JPH01201650A - Silver halide photographic sensitive material capable of obtaining high contrast image - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material which has the high contrast characteristic of a photographic image and the excellent high dot quality by incorporating a specified compd. in the title material. CONSTITUTION:The compd. shown by formula I is incorporated in the photosensitive material. In formula I, A is a heterocyclic ring residual group having at least one of sulfur or oxygen atom, R is formyl, acyl, sulfonyl, carbamoyl, sulfamoyl, alkoxycarbonyl or thioacyl group, etc. The compd. shown by formula I comprises a compd. which is substd. at least one of hydrogen atom contd. in the group -NHNH- shown by the formula with a substituting group. Thus, the photosensitive material having high contrast photographic characteristic and also having its pin-like fog generating in a dot image suppressed, is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material capable of obtaining a high-contrast photographic image.

[Prior Art] Silver halide photographic materials have been widely used in photolithography processes. This photolithography process involves converting a continuous tone original into a halftone image, i.e. converting the continuous tone density variations of the original into a set of halftone dots with an area proportional to this density. It is.

In this conversion process, an original is photographed through an intersection screen or a contact screen using a silver halide photographic light-sensitive material with high-contrast photographic properties, and a halftone image is formed by developing the photograph. That's what I was doing.

In order to give an image a high-contrast characteristic, conventional methods were
Publication No. 6-106244 and U.S. Patent No. 4,686,167
As shown in the specification, a silver halide photographic light-sensitive material contains a compound such as hydrazine as a so-called high contrast agent, and furthermore, silver halide grains are used to effectively exhibit the high contrast characteristics of this compound. and other photographic additives in appropriate combinations to obtain desired photographic materials. The silver halide photographic light-sensitive material thus obtained is certainly stable as a light-sensitive material, and high-contrast photographic images can be obtained even when processed with a rapid processing developer. .

[Problem that the invention seeks to solve]

However, with such silver halide photographic materials, when converting a continuous tone original into a halftone image, sandy pin-like fog, so-called black pins, occur in the halftone dots, which deteriorates the quality of the halftone image. This had the problem of damaging the . Therefore,
In order to solve this problem, conventional methods have been taken such as adding various stabilizers and inhibitors containing heteroatoms, but these have not always been effective.

The present invention has been made in order to solve the above-mentioned problems, and is capable of exhibiting high-contrast photographic characteristics by suppressing pin-like fog that occurs in halftone images, as well as having high-contrast photographic characteristics. The purpose of the present invention is to provide a silver halide photographic light-sensitive material that can be used.

[Structure and operation of the invention]

The silver halide photographic light-sensitive material according to the present invention contains a compound represented by the following general formula (1) A-NHNH-R in the light-sensitive material. This makes it possible to exhibit high-contrast photographic characteristics that have high contrast characteristics and suppress pin-like fog in halftone images.

In the above general formula (1), A represents a heterocyclic residue having at least one sulfur atom or oxygen atom, and R represents a formyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a thioacyl group. , or a group represented by -C-C-X.

X represents -NR, R, or -OR3, Rl +R2
and R3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R8 and Rz may form a ring together with the nitrogen atom.

The compound represented by the general formula (1) includes -NF(N
Includes H- in which at least one H is substituted with a substituent.

To further explain the above general formula in detail, specific examples of A include thiophene, furan, benzothiophene, pyran, isobenzofuran, chromene, oxazole, and thiazole, with thiophene or furan being preferred.

R is a formyl group, an acyl group (for example, an acetyl group, a trifluoroacetyl group, an α-(2,4-di-monoamylphenoxy)acetyl group, a methoxyacetyl group, a cyanoacetyl group, a benzoyl group, etc.), a sulfonyl group (e.g. methylsulfonyl group, toluenesulfonyl group, 4-dodecyloxyhenzenesulfonyl group, etc.), carbamoyl group (e.g. carbamoyl group, dodecylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, butylsulfamoyl group, etc.) basis,
dimethylsulfamoyl group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, tetradecyloxycarbonyl group, etc.), thioacyl group (e.g. thioformyl group, thioace represents -C-C-OR, R,,R
2, R, represents a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, methoxyethyl group, etc.), an aryl group (e.g., phenyl group, P-methoxyphenyl group, α-naphthyl group, etc.), a heterocyclic group (e.g., pyridyl group, etc.). group, chenyl group, etc.). R1 and R2 form a ring together with the nitrogen atom,
For example, a heterocyclic ring such as a morpholine ring may be formed. R
Among the groups represented by ○ O II II -C-C-OR, the group represented by O II II -C-C-OR is preferred.

Various substituents can be introduced into the heterocyclic group represented by A having at least one sulfur atom or oxygen atom. Examples of substituents that can be introduced include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyloxy groups, alkylthio groups, arylthio groups, sulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, and sulfamoyl groups. , an acyl group, an amino group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamide group, an arylaminothiocarbonylamino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, and the like.

The compound represented by Formula 11 [I] preferably contains at least one diffusion-resistant group or silver halide adsorption-promoting group in the molecule. The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group here is a group having 8 or more carbon atoms and relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group,
It can be selected from phenoxy groups, alkylphenoxy groups, etc.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a thiourea group, a 1,000 urethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R1 of -NHNH- in general formula (1), that is, the hydrogen atom of hydrazine, is a sulfonyl group (e.g. methanesulfonyl,
toluenesulfonyl, etc.), acyl groups (e.g., acetyl, trifluoroacetyl, etc.), oxalyl groups (e.g.,
may be substituted with a substituent such as ethoxalyl, etc.),
-i Compounds represented by formula (1) also include such compounds. Typical compounds represented by the above general formula CI) include those shown below. However, it goes without saying that the specific compounds of general formula (1) that can be used in the present invention are not limited to these compounds.

Specific compound examples: CzHs し IzHzsNHL; (JNH C.I.

COCOOCJs Next, a synthesis example of a specific compound represented by the formula (1) according to the present invention will be described.

The synthesis scheme of the above compound (2) according to the present invention is as follows.

This synthesis method can be carried out with reference to, for example, the synthesis method of JP-A No. 55-52050.

The raw material 5-nitro-2-thienylhydrazine is, for example, It can be synthesized by the following method.

The synthesis method of 3-nitro-2-thienylhydrazine is described in “J
our own fjir Praktische Ch.
emie", 21191-99 (1964), and this synthesis method can also be referred to.

On the other hand, 5-nitro-2-furylhydrazine, which is a raw material for compound (6) according to the present invention, is
a Real Academia de Farmac
ia'' 27.N (11°47-60 (1961)).

Other compounds can be similarly synthesized with reference to these documents.

The silver halide photographic light-sensitive material of the present invention contains the compound represented by the above general formula (1), and the amount of the compound represented by the general formula (1) contained in the photographic light-sensitive material of the present invention is as follows: The amount is preferably 5.times.10@-7 mol to 5.times.10@-' mole per mole of the halogenated i atom contained in the photographic light-sensitive material of the present invention.

In particular, it is preferably in the range of 5X10-' moles to 1X10-' moles.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support. The silver halide emulsion can be coated directly onto the support, or coated via another layer such as a hydrophilic colloid layer that does not contain the silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the emulsion layer. Further, the silver halide emulsion layer may be coated separately into silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, between each silver halide emulsion layer,
An intermediate layer of hydrophilic colloid may also be provided. Further, an intermediate layer may be provided between the silver halide emulsion layer and the protective layer.

That is, non-photosensitive hydrophilic colloid layers such as an intermediate layer, a protective layer, an antihalation layer, and a backing layer may be provided as necessary.

In order to incorporate the compound represented by general formula CI) into the silver halide photographic light-sensitive material of the present invention, it is preferable to incorporate it into the hydrophilic colloid layer of the light-sensitive material, particularly preferably in the λ silver halide emulsion layer. And/or it is preferably contained in a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

However, the compound of the above general formula [I] is not contained in the silver halide emulsion layer (it may be contained in another layer; for example, it may be contained in another hydrophilic colloid layer laminated and coated on this emulsion layer). Of course, it is okay to force them to do so.

The most preferred embodiment of the present invention is an embodiment in which the compound of formula -a [l] is contained in the silver halide emulsion layer, and the hydrophilic colloid consists of gelatin or a gelatin derivative.

Next, a method for incorporating the compound of general formula (1) into the hydrophilic colloid layer will be explained. This method includes, for example, adding the compound after dissolving it in appropriate water and/or an organic solvent, or dispersing the solution in an organic solvent in a hydrophilic colloid matrix such as gelatin or gelatin derivatives, and then adding the compound. Examples include a method of adding the compound to the latex, and a method of adding the compound by dispersing it in latex. Any of these methods may be used in practicing the invention. When added, the compound of general formula (1) above can obtain preferable image characteristics even when used alone;
It has been confirmed that two or more of these compounds may be used in combination in an appropriate ratio.

Another method of addition is to dissolve the compound of general formula (1) in a suitable organic solvent such as water, methanol, alcohols such as ethanol, ethers, esters, etc., and then coat the overcoat. It may also be incorporated into the silver halide photographic material by directly applying it to the outermost layer of the silver halide emulsion layer of the silver halide photographic material.

As described above (as a preferred embodiment of the present invention), the general formula (
The compound of 1) may be added to the silver halide emulsion layer, and in another preferred embodiment, the compound may be added to the hydrophilic colloid layer directly adjacent to the hydrophilic colloid layer containing the silver halide emulsion layer, or to the intermediate hydrophilic colloid layer. It is added through the layer to the adjacent hydrophilic colloid layer.

Next, the silver halide used in the silver halide photographic material of the present invention will be explained. Silver halide of any composition can be used. For example, silver chloride, silver chlorobromide,
There are silver chloroiodobromide, pure silver bromide, and silver chloroiodobromide. The average diameter of the silver halide particles is preferably in the range of 0.05 to 0.5 μm, particularly 0.10 μm.
A thickness of 0.40 μm is preferable.

Although the particle size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted so that the monodispersity value defined below is in the range of 1 to 30, more preferably in the range of 5 to 20.

Here, the degree of monodispersity is defined by the following formula.

That is, the degree of monodispersity is defined as the value obtained by dividing the standard deviation of particle diameter by the average particle diameter times 100.

For convenience, the grain size of the silver halide grains is expressed by the edge length of the cubic grains.

When carrying out the present invention, for example, silver halide particles having a multilayer structure of at least two layers can be used, for example, the core part is silver chloride, the shell part is silver bromide, Conversely, it is possible to use silver chlorobromide particles in which the core portion is silver bromide and the shell portion is silver chloride. At this time, iodine can be contained in any layer, but it is preferable that iodine is contained within 5 mol%.

Furthermore, when preparing a silver halide emulsion, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparation of the emulsion coating solution. The rhodium salt may be a simple salt or a double salt, and typical examples include rhodium chloride, rhodium trichloride, and rhodium ammonium chloride.

The amount of rhodium salt added may be arbitrarily changed depending on the required sensitivity and gradation, but a range of 10-9 to 10-4 mol per mol of silver is particularly effective.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. In particular, iridium salts are often used for the purpose of imparting high-intensity properties, and are preferably used in amounts ranging from 10@-9 to 10@-4 moles per mole of silver.

Furthermore, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example, activated gelatin, sulfur enhancer (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacinate, etc.),
Selenium sensitizer (N.

N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, silver tin chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride , ammonium chlorovaladate, potassium chloroaurate, sodium chloroparadite, and the like can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The present invention is suitably applied when surface latent image type grains are contained as silver halide grains. Here, the surface latent image type particles are particles prepared in the art so that the sensitivity when processed with a surface developer is higher than the sensitivity when processed with an internal developer.

Further, the silver halide emulsion used in the present invention includes mercapto [(1-phenyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole, etc.), benzotriazoles (5-bromobenzotriazole, 5-methylbenzotriazole, etc.), benzimidazoles (6-nidrobenzimidazole, etc.), etc. to stabilize or suppress capri. can. Incidentally, a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardening agent, etc. can also be added to the silver halide emulsion used in the present invention.

When the compound of general formula (1) according to the present invention is added to a hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used.

Examples of supports that can be used in carrying out the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

For developing the silver halide photographic material of the present invention, the following developing agents are used, for example.

Typical examples of HO-(CH=C)I)n-OR type developing agents include hydroquinone, and others such as catechol and pyrogallol.

Further, typical 80 (Cll = CH) n NHz type developers include ortho and para amine phenols or aminopyrazolones, and N-methyl-
p-aminophenol, N-β-hydroxyethyl-
Examples include p-aminophenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol.

Examples of the heterocyclic developer include 1-phenyl-3-virazolidone, ■-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4 -Methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Examples include pyrazolidones and the like.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition) pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society).
ican Chemical 5ociety) No. 73
3, p. 100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Hydroquinone is preferable when used alone, and when used in combination, hydroquinone is preferably used in combination with 1-phenyl-3-pyrazolidone, or hydroquinone and N-methyl-p-aminophenol.

Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired.

Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives.

In addition, pH adjustment and buffering functions should be provided using caustic alkali, carbonate alkali, amine, etc. used in general black and white developers, as well as inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, and ethylenediaminetetraacetic acid. metal ion scavengers such as methanol, ethanol, benzyl alcohol, development accelerators such as polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, It is optional to add hardening agents such as formalin and glyoxal, ionic strength regulators such as sodium sulfate, and the like.

The developer used in the present invention contains alkanolamines and glycols as an organic solvent [Examples] Examples of the present invention will be described below. It should be noted that, as a matter of course, the present invention is not limited only to the following examples.

Example 1 An exemplary compound represented by general formula (1) and a comparative compound (the types of which are shown in Table 1 below) were added to the silver halide emulsion layer of a photographic light-sensitive material in the following manner. , prepared the samples.

(Preparation of silver halide photographic light-sensitive material) 100 μm thick with 0.1 μm thick undercoat layer on both sides
On one of the undercoat layers of the polyethylene terephthalate film, a silver halide pore agent layer having the following formulation (1) was coated so that the amount of gelatin was 1.5 g/rrf and the amount of silver was 3.3 g/rrf. On top of that, a protective layer of the following formulation (2) was applied so that the amount of gelatin was 1.0 g/rrf, and on the other undercoat layer on the opposite side, the following formulation (3) was applied. Accordingly, a backing layer was coated with a gelatin amount of 3.5 g/rrf, and a protective layer of the following formulation (4) was further coated on top of the backing layer with a gelatin amount of Ig/rrf.
-18 was obtained.

Prescription (1) [Silver halide emulsion layer composition] Prescription (2) [Emulsion protective layer composition] 1 Methyl methacrylate prescription (3) [Backing layer composition] Prescription (4) [Backing protective layer composition] Regarding the obtained samples, A halftone quality test was conducted using the following method.

(M4-point quality test method) A part of the step wedge is attached with a halftone screen (150 lines/inch) with a halftone dot area of 50%, and the sample is brought into close contact with this screen and exposed to a xenon light source for 5 seconds. The sample was developed under the following conditions in an automatic developing machine for rapid processing using the following developer and fixer, and the halftone quality of the sample was 1.
Observe with a 00x looper and rate the one with high halftone quality as "5"
The following five ranks were set: "4", "3", "2", and "1". Note that ranks "1" and "2" are levels that are not preferred in practice.

Fog in halftone dots is also evaluated in the same way, and the highest rank is "5" when no black pins occur in the halftone dots, and the highest rank is "4" depending on the degree of occurrence of black pins in the halftone dots. ”, “
The evaluation was made in descending order of rank: "3", "2", and "1". Note that in ranks "1" and "2", the black pins are also large and are at a level that is not practical.

(Developer formulation) (Composition A) (Composition) When using a developer, dissolve the above composition A in the order of composition A and II in 500 ntf of water. , and used it.

(Fixer Prescription) (Composition A) (Composition) When using the fixer, the above composition A was dissolved in water 500+nj in that order, and the composition was finished to 12. The pH of this fixer was about 4.3.

(Development processing conditions) (Process) (Temperature) (Time) Development 38
Fixing at 28°C for 20 seconds Washing at room temperature for 20 seconds Note that the following compounds (a) to (C) were used as comparative compounds added to the silver halide emulsion layer in formulation (1).

(Test Results) Table 1 shows the compounds added to the silver halide emulsion layers and the amounts added for samples Nα1 to 15 of the present invention and samples Nα16 to 18 prepared using the above comparative compounds. The compounds of general formula (I) in Table 1 are indicated by the numbers of the above-mentioned exemplified compounds.

Table 2 shows the results of the halftone quality test, ranked for each of the above samples.

As is clear from Table 2, regarding the halftone dot quality, samples Nα1 to Nα15 according to the present invention all showed results of rank “4” or higher, with rank “5” being more common, and comparative sample Nα
16 to 18 all show a result of rank "3". Given that the ranks "1" and "2." are at a level that cannot withstand practical use, it is difficult to say that the halftone dot quality of samples N0116-18 is good, but samples Nα1-15 according to the present invention It was found that all of the halftone dots were of extremely high and good quality.

In addition, regarding the occurrence of black bottles, which is an indicator of fogging,
Samples Nα1 to 15 according to the present invention are all ranked “5”
However, comparative samples 16 to 18 were all ranked "2" or lower, showing extremely good results with no fog. In Sample Nα3 and Sample Nα6 of Example-1, the monodispersity (uniform grain size) of the silver halide grains was 4 to 40.
Samples Nα19 to Nα28 were created in place of the following, and experiments were conducted.

In addition, when preparing the particles, rhodium was added at 8 × 10-' mol/
1 mol of Ag, and 3X10-' mol of iridium/Ag
1 mol was added according to a conventional method. The silver halide composition here is a silver chlorobromide grain composition containing 98 mol% of silver chloride, and instead of adding aggravating dyes ((a), (b), (c), (d)), the following structure is used. A desensitizing dye was added.

Desensitizing dye (the sum of the polarographic anode potential and cathode potential is positive) In addition, the following filter dye is added at 50 mg/r in the protective layer.
In addition to rf, 100mg/rr of long and ultraviolet absorbing dye below? Other additions were made in the same manner as in Sample Nα3 and Sample Nα6; for example, the same exemplified compounds Nα4 and Nα7 were used as the compounds represented by general formula (1). The degree of monodispersity can be adjusted by a conventional controlled double jet method by changing the pH potential at the time of particle preparation and the supply amounts of Age ions and halide ions.

Further, exposure and development treatments were performed in substantially the same manner as in Example-1, and the photographic performance was evaluated. However, in this example, the prepared sample was exposed to light using an ultra-high pressure mercury lamp with an energy of 5 mJ.

The evaluation results are shown in Table-3. Samples Nα19 to Nα28 had good halftone dots of ¥4.5 to ¥5 and black bins of ¥4.5 to 5, indicating that the halftone dot quality was high and there was very little capri.

Table 3 [Effects of the Invention] According to the present invention, by incorporating the compound represented by the general formula (I) into a silver halide photographic light-sensitive material,
It is possible to obtain an excellent photosensitive material that has the high contrast characteristics of a photographic image and has high halftone dot quality.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, characterized in that it contains at least one compound represented by the following general formula [I]. Silver photosensitive material. General formula [I] A-NHNH-R In the formula, A represents a heterocyclic residue having at least one sulfur atom or oxygen atom, and R represents a formyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an alkoxy group. Represents a carbonyl group, thioacyl group, or a group shown by ▲, which includes mathematical formulas, chemical formulas, tables, etc. X represents -NR_1R_2 or -OR_3, R_1
, R_2 and R_3 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R_1 and R_2 may form a ring together with a nitrogen atom. In the compound represented by the general formula [I], -NHN in the formula
Includes H- in which at least one H is substituted with a substituent.