JP2995362B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having high sensitivity and high covering power, which prevents fogging during the running development of a silver halide photographic material containing a covering power improver. It relates to a photosensitive material.

[0002]

BACKGROUND OF THE INVENTION Increasing the covering power (covering power) of a silver halide emulsion is considered to be a very important technique because it can reduce the amount of silver required for obtaining a constant optical density.

Conventionally, for example, US Pat. Nos. 4,411,986, 4,434,226 and 4,413,053 disclose tabular grains having a high aspect ratio and a small grain thickness to improve the developing silver covering power.

[0004] Many compounds are also known as covering power improvers, such as dextran disclosed in JP-A-2-212833 or a water-soluble polymer disclosed in JP-A-2-298938.

Therefore, the use of the above-described covering power improver in a tabular silver halide emulsion having a high covering power is extremely advantageous for a silver halide photographic material.

However, in general, when a film containing a covering power improver is subjected to a large amount of running processing by an automatic developing machine, there has been a problem that fog increases as the number of processed sheets increases. In particular, in the case of a film using a hydrophilic compound such as dextran or a water-soluble polymer as a covering power improver, fogging was remarkable.

Therefore, the present inventors screened various antifoggants. However, in order to obtain a sufficient antifoggant effect, a large amount of addition is required, resulting in a significant decrease in sensitivity and no desensitization. The development of fog suppression technology has been desired.

[0008]

Accordingly, an object of the present invention is to provide a silver halide photographic material containing dextran or a water-soluble polymer represented by the above general formula [II], which has a high covering power and a running development process. Accordingly, it is an object of the present invention to provide a silver halide photographic material which is free from fogging, has high sensitivity and good developability.

[0009]

The above object of the present invention is achieved by the following.

That is, in a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on at least one side of a support, the silver halide emulsion layer has the following general formula [I]: Halogen containing at least one compound represented by the following general formula [II] and / or dextran in the silver halide emulsion layer and / or another layer: This is achieved by a silver halide photographic material.

[0011]

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R ₁ and R ₂ in the formula may be the same or different, and may be a hydrogen atom, an alkyl group, an alkenyl group,
Represents an aryl group.

R ₁ and R ₂ may combine with each other to form a nitrogen-containing heterocyclic ring. M _1, M ₂ represents a hydrogen atom or an alkali metal atom, an ammonium arm.

[0014]

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[0015]

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Hereinafter, the present invention will be described in detail.

In the general formula [I], R ₁ and R ₂ may be the same or different and each represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. However, the alkyl group, alkenyl group and aryl group include those having a substituent.

R ₁ and R ₂ may be bonded to each other to form a nitrogen-containing heterocyclic ring, such as a pyrrolidine ring and a morpholine ring.

M ₁ and M ₂ are a hydrogen atom or an alkali metal atom
(E.g. Na salt, etc. K salt) or an ammonium beam.

The alkyl group represented by R ₁ and R ₂ may be linear, branched or cyclic and preferably has 1 to 1 carbon atoms.
Up to 12, for example, methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, groups and the like.

Preferred examples of the substituted alkyl group include a halogen atom (eg, chlor, bromide, fluorine atom, etc.), a hydroxyl group, a carboxyl group, and a C6 group.
To 12 monocyclic or bicyclic aryl groups (this aryl group may be substituted with an alkyl group having up to 4 carbon atoms, a nitro group, a halogen atom, or the like).

The alkenyl group is an alkenyl group having up to 12 carbon atoms, preferably an alkenyl group containing only one unsaturated bond, such as an allyl group and a 2-butenyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and these aryl groups may have the same substituent as the above-mentioned alkyl group.

Hereinafter, specific examples of the compound represented by the general formula [I] of the present invention are shown, but the present invention is not limited thereto.

Examples of Specific Compounds Represented by General Formula [I] No. Compound I-1 2-Amino-4,6-dimercapto-1,3,5-triazine I-2 2-Methylamino-4,6 -Dimercapto-1,3,5-triazine I-3 2-Ethylamino-4,6-dimercapto-1,3,5-triazine I-4 2-Amino-4,6-dimercapto-1,3,5- Triazine Na salt I-5 2-Pentylamino-4,6-dimercapto-1,3,5-triazine I-6 2-Octylamino-4,6-dimercapto-1,3,5-triazine I-7 2- Chloroethylamino-4,6-dimercapto-1,3,5-triazine I-8 2-Cyanoethylamino-4,6-dimercapto-1,3,5-triazine I-9 2-acetoxyethylamino-4,6 -Dimercapto-1,3,5-triazine I-10 2-Dimethylamino-4,6-dimercapto-1,3,5-triazine I-11 2-Dipropylamino-4,6-dimercapto-1,3, 5-triazine I-12 2-di-tert-butylamino-4,6-dimercapto-1,3,5- Triazine I-13 2-N- ethyl - N- isoamyl-4,6-dimercapto-1,3,5-triazine I-14 2-pyrrolidino-4,6-dimercapto-1,3,5-triazine I- 15 2-morpholino-4,6-dimercapto-1,3,5-triazine I-16 2-N-methylanilino-4,6-dimercapto-1,3,5-triazine I-17 2-O-tolylamino-4 , 6-Dimercapto-1,3,5-triazine I-18 2-N, N-diphenylamino-4,6-dimercapto-1,3,5-triazine I-19 2-anilino-4,6-dimercapto- 1,3,5-triazine I-20 2- (2,5-xylamino) -4,6-dimercapto-1,3,5-triazine Na salt I-21 2-naphthylamino-4,6-dimercapto-1 , 3,5-Triazine I-22 2-benzylamino-4,6-dimercapto-1,3,5-triazine I-23 2-p-methoxyphenylamino-4,6-dimercapto-1,3,5- Triazine I-24 2-benzidino-4,6-dimercapto-1,3,5-triazine I-25 2-N-ethylanilino-4,6-dimercap -1,3,5-triazine sodium salt I-26 2-N-ethyl-P-tolylamino-4,6-dimercapto-1,3,5-triazine I-27 2-P-chloroanilino-4,6-dimercapto -1,3,5-triazine I-28 2-cyclopentylamino-4,6-dimercapto-1,3,5-triazine I-29 2-N, N-dicyclohexylamino-4,6-dimercapto-1,3 , 5-Triazine I-30 2-N, N-diallylamino-4,6-dimercapto-1,3,5-triazine I-31 2-N-propenylamino-4,6-dimercapto-1,3,5 -Triazine I-32 2-N-methoxybenzoic acid amino-4,6-dimercapto-1,3,5-triazine

Hereinafter, specific examples of the synthetic water-soluble polymer having a repeating unit represented by the general formula [II] of the present invention are shown, but the present invention is not limited thereto.

The numerical values shown on the right side of the chemical formula are the degree of polymerization and the number average molecular weight of the polymer.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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The water-soluble polymer has a molecular weight of 1,000 to 1
It may be 00,000, preferably 2,000 to 50,000.

These polymers may be added to any of the layers constituting the silver halide photographic light-sensitive material of the present invention.
For example, it may be used for a silver halide emulsion layer, a protective layer, an intermediate layer, an antihalation layer, a filter layer, an antistatic layer and the like, and preferably in a photosensitive silver halide emulsion layer.

The amount of addition may be at least 3% by weight of the total amount of binder in the silver halide emulsion layer, and preferably at least 5% to 30%.
% Or less.

Next, dextran used in the present invention will be described. The dextran according to the present invention preferably has a weight average molecular weight of 10,000 to 300,000, preferably 5,000 to 100,000, more preferably 20,000 to 70,000.

Specifically, the following Dextran Chemical Pure
(Tomen Chemical Sales Co., Ltd.), which can be easily obtained.

(A) Dextran 40,000 (B) Dextran 70,000 (C) Dextran 110,000 These dextrans may be added to any of the layers constituting the silver halide photographic light-sensitive material of the present invention. Protective layer, intermediate layer, antihalation layer,
It may be used for a filter layer, an antistatic layer and the like, and preferably a photosensitive silver halide emulsion layer.

The amount of addition may be from 5 to 50% by weight, preferably from 15 to 30% by weight, of the total amount of binder in the silver halide emulsion layer. In addition, it may be used in combination with the above-mentioned water-soluble polymer, and in that case, the amount of addition may be appropriately selected.

The timing of adding the covering power improver according to the present invention to the emulsion may be at any time during the emulsion production process.
Preferably, it may be added during chemical ripening or at an appropriate stage after completion of chemical ripening.

The silver halide emulsion of the silver halide photographic light-sensitive material of the present invention may be silver bromide, silver iodobromide, or a silver iodochlorobromide emulsion containing a small amount of silver chloride. Is a silver iodobromide emulsion containing 0 to 4 mol% of silver iodide.

The halogenated grains may be of any crystal type, for example, may be single crystals such as cubic, octahedral, or tetrahedral, and may be polytwin grains having various shapes. There may be.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22
~ 23, or the method described in (RD) No. 18716 (November 1979), page 648, described in "Emulsion Preparation and Types".

Emulsions used in the silver halide photographic light-sensitive material of the present invention are described in, for example, "The Theory of the
Photographic process ”4th edition, published by Macmillan (1977
The method described on pages 38-104, GFDuffin, “Photograph
ic Emulsion Chemistry ”, Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Paul Montel (1967) or VLZelikman et al. “Makin
g And Coting Photographic Emulsion "by Focal Press (1964).

That is, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, and a control double jet method under solution conditions such as an acidic method, an ammonia method, and a neutral method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is present inside the grains. Monodisperse here means, when the average particle diameter is measured by an ordinary method,
Silver halide grains in which at least 95% of the grains by number or weight are within ± 40%, preferably ± 30% of the average grain size.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a core portion of high silver iodide is covered with a shell layer of low silver iodide may be used.

The method for producing the above-mentioned monodispersed emulsion is known.
J. Phot. Sci, 12.242-251, (1963), JP-A-48-36890,
Nos. 52-16364, 55-142329, 58-49938, British Patent 1,413,748, U.S. Pat. Nos. 3,574,628, and 3,655,394.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is prepared by, for example, using a seed crystal as a method for obtaining the above monodisperse emulsion, and supplying silver ions and halide ions using the seed crystal as a growth nucleus. An emulsion that has been grown may be used. The method for producing the above-mentioned core / shell type emulsion is known, for example, J. Phot. Sci, 24.198. (1976), U.S. Pat.
Nos. 3,505,068, 4,210,450, 4,444,877 and JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain diameter / grain thickness) of 3 or more. The advantages of such tabular grains are disclosed in, for example, British Patent No. 2,112,157, U.S. Patent Nos. 4,414,310, and 4,434,226, as they can improve spectral sensitization efficiency and improve image graininess and sharpness. Emulsions can be prepared by the methods described in these publications.

The emulsions described above are either of a surface latent image type in which a latent image is formed on the grain surface, an internal latent image type in which a latent image is formed inside the grain, or a latent image type in which a latent image is formed on both the surface and inside. It may be an emulsion.

These emulsions may be used at the stage of physical ripening or grain preparation, for example, using cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof. You may.

The emulsion may be subjected to a Nudel washing method or a flocculation sedimentation method to remove soluble salts. Preferred examples of the washing method include aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin and a desalting method using G-3, G-8, etc., which are polymer flocculants described in JP-A-63-158644.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. As the compound used in such a step, for example, the aforementioned (RD) No. 1
7643, (RD) No. 18716 and various kinds of compounds described in (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 page classification page page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV desensitizing dye 23 IV
998 B dye 25-26 VIII 649-650 1003
VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 left 1004-5 X Surfactant 26-27 XI 650 right 1005 ~ 6 XI plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII Used in the silver halide photographic light-sensitive material of the present invention. Examples of the support include those described in the above RD,
A suitable support may be a plastic film or the like, and the support surface may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The photographic processing of the light-sensitive material of the present invention can be performed, for example, by the above-mentioned RD-17643 XX to XXI, pp. 29 to 30 or 308119 to XX to XXI.
XI, pages 1011 to 1012, may be treated with a processing solution. This processing may be either black-and-white photographic processing for forming a silver image or color photographic processing for forming a dye image. The processing temperature is usually in the range of 18 ° C to 50 ° C.

As a developer in black-and-white photographic processing, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), and aminophenols (for example, N-methyl-P-aminophenol) Etc. can be used alone or in combination. In the developer, for example, known preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants,
An antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

When a dye is formed by color photographic processing, for example, a color processing such as a negative-positive method or a color reversal method may be performed. Color developers are phenylenediamines such as primary aromatic amine developers known as color developing agents (e.g., 4-amino-N, N-dimethylaniline,
4-amino-3-methyl-N, N-diethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline, etc.) can be used.

Known color developing solutions include, for example, preservatives, organic solvents, pH buffering agents, antifoggants, development accelerators, surfactants, defoamers, water softeners, polycarboxylic acid type chelating agents, It may contain an antioxidant and the like.

After color development, a normal bleaching process may be performed, or a bleach-fixing process in which bleaching is performed simultaneously with fixing.

[0061]

EXAMPLES The present invention will be described below with reference to specific examples, but embodiments of the present invention are not limited thereto.

Example 1 Silver iodide 2 mol% prepared by double jet method, average grain size
The 0.6 μm silver iodobromide monodisperse emulsion was chemically ripened by the optimal gold and sulfur sensitization method. Then the following spectral sensitizing dye
(a) and (b) were added in appropriate amounts to ortho-sensitize and
-6-Methyl-1,3,3a, 7-tetrazaindene was added to obtain a photosensitive emulsion.

(A): 5,5'-dichloro-9-ethyl-3,3'-di-
(3-sulfopropyl) oxacarbocyanine sodium salt anhydride (b): 5,5′-di- (butoxycarbonyl) -1,1′-diethyl-
Anhydrous 3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt Then, the emulsion was divided into 21 parts, and as shown in Table 1 below, each of the CP improvers according to the present invention was Dextran and the compound of the general formula [II] were added, followed by the fog inhibitor of the general formula [I] and a comparative fog inhibitor.

To each emulsion, an appropriate amount of sodium-isoamyl-n-decyl-sulfosuccinate was added as a coating aid to prepare an emulsion coating solution.

A gelatin solution containing the following was prepared as a coating solution for the protective layer. The amount added is the amount per 1 g of gelatin.

Polymethyl methacrylate (matting agent having an average particle size of 7 μm) 25 mg Colloidal silica (average particle size 0.013 μm) 70 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 48 mg Bis-vinylsulfonyl methyl ether 36 mg As samples according to the present invention, Sample Nos. 20 and 21 are CP
This is a sample obtained by adding an enhancer to a protective layer.

[0067]

[Table 1]

[0068]

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The coating solution obtained was uniformly coated on both sides on a polyethylene terephthalate film base having a thickness of 180 μm and having been subjected to an undercoating process and colored blue to prepare samples as shown in Table 1. The amount of silver applied per side was 2 g / m
² , the amount of gelatin was 2.2 g / m ^{2 for} the emulsion layer and 1.2 g / m ^{2 for} the protective layer.
^It adjusted so that it might become ² , and applied.

The performance of the obtained sample was evaluated. The development was carried out as follows.

[0071] developer XD-SR in an automatic developing machine SRX-501, as a static <br/> COMPUTER XD-SR · S, XF- SR as a fixing solution (both manufactured by Konica Corporation]) Processing was performed in a 45 second mode with development at 35 ° C. and fixing at 33 ° C.

After preparing the developer XD-SR, the concentration was ±
A liquid obtained by treating 10 sheets of a quarter-cut film which was exposed to the entire surface so as to be 1.1 was used as a new liquid. Also, a developing solution in which each film prepared in this example was processed into 1,000 sheets in terms of quarters
XD-SR was prepared and used as a developer for measuring covering power (CP). Similarly, processing was performed at a rate of 100 sheets per day in terms of quarters, and a liquid whose number of processed sheets reached 1000 sheets was defined as a liquid after running.

Evaluation Method Measurement of Covering Power (CP) After the obtained sample was exposed so as to reach the maximum density (Dmax), the sample was processed with the developing solution for measuring the covering power by the automatic developing machine. The amount of silver (mg
/ Dm ² ) was measured and the CP was determined by the following equation. The larger the value, the higher the covering power.

CP = Dmax / silver content (mg / dm ² ) × 1000 Measurement of relative sensitivity and fog One set of samples 1 to 21 was inserted into a fluorescent intensifying screen for ortho, and 0.06 at a tube voltage of 90 KVP and a tube current of 100 mA. Exposure was performed with X-rays through the aluminum wedge for seconds. Then sample treated with fresh solution and running liquid developer described above was densitometry determined the sensitivity S ₂ from the obtained characteristic curve, and the relative sensitivity.

The relative sensitivity was as follows: the blackening density was fog +1.0
Sample No. 1 was calculated as the reciprocal of the exposure X-ray dose,
And expressed as sensitivity. Another one of the obtained samples
The set was developed with the running solution without exposure and the fog density was measured.

The results obtained are shown in Table 2 below.

[0077]

[Table 2]

As is clear from the table, according to the method of the present invention, even when a film containing a covering power improver is processed with a developing solution which has been subjected to a running process, generation of fog is extremely small, and sensitivity, CP (covering power) ) Shows no deterioration.

The comparative fogging inhibitor did not show any fogging prevention effect with the running solution.

[0080]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and high covering power without fogging even during running development processing can be obtained.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of a support, wherein the silver halide emulsion layer has the following general formula [I]: And at least one compound represented by the following general formula [II] and / or dextran in the silver halide emulsion layer and / or another layer. Characteristic silver halide photographic material. Embedded image R ₁ and R ₂ in the formula may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. R ₁ and R ₂ may combine with each other to form a nitrogen-containing heterocyclic ring. M _1, M ₂ represents a hydrogen atom or an alkali metal atom, an ammonium arm. Embedded image In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group (including those having a substituent), a halogen atom, or —CH ₂ COOM ₁ . L is -CONH-, -NHCO-, -COO-, -OCO
-, - CO -, - SO 2 -, - NHSO 2 -, - representing the SO ₂ NH- or -O-.
J represents an alkylene group (including those having a substituent) and an arylene group. Q is Represents a hydrogen atom or R ₃ , wherein M ₁ and M ₂ represent a hydrogen atom or a cationic group, and R ₉ is an alkyl group having 1 to 4 carbon atoms (including those in which a substituent is added to the alkyl group)
Wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (including those in which a substituent is added to the alkyl group) , An alkenyl group (including a substituent), a phenyl group (including a substituent), an aralkyl group (including a substituent), X represents an anion, and p represents And q
Represents 0 or 1, respectively. Y is a hydrogen atom or-
(L) represents _p- (J) _q- Q.