JPH02285342A - Silver halide photographic sensitive material capable of forming image high in contrast - Google Patents

Abstract

PURPOSE:To enhance contrast in a photographic image and halftone quality by incorporating a specified hydrazide compound in a silver halide photographic sensitive material. CONSTITUTION:The silver halide photographic sensitive material contains the hydrazide compound represented by formula I or II in which Z is formyl, acyl, or the like; R1 is alkyl; R1(O)n- group is substituted at the o- or p-position of the hydrazide, n is 0 or 1, R2 is substituted OH, alkyl or amino group at the o- or p-position of the hydrazide; R3 is alkyl, and when R2 is OH or alkyl, R3 has a diffusion resistant group, and when R2 is amino, R3 has a diffusion resistant group or a group promoting adsorption to silver halide, thus permitting high contrast photographic characteristics to be obtained, and fog occurring in a halftone image to be restrained.

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.

[Conventional technology]

Conventionally, 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, a silver halide photographic light-sensitive material with high-contrast photographic properties is used to draw images on the original through an intersection screen or contact screen, which is then developed to form a halftone image. I was trying to do that.

In order to give an image a high-contrast characteristic, conventional methods were
Publication No. 6-106244, European Patent 301799
As shown in the specification etc., a silver halide photographic light-sensitive material contains a compound such as hydrazine as a so-called high contrast agent, and silver halide grains are further added to effectively exhibit the high contrast characteristics of this compound. The desired photographic materials have been adjusted by using them or by appropriately combining them with other photographic additives. 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 bins, 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.The present invention has been made to solve the above-mentioned problems. The purpose is to provide a silver photographic material.

[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) or (II) general formula (1) general formula [■] R2 in this material. With this configuration, it is possible to exhibit high-contrast photographic characteristics that have high contrast characteristics and suppress pin-like fog in halftone images.

In the formula, Z represents a formyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or a thioacyl group.

R6 represents an alkyl group and includes a diffusion-resistant group.

The R1-(o), - group is substituted at the ortho or para position of the hydrazide.

n represents O or 1.

R2 represents a hydroxy group, an alkyl group, or an amino group, and is substituted at the ortho or para position of the hydrazide.

R3 represents an alkyl group.

When R2 represents a hydroxy group or an alkyl group, R1 shall contain a diffusion-resistant group, and when R2 represents an amino group, R
1 contains a diffusion-resistant group or a group that promotes adsorption to silver halide.

-a Compounds represented by formulas (1) and (■) include those in which at least one of H in -N HN 11- is substituted with a substituent.

The silver halide photographic material of the present invention may contain one or more compounds represented by general formula (1), or may contain one or more compounds represented by general formula (n). (, also, the compound represented by the general formula (1) and the general formula (
TI). When two or more of these compounds are contained, the combination is arbitrary.

A more detailed explanation of general formulas (1) and (II) is as follows.

Z is a formyl group, an acyl group (e.g., acetyl group, trifluoroacetyl group, α-(2,4-di-t-amylphenoxy)acetyl group, methoxyacetyl group, cyanoacetyl group, benzoyl group, etc.), sulfonyl groups (for example, methylsulfonyl group, toluenesulfonyl group, 4-dodecyloxybenzenesulfonyl group, etc.), carbamoyl group (for example, carbamoyl group, dodecylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (
For example, it represents a sulfamoyl group, a butylsulfamoyl group, a dimethylsulfamoyl group, etc.), an alkoxycarbonyl group (eg, a methoxycarbonyl group, a tetradecyloxycarbonyl group, etc.), or a thioacyl group (eg, a thioformyl group, a thioacetyl group, etc.).

Examples of the alkyl group represented by R1 or R1 include methyl, ethyl, propyl, butyl, and benzyl groups.

Various substituents can be introduced into the alkyl group represented by R or R8, and examples thereof include a carbamoyl group, a ureidocarbonyl group, an oxycarbonyl group, an acylamino group, a sulfonamide group, a carbonyloxy group, a sulfamoyl group, and the like.

Through these substituents, a diffusion-resistant group can be introduced into R, and a diffusion-resistant group or a silver halide adsorption-promoting group can be introduced into R1.

The diffusion-resistant group is preferably a ballast group that is commonly used in immobile photographic additives such as couplers.The ballast group is a group that has 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group. group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkino (
You can choose from phenoxy 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 thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R2 is a hydroxy group, an alkyl group (for example, a methyl group,
ethyl group, propyl group, butyl group, benzyl group, etc.) or amino group (e.g. amino group, dimethylamino group,
diethylamino group, morpholino group, piperidino group, benzylamino group, anilino group, etc.).

1119 The phenyl groups of formulas (1) and (II) include R,
Various substituents can be introduced in addition to -(0), -1R2 and R1. 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. , acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group, hydroxy group,
Examples include carboxy group, sulfo group, nitro group, and cyano group.

In general formula (1), R2 of -N HN H-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, ethoxycarbonyl, etc.)
, oxalyl group (eg, ethoxalyl, pyruvoyl, etc.), and the compounds represented by general formulas (1) and (II) also include such groups.

In the present invention, more preferred compounds are -e formula (I)
and a compound in which Z in (II) is a formyl group or an acyl group.

Representative compounds represented by the above general formulas CI) and (II) include those shown below. However, as a matter of course, general formulas (1) and (
The specific compounds of II) are not limited to these compounds.

In addition, the following exemplary compounds (1) to (6), (23), (2
4), (27) to (30) are general formulas [! The following are specific examples of compounds represented by the general formula.

CzHs C11i% CI (CBS)! The compound of the present invention can be easily synthesized according to the synthesis method described in British Patent No. 2011391, European Patent No. 301799, and the like.

For example, the exemplified compound (1) can be synthesized by the following method.

The following margin The silver halide photographic light-sensitive material of the present invention contains a compound represented by the above general formula (1) or (II), but the general formula ( The amount of the compound 1) or (II) is preferably from 5X10"' mole to 5X10" mole per mole of silver halide contained in the photographic light-sensitive material of the present invention.

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

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 layer may be provided on each side 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 banking layer may be provided as necessary.

In order to incorporate the compound represented by general formula (1) or (I[) into the silver halide photographic light-sensitive material of the present invention, it is preferable to incorporate it into a hydrophilic colloid layer in the material, and it is particularly preferable to incorporate it into a hydrophilic colloid layer in the material. It is preferably contained in a silver emulsion layer and/or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

However, the compound of the above general formula (1) or (II) may be contained not in the silver halide emulsion layer but in another layer. Of course, it may be contained in the layer.

The most preferred embodiment of the present invention is an embodiment in which the compound (1) or (n) 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) or (II) 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 lathe lath, and a method of adding the compound by dispersing it in latin lath.

Any of these methods may be used in practicing the invention. When adding, the compound represented by the general formula (1) or CI can obtain preferable image characteristics even when used alone, but this compound may be used in combination of two or more in an appropriate ratio. It has been confirmed that it is also good.

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

As mentioned above, the present invention has the general formula (
In another preferred embodiment, the compound of 1) or (If) is added to the silver halide emulsion layer, and in another preferred embodiment, the hydrophilic colloid immediately adjacent to the hydrophilic colloid layer containing the silver halide emulsion layer is added. layer, or an adjacent hydrophilic colloid layer via an intermediate 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 a 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 ear length of the cubic grains.

When carrying out the present invention, for example, silver halide particles having a multilayer structure of at least 2N can be used, for example, the core part is silver chloride, the shell part is silver bromide, and vice versa. For example, silver chlorobromide particles having a core portion of silver bromide and a shell portion of silver chloride can be used. 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 mol to 10@-4 mol per mol of silver.

Furthermore, silver halides can be sensitized by various chemical enhancers. Examples of exacerbating agents include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacinate, etc.),
Selenium sensitizer (N.

N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, stannous chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride , ammonium chloroparadate, potassium chlorooleate, 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 compounds (for example, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (for example, 5-prombenzotriazole,
5-methylbenzotriazole), benzimidazoles (for example, 6-nidrobenzimidazole), etc., can be used to stabilize or suppress fog. The silver halide emulsion used in the present invention contains a sensitizing dye,
Plasticizers, antistatic agents, surfactants, hardeners, etc. can also be added.

When adding the compound of the general formula [summer] or (n) according to the present invention to a hydrophilic colloid layer, gelatin is suitable as a binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin may also be used. I can do it.

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-(C1l=CH) n -OH type developing agents include hydroquinone, and others include catechol, pyrogallol, and the like.

In addition, typical NO(C1(=CI) n NHz type developers include ortho or para aminophenol or aminopyrazolone, and N-methyl-p-
Aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid,
2-aminonaphthol and the like.

Examples of the heterocyclic developer include 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. - Pyrazolidones, etc. can be mentioned.

Others, T, 11. James, The Theory of the Photographic Process, 4th Edition
Theory of the Photography
icProcess.

Fourth Edition) pages 291-334,
and Journal of the American Chemical Society.
erican Chemical 5ociety
) Vol. 73, p. 3.100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination.When used alone, hydroquinone is used; when used in combination, hydroquinone is used as 1-phenyl-3 -Pyrazolidone or a combination of hydroquinone and N-methyl-p-aminophenol are preferred.

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, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, ethylenediaminetetraacetic acid, etc. metal ion scavengers, methanol, ethanol, benzyl alcohol, development accelerators such as polyalkylene oxides, sodium alkylarylsulfonates, natural saponins, surfactants such as Ill or alkyl esters of the above compounds, glutaraldehyde, formalin. , hardening agents such as glyoxal,
It is optional to add an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent.

〔Example〕

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) or (Ill) or a comparative compound (
The types are shown in Table 1 below. ) was added in the following manner to prepare a sample.

(Preparation of silver halide photographic light-sensitive material) 100 μm thick with 0.1 μm thick undercoat layer on both sides
A silver halide emulsion layer of the following formulation (11) was coated on one undercoat layer of a polyethylene terephthalate film with a gelatin amount of 1.5 g/n? and a silver amount of 3.3 g/cd. Further, on top of that, a protective layer according to the following formulation (2) was applied so that the amount of gelatin was 1.0 g/n?, and on the other undercoat layer on the opposite side, according to the following formulation (3). A banking layer was applied so that the amount of gelatin was 3.5 g/d, and then a protective layer of the following formulation (4) was applied on top of it so that the amount of gelatin was Ig/mr. 14
I got it.

Prescription +11 [Silver halide emulsion layer composition] Prescription (2) [Emulsion protective layer composition] Prescription (3) [Backing layer composition] ITO: Charge modifier that is a mixed oxide of indium and tin and has an indium content of 95% or more Prescription (4) [Backing protective layer composition] The obtained sample was subjected to a halftone quality test according to the following method.

(W 4-point quality test method) A part of the step wedge is attached with a return mesh 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 magnifying glass and rate the one with high halftone quality as "5"
The following five ranks were set: "4", "7", "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 there are no black pins in the halftone dots, and the highest rank is ``4'' depending on the degree of occurrence of black pins in the halftone dots. ”, “
3", "2", and rlJ, and their ranks were sequentially lowered for evaluation. Incidentally, in ranks "1" and "2", the black bottles are also large and are at a level that is not practical.

(Developer Prescription) (Composition A) (Composition) When using a developer, the above composition A was dissolved in 500 ml of water in the following order and finished to 11 before use.

(Fixer formulation) (Composition A) Set fixation 28°C 20 seconds Water washing Room temperature 20 seconds The following compounds (a) to (d) were used as comparative compounds added to the silver halide emulsion layer in formulation +1). .

The following margin (composition): When using the fixer, the fixer was dissolved in 500 ml of water in the order of the composition name and the composition above, and was finished to 11 and used. This fixer p
H was approximately 4.3.

(Development processing conditions) (Process) Development (temperature) 38°C (time) 30 seconds (c) (d) (Test results) Table 1 shows the results using samples at to 10 of the present invention and the above comparative compounds. The compounds added to the silver halide emulsion layers and their amounts added are shown for samples m11 to m14 prepared in the following manner.

In addition, the compounds of general formula (1) or (n) in Table-1 are:
It is shown by the number of the above-mentioned exemplified compound.

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 +1-io according to the present invention all showed results of rank "4" or higher, and rank "5" showed more results, and comparison sample Fil.
1 to 14 all show a result of rank "3". Given that ranks "1" and "2" are at a level that cannot withstand practical use, it is difficult to say that samples 11 to 14 have good halftone dot quality, but sample rank 1 according to the present invention
It was found that all of the samples No. 1 to 10 had extremely high halftone dot quality and were good.

Also, regarding the occurrence of black pins, which is an indicator of fogging,
All samples Nl l-10 according to the present invention have a rank of “
Comparative samples 11 to 14 were all ranked "2" and showed extremely good results with no fog, indicating results that were difficult to withstand in practical use. Understood.

The following margin table-1 Table-2 Example-2 In Sample No. 1 and Sample No. 6 of Example-1, the monodispersity (uniform grain size) of the silver halide grains was changed from 4 to 40, and the sample area was 15 to 24 were created and tested.

In addition, when preparing the particles, rhodium was added at 8 x 10 mol/^g1.
mol, and iridium was added in an amount of 3 x 10-' mol/^g1 mol according to a conventional method. The silver halide composition here is a silver chlorobromide grain composition of 98 mol% silver chloride, and a sensitizing dye (
Instead of adding (a), (b), (c), and (d)), a desensitizing dye having the following structure 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/d in the protective layer.
In addition, in the example in which 100 mg/m of the following ultraviolet absorbing dye was added, the prepared sample was exposed to light using an ultra-high pressure mercury lamp,
Irradiation was performed with an energy of 5a+J.

The evaluation results are shown in Table-3. Sample areas 15 to 24 are halftone products! 4.5-5 and black bottle 4.5-5, both of which were good, indicating that the halftone dot quality was high and there was very little fog.

Table 3 SO, Na Other conditions were the same as those for Sample No. 1 and Sample No. 11h6, and for example, the same Exemplary Compound 141 and No. 8 were used as the compounds represented by the general formula (1) or (II).

The degree of monodispersity can be adjusted by a conventional controlled double jet method by changing the pH potential at the time of charging the particles and the amount of AgΦ ions and halide ions supplied.

Further, exposure and development treatments were performed in substantially the same manner as in Example-1, and the photographic performance was evaluated. However, according to the present invention, by incorporating the compound represented by general formula (1) or (II) into a silver halide photographic light-sensitive material, it is possible to obtain high-contrast characteristics of a photographic image. , and an excellent photosensitive material with high halftone dot quality can be obtained.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer, characterized by containing at least one compound represented by the following general formula [I] or [II]. A silver halide photographic light-sensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z is a formyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, Represents an alkoxycarbonyl group or a thioacyl group. R_1 represents an alkyl group and includes a diffusion-resistant group. The R_1-(O)_n- group is substituted at the ortho or para position of the hydrazide. n represents 0 or 1. R_2 represents a hydroxy group, an alkyl group, or an amino group, and is substituted at the ortho or para position of the hydrazide. R_3 represents an alkyl group. When R_2 represents a hydroxy group or an alkyl group, R_
3 shall contain a diffusion-resistant group, and when R_2 represents an amino group, R_3 shall contain a diffusion-resistant group or a group promoting adsorption to silver halide. The compounds represented by the general formulas [I] and [II] include compounds in which at least one H of -NHNH- in the formulas is substituted with a substituent.