JPS63249142A - Silver halide photographic sensitive material with reduced uneven development - Google Patents

Abstract

PURPOSE:To obtain the titled material having the high contrast and reduced unevenness of image density caused by uneven developing by incorporating a specified compd. in at least one layer of emulsion layers, and an another specified compd. in the hydrophilic colloidal layer adjacent to said emulsion layer respectively. CONSTITUTION:At least one layer of the titled material contains at least one kind of the compds. shown by formula I, and the hydrophilic colloidal layer adjacent to the emulsion layer contains at least one kind of the compds. shown by formula II. In formulas, Y1 and Y2 are each hydrogen atom. or mercapto group, R<4> is alkyl or alkenyl group which is substd. or unsubstd., A is nitrogen, carbon or oxygen atom., B is nitrogen or carbon atom. The preferable example of R<1>-R<3> groups is alkyl or amino group, etc. The anionic group shown by X<-> is exemplified by a halogen ion or an acid radical of an inorg. acid, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has a high contrast and is free from non-uniform image density due to non-uniform development during development. This invention relates to a silver halide photographic material with reduced so-called development unevenness.

[Conventional technology]

The photoengraving process using silver halide photographic light-sensitive materials involves the process of replacing a continuous tone original with a halftone image, that is, the process of converting continuous tone density changes into a set of halftone dots having an area proportional to the density. and a step of converting the halftone dot image obtained in this step into a halftone dot image with better sharpness, that is, a turning step.

It is essential that the photosensitive materials used in these processes have high contrast in order to obtain good halftone dot quality.

Conventionally, a method to obtain such characteristics is to process a photosensitive material made of a silver chlorobromide emulsion with relatively fine grains, a narrow particle size distribution, and a high silver chloride content using an alkaline hydroquinone developer with a very low sulfite ion concentration. A so-called lithographic development method is known.

However, when this method is used, the storage stability is extremely poor because the concentration of sulfite ions in the developer is low, and since hydroquinone is used as a single main agent, the development speed is slow and rapid processing is not possible.

Therefore, so-called PQ contains a super-additive developing agent that has good storage stability and can be processed quickly, and contains a relatively high concentration of sulfite.
It is desired to develop a new photosensitive material that can obtain high contrast by processing with a type or MQ type developer.

One of the things related to this new photosensitive material is Japanese Patent Publication No. 59-17825, Japanese Patent Publication No. 59-17sts, Japanese Patent Publication No. 59-17825,
No. 17819, No. 59-17820, No. 59-178
No. 21, No. 59-17826, and No. 59-17822 disclose silver halide photographic materials containing a tetrazolium compound.

The method of processing a photosensitive material containing these tetrazolium compounds with a superadditive developer to obtain a silver image with high contrast can be said to be an extremely innovative technology compared to conventional techniques.

However, when the gradation of a silver halide photographic light-sensitive material is made to have a very high contrast, slight nonuniformity in development, such as nonuniformity in the diffusion of a developing agent or nonuniformity in the diffusion of development inhibitors such as Br- ions, can cause The image density changes slightly,
There was a problem that it was not suitable for use. The phenomenon of "rBr-drug" in the above-mentioned Lith development method is also an example of this.

Methods for improving rBr"drag" in lithographic development include: (1) reducing the Br content in the silver halide composition of the lithographic photosensitive material;

(2) A method of using an amine compound in a sensitive material is known, but this method causes desensitization and increase in fog, and its effects are insufficient. Furthermore, the photosensitive material containing tetrazolium mentioned above also has a development speed about three times that of lithium development.
Nonuniform development due to high contrast may become more pronounced depending on processing conditions.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned prior art and to provide a silver halide photographic light-sensitive material which has high contrast and reduces unevenness in image density due to uneven development during development.

[Means to achieve the purpose]

The above object is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one layer contains at least one compound represented by the following general formula [I], and is adjacent to the emulsion layer. This is achieved by using a silver halide photographic material containing at least one compound represented by the following general formula (II) in the hydrophilic colloid layer.

General formula (1) General formula [■] [In the formula, Yl and Y2 represent a hydrogen atom or a mercapto group, and R4 is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkoxy group, or hydrogen Atom, ) represents a λ rogen atom, a nitro group, an amino group, a cyano group, a hydroxycarbonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a hydroxy group, a mercapto group, or a sulfo group.

Also, A represents a nitrogen atom, a carbon atom, or an oxygen atom, and B
represents a nitrogen atom or a carbon atom. When A represents a carbon atom, n! is 2, and when A represents a nitrogen atom, R2
is 1, and when A represents an oxygen atom, R2 is O.

Further, when B represents a carbon atom, n is 1, and when B represents a nitrogen atom, n is 0. ] Note that the above general formula (
In 1), preferred examples of the substituent represented by R1-R2 include an alkyl group, an amino group, an acylamino group, a hydroxyl group, an alkoxy group, an acyloxy group, a halogen atom, a carbamoyl group, an acylthio group, an alkoxycarbonyl group, and a carboxyl group. , an acyl group, a cyano group, a nitro group, a mercapto group, a sulfoxy group, and an aminosulfoxy group.

Examples of the anion represented by Xe include halogen ions, acid groups of inorganic acids, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, specifically lower alkylbenzenesulfonic acid anions, higher alkylbenzenesulfonic acids Examples include polymers with acid groups attached, such as anions, higher alkyl sulfate anions, boric acid anions, dialkyl sulfofosuccinate anions, polyether alcohol sulfate anions, higher fatty acid anions, and polyacrylate anions.

Specific examples of the compounds represented by the general formula (I) used in the present invention are listed in Table 1 below. (Chemical Revie
It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula (1) used in the present invention is about 1 mg or more and about 10 g per mole of silver halide contained in the silver halide photographic material of the present invention.
It is preferable to use the amount up to about 10 g to about 2 g.

Next, typical examples of the compound of general formula (II) will be given, but the present invention is not limited thereto.

(Exemplary compounds) (II-1) Benzotriazole (II-2) 5-methylbenzotriazole (II-3
) 5-chlorobenzotriazole (II-4) 5-nitrobenzotriazole (n-5) 5-ethylbenzotriazole (II-6) hydroxycarbonylbenzotriazole (II-7) 5-hydroxybenzotriazole (II
-8) 5-Aminobenzotriazole (If-9) 5-
Sulfonebenzotriazole (n-10) 5-cyanobenzotriazole (n-11) 5-methoxybenzotriazole (II-12) 5-ethoxybenzotriazole (U-13) 5-mercaptobenzotriazole (II-14) Benzimidazole (II-15) 5-sulfobenzimidazole (n
-16) 5-methoxybenzimidazole (n-1
7) 5-chlorobenzimidazole (n-18)
5-Nitroindazole (n-19) 6-Nitroindazole (n-20) 5-Sulfoindazole (II-21) Benzoxazole (II-22) 2-Mercapto-5-sulfobenzimidazole (n-23) 2- Mercaptobenzoxazole The amount of the compound of general formula (II) used in the present invention is:
It depends on the amount of silver halide used, the amount of the compound of general formula CI), etc. - Although it cannot be generalized, it is preferable to use an appropriate amount at the right time, but in general, silver halide photosensitive material 1 0.1 - 1 g is preferable, and 1 - 100
The range (2) is particularly preferred.

The silver halide photographic light-sensitive material of the present invention is formed by coating a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, and this silver halide emulsion layer is coated directly onto the support. Alternatively, it may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer as a protective layer may be further coated on the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, for example high and low sensitivity. An intermediate layer of a hydrophilic colloid layer may be provided between the silver halide emulsion layers, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer.

Specifically, the silver halide emulsion layer, which is a photosensitive layer, is provided on one side of the support, one layer is provided on both sides of the support, and one layer is provided on one side of the support, and one layer is provided on the other side. Examples include those in which two or more layers are provided via an intermediate layer belonging to a non-photosensitive layer, and those in which two or more layers are provided on both sides of the support with non-photosensitive layers interposed therebetween. Note that the surface of the support may be provided with a base layer belonging to a non-photosensitive layer, the outermost layer may be provided with a protective layer, and various other materials may be provided as long as performance is not degraded.

The hydrophilic colloid layer can be roughly divided into a photosensitive layer and a non-photosensitive layer. The photosensitive layer is typically a silver halide emulsion layer, and the non-photosensitive layers include an underlayer, an intermediate layer, a protective layer, and the like.

The layer containing the tetrazolium compound represented by the general formula (I) used in the present invention is a silver halide emulsion layer, and the layer containing the compound represented by the general formula (H) is the silver halide emulsion layer. A hydrophilic colloid layer adjacent to the emulsion layer.

In order to incorporate the tetrazolium compound represented by the general formula (I) and the compound represented by the general formula [■] used in the present invention into the hydrophilic colloid layer, both are dissolved in appropriate water and/or an organic solvent. Examples include a method in which a solution dissolved in an organic solvent is added after being dispersed in a hydrophilic colloid matrix such as gelatin or a gelatin derivative, or a method in which a solution is added after being dispersed in latex. The present invention may use any of these methods.

The tetrazolium compound represented by the general formula (1) used in the present invention may be used alone or in combination of two or more in an appropriate ratio. Furthermore, the tetrazolium compound of the present invention and the tetrazolium compound outside the present invention may be used in combination in an appropriate ratio. .

In the present invention, particularly favorable results can be obtained when an anion that binds to the tetrazolium compound used in the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and specifically lower alkylbenzenes such as p-1 luenesulfonic acid anions. Dialkyl sulfosuccinate anions such as sulfonate anions, p-dodecylbenzenesulfonate anions, alkylnaphthalenesulfonate anions, lauryl sulfate anions, tetraphenylborons, di-2-ethylhexylsulfosuccinate anions, etc. , polyether alcohol sulfate anions such as cetyl polyethenoxysulfate anions, stearate anions, and polyacrylate anions.

Such anions may be added to the hydrophilic colloid layer after being premixed with the tetrazolium compound of the present invention, or may be added alone to the silver halide emulsion layer or hydrophilic colloid containing or not containing the tetrazolium of the present invention. Can be added to the layer.

Silver halide used in the silver halide photographic light-sensitive material of the present invention
- Silver halide is not particularly limited, but silver chloride or silver chlorobromide is preferred. The composition of silver chlorobromide is 8 gcf
fi/AgBr=100/O~2/98, preferably AgC1/AgBr=
The molar ratio is 80/20 to 30/70. The average grain size of the silver halide grains is preferably 0.10 μm to 0.40 μm, and has a narrow grain size distribution with a coefficient of variation expressed by (standard deviation of grain size)/(average grain size) x lOO of 15% or less. is more preferable.

For the silver halide used in the present invention, various sensitizers, sensitizing dyes, stabilizers, etc. can be used.

The silver halide and tetrazolium compounds according to the present invention and the compound represented by the general formula (I[) are added to the hydrophilic colloid layer, and the hydrophilic colloid particularly advantageously used in the present invention is gelatin. . Hydrophilic colloids other than gelatin can also be used.

These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, storage layers, intermediate layers, etc.

As the support used in the present invention, various supports used in the photosensitive material industry, such as polyester films, can be used.

The photosensitive material of the present invention has a protective layer having an appropriate thickness, that is, preferably 0.1 to 10 μm, particularly preferably 0.8 to 2 μm.
Preferably, a gelatin protective layer of .mu.m is coated.

The hydrophilic colloid layer used in the present invention may optionally contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, astistein agents, pHtA adjusters, Antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc. can be used within the range that does not impair the effects of the present invention. .

The silver halide photographic material' containing the tetrazolium compound of the present invention and the compound represented by the general formula [■] is
It is preferable to develop with a developer containing a compound represented by the following general formula (III).

Represented by the general formula (I[[). M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion;) -a Specific compounds represented by formula (III) include 5-nitroindazole, 6-nitroindazole, etc. However, the present invention is not limited to this in any way.

The compound represented by the general formula (I It may be added to, or may be added as is.

The compound represented by the general formula (I[[) is contained in a concentration range of preferably about 1 to 1,000, more preferably about 50 to 300, per developer.

The developing agent used for developing the silver halide photographic light-sensitive material of the present invention includes T and H. The Theory of the Photographic Process by James, 4th Edition (T
the theory of the photograp
hic Process, Fourth Edition
n) pp. 291-334 and Journal of the American Chemical Society (Journal
of the American Chemical 5
73, page 3,100 (1951)
Developers such as those described in the following can be effectively used in the present invention. Even if these developers are used alone, 2
Although more than one type may be used in combination, it is preferable to use two or more types in combination. 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, and one of the effects of the invention will be improved. This can be mentioned as a characteristic. Also, hydroxylamine as a preservative,
A hydrazide compound may also be used. 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, and ethylenediaminetetraacetic acid. Metal ion scavengers such as methanol, ethanol, etc.
Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin,
It is optional to add a hardening agent such as glyoxal, an ionic strength regulator such as sodium sulfate, etc.

The developer used for developing the photosensitive material of the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamines mentioned above include monoethanolamine, jetanolamine, triethanolamine, etc., but triethanolamine is preferably used. The preferable amount of these alkanolamines used is 5 to 500 g per 12 of the developer, and more Preferably it is 20-200g.

In addition, the above glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 2 to 200 g per 12 of the developer. These organic solvents are
They can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention can be developed with the above developer to obtain a light-sensitive material with extremely excellent storage stability.

The pH value of the developer having the above composition is preferably 9 to 12, but from the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11.

The silver halide photographic material of the present invention can be processed under various conditions. The processing conditions are, for example, the development temperature is 5
The temperature is preferably 0″C or less, particularly preferably around 30°C,
In addition, it is common for the development time to be completed within 3 minutes, but it is particularly preferable that the development time is within 1 minute, which often brings good results. It is optional to employ steps such as preduralization and neutralization as needed, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕

Examples will be specifically shown below.

(Method for Preparing Emulsion (A)) A silver chlorobromide emulsion was prepared using the following solutions of liquid A, liquid B, and liquid C.

<Solution A><SolutionB><SolutionC> After keeping solution A at 40° C., sodium chloride was added so that the EAg value was 160 mv.

Next, solutions B and C were added by a double jet method using the mixer described in JP-A-57-92523 and JP-A-57-92524.

As shown in Table 2, the addition flow rate was gradually increased over a total addition time of 80 minutes, and addition was carried out while keeping EAg constant.

The EAg value was changed from 160 mv to 120 mv using an aqueous solution of sodium chloride of 3 mol/l 5 minutes after the start of addition, and this value was maintained thereafter until the completion of mixing.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol/Il aqueous sodium chloride solution.

To measure the EAg value, a metal silver electrode and a double junction type saturated Ag/AgC1 comparison electrode were used (the electrode configuration used was a double junction fusibon disclosed in JP-A-57-197534). .

Further, a variable flow rate roller tube metering pump was used to add solutions B and C.

Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system.

Also, during addition, 3% was added to keep the pH value of the system constant at 3.0.
It was controlled with a nitric acid aqueous solution.

After addition of solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, then desalted and washed with water in a conventional manner.
After dispersion by stirring at 55° C. for 30 minutes, the volume was adjusted to 750 cc.

Example 1 Emulsion (A) was enriched with gold and sulfur, and 6 was added as a stabilizer.
-Methyl-4-hydroxy-1,3,3a,7-titrazaindene was added and 1-(β-hydroxyethyl)-3-phenyl-5-[(3-α-sulfopropyl-α-pene) was added as a sensitizing dye. 150 mg of zooxazolidene)-ethylidene cothiohydantoin was added per mole of silver halide contained in the emulsion.

Next, the compound of general formula (1) was added as shown in Table 3 per mole of silver halide, and 300 mg of sodium p-dodecylbenzenesulfonate, 2 g of styrene-maleic acid copolymer I polymer, and styrene-butyl acrylate were added.
Acrylic acid copolymer latex (average particle size approximately 0.25μ
m) Add 15g and Agf! 3.5 g/rd, gelatin amount 2.0 g/rrr
It was coated on a subbed polyethylene terephthalate film base as described in Example (1) of Publication No. 41. Gelatin then! As a spreading agent so that the amount is 1.0g/bo,
1-decyl-2-(3-isopentyl)succinate-
Sodium 2-sulfonate was added at 30 μ/rrf, and the compound of general formula (II) as shown in Table 2 was added per mole of silver halide, and a protective layer containing 25 μ/rr of formalin as a hardening agent was simultaneously layered. Coated. The samples obtained as described above are shown in Table 2.

Each of the obtained samples was divided into two parts, and the other half was exposed to light using a tungsten light source using a wedge.

The other half was exposed to light at a density of 1.0.

The above test sample was processed in an automatic processor using a developer and a fixer having the following formulation.

Table 3 <Development processing conditions> (Process) (Temperature) (Time) Development 28
Fixation at 30 °C for 30 seconds Washing at 28 °C for about 20 seconds Dry at room temperature for about 20 seconds 50'C for 15 seconds (composition A) (Composition) When using a developer, dissolve the above composition A in the order of 12 in 500 d of water. I finished it and used it.

<Fixer Prescription> (Composition A) (Composition) When using a fixer, the above composition A was dissolved in 500% water in that order, and the composition was finished to 1j2. This fixer p
H was approximately 4.3.

Photographic characteristic curves were drawn for the developed samples, and the contrast was expressed as a gamma value with respect to the exposure amount giving optical densities of 0.2 and 1.5. Further, as a measure of anxiety in image density due to non-uniform development, unevenness in a sample with a density of 1.0 was sensory evaluated. Rank 3 indicates the lower limit accepted in the industry, and rank 5 indicates a level at which there is no problem at all.

The results are summarized in Table 4.

For comparison, the following compound (A) was added.

Comparative Compound (A) O ε・ㅅ,・Table 4 As is clear from Table 4, sample No. 013 belongs to the present invention.
It can be seen that ~Nα22 has a good contrast of 25 to 27, and development unevenness has a rank of 4 or 5, which is at a level suitable for practical use. On the other hand, sample kl, 2.23 in Table 4, which belongs to Comparative Examples, had a poor contrast of 7 or a poor development unevenness of rank 2, and was not suitable for practical use.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which has high contrast and reduces unevenness in image density due to uneven development during development.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains at least one compound represented by the following general formula [I]. 1. A silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula [II] in a hydrophilic colloid layer adjacent to the emulsion layer. 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, Y_1 and Y_2 represent a hydrogen atom or a mercapto group, and R^4 Substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkoxy group, or hydrogen atom, halogen atom, nitro group, amino group, cyano group, hydroxycarbonyl group, alkoxycarbonyl group, alkylcarbonyl group, hydroxy group , represents a mercapto group or a sulfo group. Also, A represents a nitrogen atom, a carbon atom or an oxygen atom, and B
represents a nitrogen atom or a carbon atom. When A represents a carbon atom, n_2 is 2, and when A represents a nitrogen atom, n_2 is 2.
_2 is 1, and when A represents an oxygen atom, n_2 is 0
It is. Further, when B represents a carbon atom, n_1 is 1, and when B represents a nitrogen atom, n is 0. ]