JP2805248B2 - Silver halide photographic material with improved pressure resistance - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material capable of obtaining a high contrast image.

BACKGROUND OF THE INVENTION In the photomechanical process, a continuous tone original image is converted into a halftone image, that is, a continuous tone density change is converted into a halftone dot aggregate having an area proportional to the density. The method includes a step and a step of converting a halftone image obtained in the step into a halftone image having better sharpness, that is, a returning step.

It is indispensable that the photosensitive material used in these steps has a high contrast in order to obtain good halftone dot quality.

As a method of obtaining such characteristics, a photosensitive material comprising a silver chlorobromide emulsion having a relatively fine particle size, a narrow particle size distribution, and a high silver chloride content has been conventionally used in an alkali hydroquinone developer having a very low sulfite concentration. A so-called lith developing method is known.

However, when this method is used, the preservability is extremely poor due to the low sulfite ion concentration in the developing solution, and rapid processing cannot be performed due to the use of a hydroquinone simple substance.

In recent years, it has been desired that rapid processing is possible in order to shorten the processing time even in a photosensitive material capable of obtaining such a high contrast.

In addition, from the viewpoint of effective use of silver resources, it is also desired to save silver.

The present inventors have tried to reduce the amount of gelatin used in the light-sensitive material in order to obtain a light-sensitive material capable of rapid processing, saving silver, and obtaining high contrast. It has been found that a decrease in the resistance causes a new problem that the pressure resistance deteriorates.

[Object of the Invention] Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of rapid processing, having excellent pressure resistance, and capable of obtaining a high-contrast image and capable of saving silver.

[Constitution of the Invention] The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer as a photographic constituent layer on a support. The total amount of gelatin in the constituent layer is 2.3 g / m ² or less, and at least one compound represented by the following general formula [I] or [II] is added to the photographic constituent layer containing the hydrophilic colloid. And a hydrazine compound.

Wherein R ¹ and R ² are each a hydrogen atom, an alkyl group,
—COOM, —SO ₃ M, —OH, —CONHR ³ or —NHCOR ³ represents each group. However, at least one of R ¹ and R ² is
—COOM, —SO ₃ M, —OH, —CONHR ³ or —NHCOR ³ group. R ³ represents an alkyl group.

M represents a hydrogen atom, an alkali metal atom or a —NH ₄ group, and Y represents an oxygen atom, a sulfur atom, a selenium atom or Represents ] Was achieved.

 Hereinafter, the present invention will be described in detail.

First, the compounds represented by the general formulas [I] and [II] will be described.

In the general formulas [I] and [II], R ¹ and R ²
The alkyl group represented by is preferably a lower alkyl group, and specific examples include a methyl group and an ethyl group.

Also, as the alkyl group represented by R ³ , a lower alkyl group is preferable, and specific examples include a methyl group and an ethyl group.

In the general formulas [I] and [II], R ¹ and R ²
At least one _{of, -COOM, -SO 3 M, -OH} , -CONHR 3
Alternatively, it needs to be a —NHCOR ³ group.

Examples of the alkali metal represented by M include potassium, sodium, and lithium.

Hereinafter, specific examples of the compounds represented by the general formulas [I] and [II] are shown, but the invention is not limited thereto.

These exemplified compounds can be easily obtained by a known method. For example, The chemistry of heterocyclic compounds (Imidazole and Derivatives)
imidazole and derivatives), Vol. 1, page 384, or can be easily synthesized according to the method.

The compound represented by the general formula [I] or [II] of the present invention is preferably used in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and preferably 1 × 10 ^-5. More preferably, it is used in the range of 1 to ^10-2 mol.

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer as a photographic constituent layer on a support.

In the present invention, a hydrophilic colloid layer such as a silver halide emulsion layer, an undercoat layer, an intermediate layer, and a protective layer may be provided as a photographic constituent layer.

The silver halide emulsion layer may be coated directly on the support, or may be coated via a hydrophilic colloid layer containing no silver halide emulsion. Further, a hydrophilic colloid layer may be further provided as a protective layer on the silver halide emulsion layer.

Further, the silver halide emulsion layer may be provided by dividing into two or more silver halide emulsion layers, for example, a high-sensitivity and a low-sensitivity silver halide emulsion layer. In this case, a hydrophilic colloid layer may be provided as an intermediate layer between the two or more silver halide emulsion layers. Further, an intermediate layer may be provided between the silver halide emulsion layer and the protective layer.

The layer containing the compound represented by the general formula [I] or [II] of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and / or a layer adjacent to the silver halide emulsion layer. It is a hydrophilic colloid layer.

In the present invention, the total amount of gelatin in the photographic constituent layer on the side having the silver halide emulsion layer refers to the sum of the amount of gelatin in all the photographic constituent layers on one side having the silver halide emulsion layer. Is 2.3 g / m
² or less.

In order for the compound represented by the general formula [I] or [II] of the present invention to be contained in the hydrophilic colloid layer, the compound of the general formula [I] or [II] is dissolved in an appropriate water and / or organic solvent. A method in which a solution dissolved in an organic solvent is dispersed in a hydrophilic colloid matrix of gelatin or a gelatin derivative and then added, or a method in which the solution is dispersed in latex and added.

The silver halide photographic light-sensitive material of the present invention contains a hydrazine compound. Examples of the hydrazine compound include a compound represented by the following general formula [H].

In the formula, R ₁ represents a monovalent organic group, R ₂ represents a hydrogen atom or a monovalent organic group, Q ₁ and Q ₂ represent a hydrogen atom or an alkylsulfonyl group (including those having a substituent), Represents an arylsulfonyl group (including those having a substituent), and X ₁ represents an oxygen atom or a sulfur atom.

Among the compounds represented by the general formula [H], a compound in which X ₁ is an oxygen atom and R ₂ is a hydrogen atom is particularly preferable.

As the monovalent organic group for R ₁ and R ₂ , an aromatic group,
Heterocyclic groups and aliphatic groups can be mentioned.

Examples of these aromatic groups include a phenyl group, a naphthyl group, and the like. These groups include a substituent (an alkyl group, an alkoxy group, an acylhydrazino group, a dialkylamino group,
Alkoxycarbonyl group, cyano group, carboxy group, nitro group, alkylthio group, hydroxy group, sulfonyl group, carbamoyl group, halogen atom, acylamino group,
A sulfonamide group, a urea group, a thiourea group, etc.).

Specific examples of the aromatic group having a substituent include, for example,
4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-
Carboxyphenyl group, 4-diethylaminophenyl group, 4-octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4- (3-ethylthioureido) phenyl group, 4-
[2- (2,4-di-tert-butylphenoxy) butylamido] phenyl group and 1,1-dibenzylsemicarbazide group can be exemplified.

Examples of the heterocyclic group include a 5- or 6-membered monocyclic or condensed-ring heterocyclic group having at least one of oxygen, nitrogen, sulfur, and selenium atoms, and these groups may have a substituent May be provided.

Specifically, for example, a pyrroline ring, a pyridine ring, a quinoline ring, an indole ring, an oxazole ring, a benzoxazole ring, a benzothiazole ring, a naphthoxazole ring, an imidazole ring, a benzimidazole ring, a thiazoline ring, a thiazole ring, and a naphthothiazole ring , A selenazole ring, a benzoselenazole ring and a naphthoselenazole ring. Examples of the substituent which these groups may have include an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group; Examples thereof include an aryl group having 6 to 18 carbon atoms such as a group, a halogen atom such as chlorine or bromine, an alkoxycarbonyl group, a cyano group, and an amino group.

As the aliphatic group, a linear or branched alkyl group,
Mention may be made of cycloalkyl groups and those groups having substituents, as well as alkenyl groups and alkynyl groups.

Examples of the straight-chain and branched-chain alkyl groups include, for example, alkyl groups having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, an isobutyl group, and a 1-octyl group. And the like.

Examples of the cycloalkyl group include a cycloalkyl group having 3 to 10 carbon atoms, and specific examples include a cyclopropyl group, a cyclohexyl group, and an adamantyl group.

Examples of the substituent which the alkyl group and the cycloalkyl group may have include an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group and a butoxy group), an alkoxycarbonyl group, a carbamoyl group, a hydroxy group, an alkylthio group, and an amide group. Group, acyloxy group, cyano group, sulfonyl group, halogen atom (for example, chlorine, bromine,
Fluorine and iodine), an aryl group (for example, a phenyl group,
Halogen-substituted phenyl group and alkyl-substituted phenyl group).

Specific examples of the substituted alkyl group and cycloalkyl group include, for example, 3-methoxypropyl group, ethoxycarbonylmethyl group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, p-chlorobenzyl group and the like. Can be mentioned.

Examples of the alkenyl group include an allyl group, and examples of the alkynyl group include a propargyl group.

Preferred specific examples of the hydrazine compound used in the present invention are shown below.

In the present invention, the hydrazine compound is added to the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer on the side of the silver halide emulsion layer, but is added to the silver halide emulsion layer and / or a layer below the silver halide emulsion layer. Is preferred.

The amount of the hydrazine compound to be added is preferably 1 × 10 ^-5 to 1 × 10 ^-1 mol / mol of silver, more preferably 1 × 10 ^-4 to 1 mol.
× 10 ^-2 mol / mol of silver.

Next, the silver halide used in the silver halide photographic light-sensitive material of the present invention will be described.

As the silver halide preferably used in the present invention,
For example, 4 mol% or less of silver iodide, more preferably 3 mol%
The following silver iodobromide or silver iodobromide containing silver iodide can be mentioned.

The average diameter of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, and particularly preferably 0.10 to 0.40 μm.

The particle size distribution of the silver halide grains used in the present invention is arbitrary, but preferably has a monodispersity of 1 to 20%, more preferably 5 to 15%.

Here, the monodispersity is defined as a value (%) obtained by multiplying a value (coefficient of variation) obtained by dividing the standard deviation of the particle size by the average particle size by 100. The grain size of silver halide grains is represented by a ridge length in the case of cubic grains, and other grains (octahedral,
In the case of a tetrahedron, etc., it is represented by the square root of the projected area.

In practicing the present invention, for example, silver halide grains having a multilayer structure of at least two layers may be used. At least two of these
Examples of the type having a multilayered structure of layers include silver iodobromide grains having a core portion of silver iodobromide and a shell portion of silver bromide. Further, iodine can be contained in any layer of the multilayer structure within 5 mol%.

In the silver halide grains used in the silver halide emulsion of the present invention, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), Metal ions can be added using at least one selected from rhodium salts (including complex salts) and iron salts (including complex salts), and these metal elements can be contained inside the particles and / or on the surface of the particles, Also,
By placing in a suitable reducing atmosphere, the inside of the particles and / or
Alternatively, reduction sensitization can be imparted to the surface of the grains.

Furthermore, silver halide can be sensitized by various chemical sensitizers.

Examples of the chemical sensitizer include active gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiacinate, etc.), selenium sensitizer (N, N
Dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, stannous chloride, etc.) such as potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, Various noble metal sensitizers represented by ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite and the like can be used alone or in combination of two or more. When a gold sensitizer is used, rhodamonmon can be used as an auxiliary agent.

The silver halide emulsion used in the present invention may be a mercapto compound (1-phenyl-5-mercaptotetrazole,
-Mercaptobenzthiazole, etc.), benzotriazoles (5-bromobenzotriazole, 5-methylbenzotriazole, etc.), and benzimidazoles (6-nitrobenzimidazole, etc.) can be used to stabilize or suppress fog. .

In the silver halide emulsion layer or its adjacent layer, the sensitivity is increased,
Research Disclosure 17463, XXI for the purpose of increasing contrast or accelerating development
The compounds described in the sections B to D can be added.

The silver halide emulsion used in the present invention may contain a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener, and the like.

When the hydrazine compound of the present invention is added to a hydrophilic colloid layer, gelatin is suitable as a binder for the hydrophilic colloid layer, but a hydrophilic colloid other than gelatin can also be used.

As the support, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, for example, a polyester film such as polyethylene terephthalate can be used. It is appropriately selected according to the purpose of use of the photosensitive material.

For the development processing of the silver halide photographic light-sensitive material of the present invention, for example, the following developing agents are used.

HO- (CH = CH) _n -OH-type developing agent Representative examples include hydroquinone, and catechol and pyrogallol.

HO- (CH = CH) _n -NH ₂ type developer Ortho and para aminophenols or aminopyrazolones are typical, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol , P-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Heterocyclic developer 1-phenyl-3-pyrazolidone, 1-phenyl-4,
4-dimethyl-3-pyrazolidone, 1-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
And 3-pyrazolidones such as pyrazolidone.

In addition, The James of the Theory of the James
Photographic Process 4th Edition (The Theory of th
e Photographic Process, Fourth Edition) 291-334
And Journal of the American Chemical Societ
y) Developers described in Vol. 73, p. 3, 100 (1951) can also be effectively used in the present invention.

These developing agents may be used alone, but it is preferable to use two or more of them in combination.

Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in a developer used for developing the light-sensitive material of the present invention, the effect of the present invention is not impaired. Further, a hydroxylamine or a hydrazide compound may be used as a preservative. In addition, it can have a pH adjustment and a buffer function with a caustic alkali such as sodium hydroxide or potassium hydroxide, an alkali carbonate or an amine used in a general black-and-white developer.

The light-sensitive material of the present invention can be developed using a developer having a pH of less than 11.

Further, in the developer, an inorganic development inhibitor such as bromkari and an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, ethylenediamine Metal ion scavengers such as tetraacetic acid, methanol, ethanol, benzyl alcohol, development accelerators such as polyalkylene oxide, sodium alkylaryl sulfonate, natural saponin,
It is optional to add a surfactant such as a saccharide or an alkyl ester of the compound, a hardening agent such as glutaraldehyde, formalin or glyoxal, or an ionic strength modifier such as sodium sulfate.

The developer used for developing the light-sensitive material of the present invention includes, as an organic solvent, alkanolamines such as diethanolamine and triethanolamine and diethylene glycol,
Glycols such as triethylene glycol may be contained. Alkylamino alcohols such as diethylamino-1,2-propanediol and butylaminopropanol can be particularly preferably used.

[Examples] Specific examples of the present invention will be described below.
It is not limited by these examples.

Example (Preparation of Silver Halide Emulsion) A mixed aqueous solution of potassium iodide and potassium bromide and an aqueous solution of silver nitrate were stirred at a temperature of 50 ° C., a pAg of 7.8 and a pH of 2.0, and the addition flow rate was controlled. While adding to the aqueous gelatin solution and mixing. During this mixing, 8 × 10 _-7 mol of K ₂ IrCl ₆ was added per mol of silver. To this emulsion was added 6.5 cc of a 1% aqueous solution of potassium iodide per mole of silver, and then modified gelatin (exemplified compound G-8 described in Japanese Patent Application No. 1-180787). Example 1 described in
Water washing and desalting were performed in the same manner as described above. PAg at 40 ° C after desalting
Was 8.0.

The finally obtained emulsion was a silver bromoiodide emulsion (containing 2 mol% of silver iodide) composed of cubic grains having an average grain size of 0.20 μm.

(Preparation of silver halide photographic material) One undercoat layer of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On top of this, a silver halide emulsion layer having the composition shown in the following formula (1) was provided, and further thereon, an emulsion protective layer having the composition shown in the following formula (2) was provided. On the other undercoat layer, the following formulation (3)
A backing layer of the composition shown in is applied, and further thereon,
Sample Nos. 1 to 30 were obtained by coating a backing protective layer having the composition shown in the following formulation (4).

A step wedge was adhered to the obtained sample and exposed to tungsten light of 3200 ° K for 5 seconds. Then, using a developing solution and a fixing solution having the following composition, a processing was performed by an automatic developing machine for rapid processing under the following conditions. Then, the developed silver amount and gamma were measured.

Gamma is specified in a density range of 0.3 to 3.0.

When the gamma is 5 or less, the thin line is broken, and practical use is difficult.

(Processing conditions) (Process) (Temperature) (Time) Current 40 ° C 15 seconds Fixed 35 ° C 15 seconds Rinse 30 ° C 10 seconds Dry 50 ° C 10 seconds Developer formulation Ethylenediaminetetraacetic acid disodium salt 1 g Sodium sulfite 60 g Hydroquinone 22.5 g Sodium hydroxide 8.0 g 3- (dimethylamino) -1,2-propanediol 30 g Sodium bromide 3.0 g 5-Methylbenzotriazole 0.1 g 1-Phenyl-5-mercaptotetrazole 0.08 g 1- Phenyl-4,4-dimethyl-3-pyrazolidone 0.2 g /
m ² water was added to 1 and the pH was adjusted to 10.7 with sodium hydroxide.
Adjust to

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g (Composition B) Pure water (ion exchange water) 17 ml sulfuric acid (50% w / w aqueous solution) 4.7 g aluminum sulfate (aqueous solution with 8.1% w / w content in terms of Al ₂ O ₃ ) 26.5 g The above composition A and composition B in 500 ml of water when using a fixing solution
Was added in the order of composition A and composition B, and finished to 1 for use.
The pH of the fixing solution was adjusted to 4.8 with acetic acid.

 The pressure resistance was evaluated as described below.

Evaluation of pressure resistance After a 95% net image was taken of each sample, the exposed sample was bent at a constant pressure and developed. A sample having a large change in density due to pressurization was ranked 1 and a sample without a change in density was ranked 10 and evaluated on a 10-point scale.

 Rank 4 is a practically problematic level.

 Table 4 shows the results.

From the results in Table 4, it can be seen that the sample of the present invention is excellent in pressure resistance and hard in contrast to the comparison.

[Effects of the Invention] According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having excellent pressure resistance, effectively developing silver in the light-sensitive material, and obtaining a high contrast image even in ultra-rapid processing. Was.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-61-222642 (JP, A) JP-A-2-3031 (JP, A) JP-A-2-129626 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03C 1/06 501 G03C 1/047

Claims (1)

(57) [Claims] In a silver halide photographic material having at least one silver halide emulsion layer as a photographic constitutional layer on a support, the amount of gelatin in the photographic constitutional layer on the side having the silver halide emulsion layer is determined. The total amount is 2.3 g / m ² or less, and the photographic constituent layer containing the hydrophilic colloid contains at least one compound represented by the following general formula [I] or [II]; A silver halide photographic material characterized by containing a compound. Wherein R ¹ and R ² are each a hydrogen atom, an alkyl group,
COOM, representing each group of -SO ^₃ M, -OH, -CONHR ₃ or -NHCOR ^3. However, at least one of R ¹ and R ² is-
COOM, —SO ₃ M, —OH, —CONHR ³ or —NHCOR ³ group. R ³ represents an alkyl group. M represents a hydrogen atom, an alkali metal atom or a —NH ₄ group, and Y represents an oxygen atom, a sulfur atom, a selenium atom or Represents ]