or amine without coarsening the particles. Further, an iron compound such as a salt of a noble metal such as rhodium or iridium or a red blood salt may be allowed to be present during physical ripening or nucleation of silver halide grains. In particular, addition of a rhodium salt or a complex salt thereof is preferable because it further promotes the effect of the present invention of achieving photographic characteristics of ultrahigh contrast in a short developing time.

In the present invention, the surface latent image type silver halide emulsion means an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. No. 4,224,224. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of No. 401. It is desirable that the silver halide emulsion be monodisperse, and in particular, the above-mentioned US Pat.
An emulsion having the monodispersity defined in No. 224,401 is preferable.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopo-la-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
Cyanine dyes, merocyanine dyes, and composite merocyanine dyes. These sensitizing dyes may be used alone, or a combination thereof may be used.
A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may 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, gelatin is advantageously used, 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 sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. It is possible to use various kinds of synthetic hydrophilic polymer substances such as a partial or acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and other single or copolymers. . As gelatin, lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, oxygen-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an oxygen-decomposed product of gelatin may also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azole,
For example, benzothiazolium salt, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles; mercaptopyrimidines, mercaptotriazines, thioketo compounds; azaindenes, etc. Many compounds conventionally known as antifoggants or stabilizers can be added. Among these, particularly preferred are benzotriazoles (eg 5-methylbenzotriazoles) and nitroindazoles (eg 5-methylbenzotriazoles).
Nitroindazole). These compounds may be contained 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 (24-dichloro-6-). Hydroxy-S-triazine, etc.) or the like can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration) , Hardening, and sensitization) may be included for various purposes. Non-ionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulfates,
Carboxyl group, such as alkyl esters
Anionic surfactants containing an acidic group such as a sulfo group, a phospho group, a sulfate ester group, and a phosphate ester group; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters; cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium Can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid,
A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing sufficient sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Especially 10.5-1
With the developer of 2.3, a super-high contrast negative image can be sufficiently obtained.

The developing agent that can be used in the method of the present invention is not particularly limited, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination.

In addition to the above, the developing solution also includes pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or Development inhibitors or antifoggants such as benzotriazoles). In addition, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant defoaming agent, a film hardener, a film silver stain inhibitor (for example, 2-mercaptobenzimidazole acids), etc. May be included. Specific examples of these additives are Research Disclosure 17
No. 6, 17643, etc.

As the fixing solution, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used.
Further, the fixing solution may contain a water-soluble aluminum salt as a hardening agent.

In the present invention, a method of incorporating a developing agent in the light-sensitive material and processing with an alkaline activator solution may be adopted. (JP-A-57-129436, 57-129433, 57-129434, 5)
7-129435, U.S. Pat. No. 4,323,643, etc.). The treatment temperature is usually selected from 18 ° C to 50 ° C, but it 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 when the total processing time from putting the light-sensitive material in the automatic developing machine until it comes out is set to 60 seconds to 120 seconds, a sufficiently high-hardness negative tone gradation photographic characteristic can be obtained.

[0054]

【Example】

Example 1 A silver iodobromide emulsion composed of cubic crystals having an average grain size of 0.25 micron and containing 97% AgBr and 3% AgI was prepared by the double jet method, washed with water and redissolved by a conventional method, Chemical sensitization was performed using sodium thiosulfate. This silver iodobromide emulsion was divided into 7 parts, and the addition amounts shown in Table 1 were added to the polyesters of Chemical Formula 4, Chemical Formula 5, Chemical Formula 6 and Chemical Formula 12 of the present invention and the following Chemical Formulas 21 and 22 as comparative compounds. It was coated on the film so that the amount of silver was 3.7 g per 1 m ² .

[0055]

[Chemical 21]

[0056]

[Chemical formula 22]

On the other hand, a developing solution was prepared according to the following formulation, which was further filled in an automatic developing machine [A] and used immediately after reaching 20 ° C. (fresh developing solution). [B] After being filled in an automatic processor, left in that state for 1 week before use (air fatigue solution). [C] After filling in an automatic processor, a DCL-EHF film (a bright room light-sensitive material manufactured by Mitsubishi Paper Mills, Ltd.) 50.8 cm ×
A sheet of 61.0 cm exposed so as to develop 50% of the area is processed for 200 sheets a day and repeatedly used for 5 days (100 cc of developer is replenished per sheet processed). ). The film samples were classified into three types and subjected to wedge exposure to the above film samples, and developed at 20 ° C. for 3 minutes. The results are shown in Table 1.

<Developer> Hydrokin 30 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.3 g Sodium sulfite 75 g EDTA.2Na 1.0 g Cipotassium phosphate 80 g Potassium bromide 2.0 g NaOH 13 g 5-Methylbenztriazole 0.3 g 1-Diethylamino-2,3-dihydroxypropane 17 g Water is added and adjusted to pH 11.5 with 1 l potassium hydroxide.

[0059]

[Table 1]

1) Sensitivity: The amount of exposure required to give a density of 1.0 is expressed as relative sensitivity. 2) Gamma: density 0.5
Represents an average slope of from 2.0 to 2.0. 3) ΔS _BA : The difference between the sensitivity (S _B ) when developed with an air fatigue solution and the sensitivity (S _A ) when developed with a fresh developer. 4) ΔS _CA : The difference between the sensitivity (S _C ) when developed with a large amount developing solution and the sensitivity (S _A ) when developed with a fresh developing solution.

From the viewpoint of processing running stability, it is desirable that the photographic characteristics obtained with the developers [B] and [C] are not different from those of [A]. As can be seen from Table 1, when the hydrazine compound of the present invention is used, the sensitivity change is extremely small even though the developer is fatigued.

Example 2 A part of the film sample obtained in Example 1 was heated at 40 ° C. for 30 days, and then exposed and developed with a fresh developer (20 ° C., 3 minutes) as in Example 1. Then, the sensitivity and fog value immediately after coating were compared. The results are shown in Table 2.

[0063]

[Table 2]

As is clear from Table 2, the compounds of the present invention have no problem in sensitivity change and fog sensitization with storage.

Example 3 Another half of the film sample obtained in Example 1 was tested for dot quality. That is, each film sample was exposed through a sensitometric exposure wedge using a 150-line gray contact screen, and then developed with a fresh developer as described above at 38 ° C. for 30 seconds to check the halftone dot quality. It was The results are shown in Table 3.

[0066]

[Table 3]

The halftone dot quality was visually evaluated on a scale of 5, with 5 being the best and 1 being the worst. As the halftone dot original plate for plate making, 5 and 4 are practical, 3 is poor, but it is barely usable, and 2 and 1 are practically unusable qualities. As is clear from Table 3, the comparative compound has poor quality due to uneven development, but the compound of the present invention exhibits good halftone dot quality.

[0068]

According to the image forming method of the present invention, there is no problem in storage stability over time, and it is possible to obtain photographic characteristics of extremely high tone negative gradation having a gamma of more than 10, which is excellent in running stability.

Claims (1)

[Claims] 1. A method of forming an image, which comprises developing a silver halide light-sensitive material in the presence of a compound represented by the following chemical formula 1. [Chemical 1] [Wherein Y represents a 1-phenyl-3-pyrazolidino group,
Z is a divalent linking group and represents —SO ₂ — or Chemical formula ₂ . A
₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an acyl group, and A ₂ and A ₃ may be the same or different and each represents a hydrogen atom, an acyl group or a sulfonyl group. Ar is an aromatic residue or a heteroaromatic residue, and X is a formyl group, an acyl group, a sulfonyl group, an alkoxyoxalyl group, or a substituted oxamoyl group. ] [Chemical 2]