JP3243661B2 - 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 light-sensitive material for printing plate making and, more particularly, to a silver halide photographic light-sensitive material having high sensitivity, low fog and excellent preservability without impairing coatability.

[0002]

2. Description of the Related Art In a photosensitive silver halide photographic material,
It is known to add various additives for the purpose of reducing fog during processing, suppressing fog during storage, and stabilizing latent images.

[0003] However, many of these additives are hardly soluble in water, and they are dissolved in a commonly known organic solvent such as methanol and mixed or dispersed in a hydrophilic colloid solution for coating. Therefore, as the amount of addition increases, the amount of the organic solvent in the coating solution also increases, which often causes coating failure, and the amount of addition is often limited except for the performance of the photosensitive material.

For example, in the processing of a photosensitive material for printing plate making, a hydrazine derivative or a hydrazine derivative is used in order to further improve the processing stability while maintaining a high contrast performance comparable to the lith development in place of the conventional lith development. A PQ developing method using a so-called high contrast agent such as a tetrazolium compound has been widely used.

Particularly, in a method of obtaining a high-contrast image by using a silver halide photographic light-sensitive material containing a tetrazolium compound and an ordinary PQ developing solution, the general formula [1] , [2], [3] (Formula 1)
Requires a stabilizer such as When the above stabilizer is added only to a light-sensitive material by this method, no remarkable contrast-enhancing ability is observed, and when the added amount is large, it is hardly soluble in water, so that there is a problem that coating properties are deteriorated and sensitivity is lowered. When added to the processing agent, the high contrast is maintained, but as the processing proceeds, the stabilizer in the processing liquid is taken out of the liquid by the photosensitive material, and the high contrast ability is deteriorated. It becomes necessary to include a stabilizer.

In the case of medical photosensitive materials and photosensitive materials for printing plate making, there is a strong need for rapid development processing, and rapid processing has become widespread. Therefore, there is a problem that the fog needs to be suppressed as compared with the related art in order to be processed with a more active processing solution. Therefore, it is necessary to add a fog inhibitor to the light-sensitive material.

[0007] In order to improve coating properties, a method is known in which a poorly water-soluble compound such as an antifoggant or a stabilizer is finely pulverized with a ball mill or the like in a solid state and added to a hydrophilic colloid solution. In most cases,
In addition, there is a drawback that the originally desired performance (fog suppression and maintenance of high contrast in the case of a tetrazolium compound-containing photosensitive material) cannot be obtained.

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, low fog and excellent preservability without impairing coatability. To provide.

Another object of the present invention is to provide a silver halide photographic light-sensitive material in which a high-contrast processing system using a tetrazolium compound has an improved high-contrast ability without a decrease in sensitivity.

[0010]

The object of the present invention is to provide a silver halide photographic light-sensitive material having, on at least one side of a support, at least one layer of a hydrophilic colloid containing a light-sensitive silver halide photographic emulsion. Wherein the silver halide photographic light-sensitive material contains at least one compound which can include at least one antifoggant or at least one stabilizer.
Alternatively, the support has at least one silver halide emulsion layer on a support, and the emulsion layer or another hydrophilic colloid layer contains a tetrazolium compound, and has the general formula [1]
Or a silver halide photographic material characterized by containing at least one compound which includes the compound represented by [2] or [3] (formula 1).

It is a preferred embodiment of the present invention that the compound to be included is a cyclodextrin compound.

Hereinafter, the present invention will be described specifically.

The antifoggants and stabilizers used in the present invention include the following. Antifoggants, stabilizers, U.S. Pat.Nos. 2,713,541 and 2,743,180,
Pentazaindenes described in 2,743,181, U.S. Pat.Nos. 2,716,062, 2,444,607, 2,444,605,
No. 2,756,147, No. 2,835,581, No. 2,852,375, Research Disclosure 148
No. 51, tetrazaindenes described in U.S. Pat.
Triazaindenes described in JP-A-2,164,
Azaindenes such as polymerized azaindenes described in 7-211142; U.S. Pat. Nos. 2,131,038 and 3,342,596
And quaternary onium salts such as the thiazolium salts described in U.S. Pat. No. 3,954,478, the pyrilium salts described in U.S. Pat. No. 3,148,067, and the phosphonium salts described in JP-B-50-40665; U.S. Pat. 927, 3
266,897, 3,708,303, JP-A-55-135835
No. 59-71047, mercaptotriazoles, mercaptotriazoles, mercaptodiazoles, mercaptothiazoles described in U.S. Pat.No. 2,824,001, mercaptobenzthiazoles described in U.S. Pat.No.3,937,987 Mercaptobenzimidazoles, mercaptooxadiazoles described in U.S. Pat. No. 2,843,491, mercapto-substituted heterocyclic compounds such as mercaptothiazoles described in U.S. Pat. No. 3,364,028; U.S. Pat. No. 3,236,652; 43-1025
Catechols described in No. 6, resorcines described in JP-B-56-44413, and polyhydroxybenzenes such as gallic acid esters described in JP-B-43-4133;
Tetrazoles described in West German Patent No. 1,189,380,
Triazoles described in U.S. Patent No. 3,157,509,
Benztriazoles described in U.S. Pat.No. 2,704,721, urazoles described in U.S. Pat.No. 3,287,135, pyrazoles described in U.S. Pat.No. 3,106,467, indazoles described in U.S. Pat.No. 2,271,229, and Azoles such as polymerized benzotriazoles described in JP-A-59-90844 and U.S. Pat.
Pyrimidines described in No. 5, 3-pyrazolidones described in U.S. Pat.No. 2,751,297, and U.S. Pat.
Heterocyclic compounds such as polymerized pyrrolidone or polyvinylpyrrolidone described in JP-A-213;
No. 9, No. 59-137945, No. 59-140445, UK Patent No. 1,35
No. 6,142, U.S. Pat. Nos. 3,575,699 and 3,649,267; various inhibitor precursors described in U.S. Pat.
Sulfinic acid and sulfonic acid derivatives described in US Pat. No. 7,939, US Pat. Nos. 2,566,263, 2,839,405, and 2,488,
No. 709 and 2,728,663.

Particularly preferably used antifoggants and stabilizers include mercaptotetrazole, mercaptotriazoles, mercaptothiazoles, mercaptobenzthiazoles and catechols.

In a high contrast processing system using a tetrazolium compound, the general formula [1]
[2] and [3] (Formula 1) are used.

Typical examples represented by the general formula [1] are shown below, but are not limited thereto.

1-1 5-nitroindazole 1-2 6-nitroindazole 1-3 5-sulfindazole 1-4 5-cyanoindazole 1-5 6-cyanoindazole 1-6 2-mercaptoindazole General formula [2] Representative specific examples of the compound represented by are shown below, but are not limited thereto.

2-1 Benzotriazole 2-2 5-Methylbenzotriazole 2-3 5-Chlorobenzotriazole 2-4 5-Nitrobenzotriazole 2-55-Ethylbenzotriazole 2-6 5-Carboxybenzotriazole 2- 7 5-hydroxybenzotriazole 2-8 5-aminobenzotriazole 2-9 5-sulfobenzotriazole 2-10 5-cyanobenzotriazole 2-11 5-methoxybenzotriazole 2-12 5-ethoxybenzotriazole 2-135 -Mercaptobenzotriazole Typical specific examples represented by the general formula [3] are shown below, but are not limited thereto.

3-1 Benzimidazole 3-2 5-Sulfobenzimidazole 3-3 5-Methoxybenzimidazole 3-4 5-Chlorobenzimidazole 3-5 5-Nitrobenzimidazole 3-6 2-Mercapto-5-sulfo Benzimidazoles These compounds are known in the photographic field as antifoggants and can be synthesized by known synthetic methods, and some compounds are commercially available as chemical reagents.

The compound represented by the above formulas (1) to (3) (Chemical Formula 1) is used in an amount of about 0.1 mg to 10 g per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. More preferably, it is used in the range of about 1 mg to 1 g.

The clathrate compound according to the present invention forms an clathrate compound by performing a clathrate action with a fog inhibitor and a stabilizer.

The inclusion compound is, for example, F. Cramer, "Einschlus verbindungen" Springer (1954) or M. Hagan, "Clathrate inclusion". Compound ”(Clathrate Inclusion
As described in Reinheld (1962), there is a hole of an appropriate size inside a three-dimensional structure formed by combining atoms or molecules, and another atom or molecule has a certain composition ratio in it. The substance that forms a specific crystal structure by entering at

Next, the cyclodextrin compound used as an inclusion compound in the present invention will be described.

The term "cyclodextrin compound" means ordinary cyclodextrin, cyclodextrin derivative (cyclodextrin substituted with ether or ester group, branched cyclodextrin bound with glucose or maltose, cyclodextrin polymer, etc.).

The cyclodextrin used in the present invention is represented by the following general formula [4].

[0026]

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Among them, those particularly useful in the present invention are n ₁ =
4 of α- cyclodextrin, n ₁ = 5 of β- cyclodextrin, a γ- cyclodextrin n ₁ = 6.

Next, the cyclodextrin derivative used in the present invention will be described.

Derivatives in which the hydroxyl group of the cyclodextrin represented by the general formula [4] is converted to an ether, ester, amino group or the like are also known. These cyclodextrins are described in detail in MI Vendor, M. Koyama, Cyclodextrin Chemistry, Springer-Verlag, 1978.

The cyclodextrin derivative used in the present invention is represented by the general formula [5] or [6].

[0031]

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R _{1 to} R ₃ may be the same or independently different and represent hydrogen, an alkyl group or a substituted alkyl group. Particularly, those in which R ₁ and R ₃ are alkylated are preferable.

As an example, heptakis-2,6-dimethyl-β
-Cyclodextrin, hexakis-2,6-dimethyl-α-cyclodextrin, octakis-2,6-dimethyl-γ-cyclodextrin and the like.

In the cyclodextrin represented by the general formula [6] CD- (O-R) ₁ , R is hydrogen, R ² CO ₂ H, R ²
SO ₃ H, R _² NH ² or _{^{(R 2) 2 N- (R}} 2 represents an alkylene of straight or branched chain of 1 to 5 carbon atoms) and l represents an integer of 1 to 5.

Specific examples are shown below, but the present invention is not limited to these.

[0036] Next, the branched cyclodextrin used in the present invention will be described.

The branched cyclodextrin used in the present invention is a known cyclodextrin in which a water-soluble substance such as a monosaccharide or disaccharide such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine is branched or added. Preferably, maltosyl rodextrin in which maltose is bound to cyclodextrin (the number of molecules of maltose bound is one,
Glucosylcyclodextrin in which glucose is bound to cyclodextrin (the number of binding molecules of glucose may be one, two, or three, etc.).

Specific methods for synthesizing these branched cyclodextrins are described, for example, in Starch Chemistry, Vol. 33, No. 2, p. 119.
-126 (1986), P.127-132 (1986), Starch Chemistry, No.3
Vol. 0, No. 2, pp. 231 to 239 (1983) can be synthesized by a known synthesis method. For example, maltosyl cyclodextrin is obtained by using cyclodextrin and maltose as raw materials and isoamylase or pullulanase sugar. It can be produced by a method of binding maltose to cyclodextrin using an enzyme. Glucosylcyclodextrin can be produced in a similar manner.

In the present invention, examples of the branched cyclodextrin preferably used include the following specific compounds.

[Exemplary Compounds] D-1 α-cyclodextrin with one molecule of maltose bound, D-2 β-cyclodextrin with one molecule of maltose bound, D-3 γ-cyclodextrin with one molecule of maltose bound, D -4 α-cyclodextrin with two molecules of maltose bonded, D-5 β-cyclodextrin with two molecules of maltose bonded, γ-cyclodextrin with two molecules of maltose bonded, and three molecules of D-7 maltose bonded α-cyclodextrin, D-8 β-cyclodextrin in which three molecules of maltose are bonded, D-9 γ-cyclodextrin in which three molecules of maltose are bonded, D-10 α-cyclodextrin in which one molecule of glucose is bonded, D-11 Β-cyclodextrin with one molecule of glucose bound, D-12 one molecule of glucose bound -Cyclodextrin, α-cyclodextrin having two molecules of D-13 glucose bonded thereto, β-cyclodextrin having two molecules of D-14 glucose bonded, γ-cyclodextrin having two molecules of D-15 glucose bonded, D-16 glucose Are α-cyclodextrins having three molecules bonded thereto, β-cyclodextrins having three molecules of D-17 glucose, γ-cyclodextrins having three molecules of D-18 glucose bonded, and the structures of these branched cyclodextrins are described in HPL.
C, NMR, TLC (thin layer chromatography), INEPT method (In
scnsitive nuclei enhanced by polarization transfe
Although various measurement methods such as r) have been studied, they have not yet been determined even with current science and technology, and are in the stage of estimation structure. However, the fact that each monosaccharide or disaccharide or the like is bound to cyclodextrin is that there is no error in the above measurement method. Therefore, in the present invention,
When multiple molecules of monosaccharides or disaccharides are bonded to cyclodextoline, for example, as shown in the figure below, when they are individually bonded to each glucose of cyclodextrin, And both of those bound to

[0041]

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Since the ring structure of the existing cyclodextrin is kept as it is, it exhibits the same inclusion function as that of the existing cyclodextrin, and is added with highly water-soluble maltose or glucose, so that the solubility in water is greatly increased. The feature is that it has been improved.

The branched cyclodextrin used in the present invention can be obtained as a commercial product, and for example, maltosyl cyclodextrin is commercially available as Isoelite (registered trademark) manufactured by Saltwater Port Refining Co., Ltd.

Next, the cyclodextrin polymer used in the present invention will be described.

As the cyclodextrin polymer used in the present invention, those represented by the following general formula [7] are preferable.

[0046]

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The cyclodextrin polymer used in the present invention can be produced by subjecting cyclodextrin to a cross-linking polymerization with, for example, epilorhydrin.

It is preferable that the cyclodextrin polymer has a water solubility, that is, a solubility in water of not less than 20 g per 100 ml of water at 25 ° C., and for this purpose, the polymerization degree n ₂ in the general formula [7] is 3 to 3. The smaller the value, the higher the water solubility of the cyclodextrin polymer itself and the higher the solubility effect of the substance.

These cyclodextrin polymers are described, for example, in JP-A-61-97025 and German Patent 3,544,842.
It can be synthesized by a general method described in the specification and the like.

The cyclodextrin polymer may be used as an inclusion compound of the cyclodextrin polymer as described above.

CF used as an inclusion compound in the present invention
(Cyclofractane) is represented by the following general formula [8].

[0052]

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Next, the calixarene compound used as an inclusion compound in the present invention will be described.

Calixarenes are cyclic oligomers synthesized by the condensation of phenol and formaldehyde. Acc. Chem. Res, 16, 161 (1983)
Are generally known.

The calixarene compound used in the present invention has the following general formula:

It is shown by [9].

[0056]

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The amount of the clathrate compound (cyclodextrin, dicyclofructan, calexarene) of the present invention is not particularly limited, but is preferably 0.2 to 100 g / Ag mole. Particularly preferably, it is 0.5 to 20 g / Ag mole.
Several examples of methods for obtaining an inclusion compound such as an antifoggant are given, but the method is not limited thereto. . A poorly water-soluble organic compound is dissolved in an appropriate organic solvent, mixed with a cyclodextrin compound aqueous solution, and mixed with stirring. In the case of one layer, it is spray-dried as it is, and in the case of two layers, only the aqueous layer is spray-dried and powdered. Purify using an appropriate solvent.

[0058] For poorly water-soluble organic compounds that increase in solubility by changing the pH of the solution, adjust the pH of the cyclodextrin compound to that pH, add the poorly water-soluble compound, stir to dissolve, atomize, and dry to form a powder. This is the method.

Next, a typical tetrazolium compound used in the light-sensitive material of the present invention is represented by the following general formula [T].

[0060]

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The tetrazolium compound represented by the above general formula [T] used in the present invention will be described. In the general formula [T], preferred examples of the substituent represented by R ₁ to R ₃ include an alkyl group (eg, methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), an amino group , Acylamino group (eg, acetylamino), hydroxyl group, alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.), acyloxy group (eg, acetyloxy), halogen atom (eg, fluorine, chlorine, bromine, etc.), carbamoyl group , An acylthio group (for example, acetylthio), an alkoxycarbonyl group (for example, ethoxycarbonyl), a carboxyl group, an acyl group (for example, acetyl), a cyano group, a nitro group, a mercapto group, a sulfoxy group, and a group such as an aminosulfoxy group. .

[0062] The X ^- include anions represented by, for example, chloride, bromide, halide ions such as iodide ions, nitric acid, sulfuric acid, acid roots of inorganic acids such as perchloric acid, sulphonic acids, such as carboxylic acid Organic acid acid radicals, anionic activators, specifically lower alkylbenzene sulfonic acid anions such as p-toluene sulfonic acid anion, higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion, and lauryl sulfate anion Higher alkyl sulfate anions, borate anions such as tetraphenylboron, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anion, polyether alcohol sulfate anions such as cetyl polyethenoxy sulfate anion, stearic acid Higher aliphatic anions such as anions, the polymer of polyacrylic acid anion, and the like such as those with a acid radical.

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

[0064]

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The tetrazolium compound used in the present invention may be, for example, a compound as described in Chemical Reviews.
The compound can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula [T] used in the present invention is used in an amount of about 1 mg to about 10 g, preferably about 10 mg, per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. The above is used in the range of about 2 g.

The tetrazolium compound represented by the general formula [T] used in the present invention may be used alone or
Species or more may be used in combination at an appropriate ratio.

The silver halide photographic light-sensitive material used in the present invention and various processings of black-white and reversal by a known method can be used for the processing. For example, a technique described in JP-A-3-278049 can be applied.

[0069]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of silver halide photographic emulsion A> A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by a double jet method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ⁻⁷ per mole of silver.
Mole was added. The obtained emulsion was an emulsion composed of cubic monodispersity particles having an average particle size of 0.20 μm (coefficient of variation: 9%). Washing and desalting were carried out in a conventional manner. The pAg at 40 ° C after desalting is 8.0
Met.

Using this emulsion, a sensitizing dye D-
1 and sensitizing dye D-2 were added as shown in Table 2.

Here, the concentrations of the sensitizing dye solutions were all set as follows.

0.7 g of D-1 and 0.035 g of D-2 were dissolved in
Dissolve in 0 ml.

When the compound of the present invention was added during the above-mentioned dissolution, it was added in an amount of 2.5 ml / l.

Further, the following compounds [A], [B],
The mixture of [C] was added, followed by sulfur sensitization. The structures of the sensitizing dyes D-1 and D-2 are also shown below.

[0076]

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<Preparation of silver halide photographic light-sensitive material> Using this emulsion, a light-sensitive silver halide photographic light-sensitive material was prepared according to the following formulation.

Composition of photosensitive silver halide emulsion layer Hydrazine derivative 7 × 10 ⁻⁵ mol / m ² Gelatin 2.0 g / m ² Silver halide photographic emulsion A (silver content) 3.2 g / m ² Stabilizer: 4-methyl -6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 10 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: dodecylbenzene Sodium sulfonate 0.1 g / m ² Surfactant S-1 8 mg / m ²

[0079]

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Polyethylene glycol (Mw = 4000) 0.1 g / m ² Hardener A A hydrazine derivative, a surfactant S-1, and a hardener in the composition of the above-mentioned photosensitive silver halide emulsion of 60 mg / m ² or less. The structural formula of A is shown.

[0081]

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Emulsion protective layer composition Gelatin 0.9 g / m ² Surfactant S-2 10 mg / m ² Surfactant S-3 10 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 3 mg / m ² hard Film agent: 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Backing layer composition Dye (a) 30 mg / m ² Dye (b) 75 mg / m ² Dye (c) 30 mg / m ² Gelatin 2.4 mg / m ² surfactant sodium dodecylbenzenesulfonate 0.1 g / m ² surfactant S-1 6.0mg / m ² colloidal silica 100 mg / m ² hardener B 55 mg / m ² backing protective layer composition gelatin 1 g / m ² matting agent: Monodisperse polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² Surfactant: S-2 10 mg / m ² Hardener: Glyoxal 25 mg / m ² Hardener A 35 mg / m ² A liquid having the above composition is as follows: Was coated on a polyethylene terephthalate support having been subjected to an undercoating process. That is, the above-mentioned photosensitive silver halide emulsion layer has a gelatin amount of 2.0 g / m ² and a silver amount of 3.2 g / m ^2. / m ² . or,
On the side of the support opposite to the emulsion layer (subbed), the above-mentioned backing layer was gelatinized at 2.4 g / m ² , and the backing protective layer was further coated with 1 g / g of gelatin.
It was coated so as to become a m ^2. The pH of each layer was adjusted with sodium carbonate and / or citric acid.

The following inhibitors were mixed with various clathrate compounds as shown in Table 1 and added to the emulsion layer to prepare Samples 1-1 to 1-18.
I got

Here, the clathrate compound was prepared by dissolving 20 g of sodium hydroxide in 100 ml of water, dissolving 10 g of a compound capable of clathrate, adding a desired amount of an inhibitor, homogenizing at 5000 rpm for 10 min, and spray-drying. And spray dried.

5-nitroindazole and 1-phenyl-5-
Mercaptotetrazole was added as shown in Table 1.

5-Nitroindazole 0.8% 1-phenyl-5-mercaptotetrazole 1.0% added The compound of the present invention was added to the above solution at a rate of 2 mol / l. About the obtained sample, applicability and 50 ℃, 50%
The fog increase after storage for 3 days was examined. Fog was subjected to the following development and stored at 23 ° C. and 50%. It is shown by the amount of rise relative to the Fog of the sample.

Table 1 shows the results.

[0088]

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<Confirmation of Coating Properties> The samples immediately after coating were visually evaluated for the level of uneven coating.

The ranks are: 1. Application unevenness is strong over the entire surface. 2. Coating unevenness is only partially strong. 3. Weak coating unevenness occurs. 4. Coating unevenness is slightly generated. If there is no coating unevenness at 4 or more, there is no practical problem.

<Measurement of Sensitometry> The obtained sample was exposed to tungsten light of 3200K for 5 seconds with a step wedge in close contact, and then a developer and a fixer having the following compositions were charged into Konica Corporation. Automatic processing machine GR
Processed under the following conditions with -26SR.

[0092] The obtained sample was stored at 23 ° C and 50% RH for 3 days, and the sample stored at 23 ° C and 80% RH for 3 days was subjected to the following treatment.

The processing conditions are as follows.

Developer Formulation Sodium bisulfite 40 g N-methyl-p-aminophenol sulfate 350 mg Ethylenediaminetetraacetic acid disodium salt 1 g Sodium chloride 5 g Sodium bromide 1.2 g Trisodium phosphate 75 g 5-Methylbenztriazole 250 mg 2-mercapto benzothiazole 23mg benzotriazole 83mg hydroquinone 29g diisopropylaminoethanol 2.3ml amine compound _{Am-1 0.5ml (CH 2 -CH} (CH 3) -CH 2 - [OCH 2 (CH (CH 3) x] -NH 2 (x = 2.6 average) Potassium hydroxide Amount to adjust pH of used amount to 11.6 Finished to 1 liter with water added at the time of use.

Fixer Formulation Ammonium thiosulfate (59.5% W / V aqueous solution) 830ml Ethylenediaminetetraacetic acid disodium salt 515ml Sodium sulfite 63g Boric acid 22.5g Acetic acid (90% W / V aqueous solution) 82g Citric acid (50% W / V aqueous solution) 15.7g Gluconic acid (50% W / W aqueous solution) 8.55g Aluminum sulfate (48% W / W aqueous solution) 13ml Glutaraldehyde 3g Sulfuric acid Amount to make pH 4.6 when used Water was added at the time of use to make 1L.

Development processing conditions Process Temperature Time Current image 38 ° C 20 seconds Fixed 38 ° C 20 seconds Water washing Normal temperature 15 seconds Drying 40 ° C 15 seconds Each process time includes the time required to transport the next process.

The density of the obtained sample was measured with an optical densitometer Konica PDA-65. The results are shown in Table 1.

[0098]

[Table 1]

As shown in Table 1, it was found that the sample to which the sensitizing dye solution containing the compound of the present invention was added had no coating unevenness and excellent storage stability under high humidity.

Example 2 In the presence of 2 × 10 ⁻⁶ mol of water-soluble iridium / 1 mol of silver and 4 × 10 ⁻⁷ mol of water-soluble rhodium / 1 mol of silver, 120 g of EAg was added.
V and pH were adjusted while controlling to 3.0 to obtain silver chlorobromide grains containing 30 mol% of silver bromide. The particles have an average particle size of 0.24
The distribution width was 11% for the cubic particles of μm. After gold sensitization and sulfur sensitization, an ortho sensitizing dye was added, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was used as a stabilizer per mole of silver halide. Add 1g,
As shown in Table 1, 200 mg of the tetrazolium compound T-14 was added to the inclusion body of the cyclodextrin compound represented by the general formulas [1] to [3]. These clathrates were produced by the method described in the specification, and sodium hydroxide was used as an alkaline agent in the production process. sodium n-dodecylbenzenesulfonate
600 mg and 2 g of a styrene-maleic acid copolymer were added, and the pH was adjusted to 5.8 with citric acid, followed by coating on a polyethylene terephthalate film. At that time, 30 mg / m ² of 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate was used as a spreading agent, and 25 mg / m ² of formalin was used as a hardening agent so that the amount of gelatin became 1.0 g / m ^2. The hardening protective layer was applied in multiple layers. The clathrates of the general formulas [1] to [3] are prepared by dissolving 20 g of sodium hydroxide in 100 ml of water and dissolving 10 g of an inclusion compound such as cyclodextrin.
After adding 0.1 to 1 g of the compound of [3] and homogenizing at 5000 rpm for 10 minutes, it was adjusted by spray drying with a spray dryer. As comparative samples, those obtained by dissolving the general formulas [1] to [3] in methanol, adding only the cyclodextrin compound, and not adding the same were used for the clathrate among the above methods.

Next, a backing layer having the following composition was provided on the support opposite to the emulsion layer in exactly the same manner as in Example 2 of JP-A-2-226143.

Precipitic acid propyl ester 300 mg / m ² Styrene-maleic acid copolymer 100 mg / m ² Alkali-treated gelatin (isoelectric point 4.9) 1.0 g / m ² Formalin 10 mg / m ² After adjusting to .4, it was applied.

After the obtained sample was subjected to stepwise exposure with tungsten light through a commercially available ordinary contact screen (grey negative 150L), a normal roller type automatic developing machine was developed using a developing solution and a fixing solution having the following compositions. The treatment was performed using

The obtained processed sample was measured with a Konica digital densitometer PDA-65, and the relative sensitivity was defined as 100, with the sensitivity at a density of 3.0 of Sample No. 1, and further, a density of 0.3 and 3.0.
The gamma is displayed with the tangent of. A gamma value of less than 6 cannot be used, a gamma value of 6 or more and less than 10 is still insufficient, and a gamma value of 10 or more can be said to be a very high contrast image and practical.

The running stability was evaluated by processing 100 exposed films (610 mm.times.508 mm) of the exposed film per day, and measuring the photographic performance on the 7th and 14th days from the start of processing. Table 2 shows the results.

Developer formulation (composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 1-phenyl-5-mercapto Tetrazole 30mg Potassium hydroxide, Amount to adjust pH of used solution to 10.4 Potassium silver bromide 4.5g (Composition B) Pure water (ion exchange water) 3ml Diethylene glycol 50g Disodium ethylenediaminetetraacetate 25mg Acetic acid (90% aqueous solution) 0.3ml 1-Phenyl-3-pyrazolidone 700 mg When using a developing solution, the above-mentioned composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 liter.

Fixing solution formulation (composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17 g sodium acetate trihydrate 6.5 g boric acid 6 g sodium citrate dihydrate 2 g acetic acid (90% w / v aqueous solution) ) 13.6 ml (composition B) pure water (ion-exchanged water) 17 ml sulfuric acid (50% w / v aqueous solution) 4.7 g when using aluminum sulfate (Al ₂ O ₂ converted content 8.1% w / v aqueous solution) 26.5 g fixer The composition A and the composition B were dissolved in 500 ml of water in this order, and used after finishing to 1 liter. The pH of this fixing solution was about 4.3.

Processing conditions Process temperature (° C) Time (second) Developing 28 30 Fixing 28 20 Washing 25 20 Drying 40 20

[0109]

[Table 2]

From the results shown in Table 2, it can be seen that the sample of the present invention has a high contrast and a stable running performance with respect to the comparison.

[0111] Example 3 <A solution> H ₂ O 9.7l NaCl 20g gelatin 105 g <B solution> H ₂ O 3.8l NaCl 380g gelatin _{94g KBr 420g K 3 IrCl 6 2.8μg} K 3 RhCl 0.5μg <C solution> H ₂ O 3.8 l AgNO ₃ 1700 g While keeping pH 3.5 and pAg 8.0 in the above solution A kept at 38 ° C., simultaneously add the above solution B and solution C functionally over 90 minutes and stir for another 10 minutes After that, the pH was adjusted to 5.8 with a CaCl ₂ aqueous solution, and normal desalting was performed using MgSO ₄ and polynaphthalene sulfonic acid, AgBr 35 mol%, AgCl 65m
ol%, AgBrCl particles having an average particle size of 0.25 μm were obtained.

Preparation of Coated Sample To the obtained emulsion, 0.12 g of citric acid and 3 g of NaBr were added, and the pH was adjusted to 5.
5. After adjusting to pAg7, 0.12 g of sodium thiosulfate,
0.16 g of chloroauric acid was added, and the mixture was chemically ripened at 60 ° C. so as to have the highest sensitivity.

Next, sensitizing dyes D-3 and D-4 were used, respectively.
140 mg was added for spectral sensitization.

Further, the following additives were added per 1 mol of silver halide.

Saponin (Merck) 3.4 g Compound 1.3 g Hydroquinone 4.0 g KBr 2.83 g Polymer latex of ethyl acrylate 14.16 g Citric acid 0.113 g Compound 283 mg Styrene-maleic acid polymer 2.8 g The protective layer was prepared as follows.

Gelatin 60 g Amorphous silica (average particle size 2.8 μm) 1.4 g Bis (2-ethylhexyl) sulfosuccinate 0.8 g KBr 1 g Before coating the above emulsion layer, apply a backing layer and its protective layer. did. The adjustment was prepared as follows.

Backing layer Gelatin 60 g Compound 1.5 g Compound 0.7 g Compound 10 g Saponin (manufactured by Merck) 2.5 g Sodium dodecylbenzenesulfonate 0.2 g Butyl acrylate vinylidene chloride copolymer 3 g Citric acid 0.4 g Sulfone-maleic acid polymer 0.1 g Backing protective layer Gelatin 60g PMMA (average particle size 13μm) 7.8g Bis (2-ethylhexyl) sulfosuccinate 0.6g NaCl 0.2g Polysiloxane 60g

[0118]

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[0119]

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The above solution was coated on both sides of a PET base so that the amount of gelatin in the backing layer was 3.2 g / m ² and the amount of gelatin in the backing protective layer was 1.0 g / m ^2. Glyoxal as a hardener was 11 mg / g of gelatin. And simultaneously applied.

Thereafter, silver was added so that the silver amount was 3.6 g / m ² , the gelatin of the emulsion protective layer was 0.7 mg / m ^2, and a hardener was 14 mg of triazine and 14 mg of formalin per 1 g of gelatin.

Further, the compound of the present invention was added to the emulsion layer as shown in Table 3.
Was added as described in

The inclusion compound was added in the same manner as in Example 2.

The obtained samples were evaluated for sensitometry, storage stability, and scratches.

(Evaluation of Sensitometry) The obtained sample was stored at 23 ° C. and 50% Rh, exposed to 10 ⁻⁵ through a 780 nm interference filter and a continuous wedge, and subjected to an automatic developing machine FG manufactured by Fuji Photo Film Co., Ltd. -710NH, developer LD-835, fixer LF-30
Using No. 8, processing was performed at a development temperature of 38 ° C. and Dry to Dry for 45 seconds.
The sensitivity was the reciprocal of the exposure amount giving a density of 4.0, and the results are shown in Table 3 as relative sensitivities.

Evaluation of Storage Property Further, the obtained sample was stored at 55 ° C. and 50% Rh for 3 days, and the same sensitometric evaluation was performed. The results are shown in Table 3.

(Scratch Test) A part of the rubber roller of the rack of the automatic developing machine was made uneven, and a sample which was solid-exposed to a density of 4.0 was developed.

The results are shown in Table 3 below. The results were visually evaluated according to the following criteria.

1: It is clearly white and scratched.

2: Slightly white and scratched.

3: It can be seen from the reflection that the surface is scratched.

4: Almost no scratches.

5: There is no flaw at all.

[0134]

[Table 3]

As described above, it can be seen that the sample containing the clathrate compound of the present invention is excellent in coatability and storage stability and also excellent in scratch resistance during processing in an automatic developing machine.

Example 4 Using the following solutions, monodisperse spherical seed emulsions were prepared in the following manner by the method described in JP-A-61-6643.

<Solution A> Ossein gelatin 150 g KBr 53.1 g KI 24 g Make up to 7200 ml with distilled water <Solution B> Silver nitrate 1500 g Make up to 6000 ml with distilled water <Solution C> KBr 1327 g 1-phenyl-5-mercaptotetrazole (methanol 0.3 g distilled water to make 3000 ml <Solution D> Ammonia water (28%) 705 ml Solution A and solution C were added to solution A vigorously stirred at 40 ° C for 30 seconds by the double jet method, and nuclei were added. Was generated. The pBr at this time was 1.09 to 1.15. After 1 minute and 30 seconds, solution D was added in 20 seconds and ripened for 5 minutes. K during aging
Br concentration is 0.071 mol / l, ammonia concentration is 0.6
It was 3 mol / l.

Thereafter, the pH was adjusted to 6.0, and immediately desalting and washing were performed to obtain EM-B. When this seed emulsion was observed by an electron microscope, it was a monodisperse spherical emulsion having an average particle size of 0.36 μm and a distribution of 18%.

(Preparation of Em-1) Emulsion Em-1 containing tabular silver halide grains having an average silver iodide content of 2.25 mol% was prepared using the above seed emulsion and the following liquids.

<Solution A> Ossein gelatin 85 g Propyleneoxy-polyethyleneoxydisuccinate-disodium salt (10% methanol solution) 10 ml Equivalent to the above seed emulsion 0.98 mol Equivalent to 4000 ml with distilled water <Solution B> Ossein gelatin 43.3 g KBr 36.1 g KI 21.7 g distilled water to 1082 ml <Solution C> silver nitrate 73.5 g nitric acid (specific gravity 1.38) 5.5 ml distilled water to 1082 ml <solution D> ossein gelatin 44.2 g KBr 682 g KI 2.86 g distilled water Make up 2210 ml <Solution E> Silver nitrate 977 g Nitric acid (specific gravity 1.38) 9.3 ml Make up 2210 ml with distilled water Solution A and solution C were added to solution A vigorously stirred at 75 ° C by the double jet method. During this time, the pH was 2.0 with nitric acid.
The pAg was kept at 8.0 throughout. The addition time was 16 minutes, and the addition rate was increased linearly so as to be 1.27 times at the beginning and at the end.

Next, Solution D and Solution E were added to the same solution by the double jet method. At this time, the pH was kept at 2.0 and the pAg was kept at 9.0. The addition time was 38 minutes, and the addition rate was increased linearly so as to be 1.80 times at the beginning and at the end. After completion of the addition, desalting treatment for removing excess salts is performed as follows, and p
An emulsion having an Ag of 8.5 and a pH of 5.85 was obtained.

That is, the silver halide emulsion obtained above was kept at 40 ° C., and 5 g of a formaldehyde resin of naphthalenesulfonic acid sodium salt (average degree of polymerization of 4 to 6) per mol of silver halide and magnesium sulfate were added to silver halide. 8 g was added per mole, and the mixture was stirred for 5 minutes and then allowed to stand. Thereafter, the supernatant was drained to a liquid volume of 200 ml per mol of silver halide.

Next, 1.8 L of pure water at 40 ° C. was added per mol of silver halide, and the mixture was stirred for 5 minutes. Next, 20 g of magnesium sulfate was added per 1 mol of silver halide, and the mixture was stirred and allowed to stand in the same manner as above, and the supernatant was removed to remove salts.
After stirring, the silver halide was dispersed again, gelatin was added, and the mixture was dispersed for 55 minutes.

When the obtained emulsion was observed by an electron microscope, it was a silver halide emulsion having 100% of twin grains, an average grain size of 0.73 μm, and a distribution area of 11%. The aspect ratio (ratio of particle diameter / particle thickness) was 3.2.

The obtained emulsion was optimally subjected to gold-sulfur sensitization. Immediately before the end of the chemical sensitization, the following sensitizing dyes were mixed with A: B =
Add 1000 mg / mol AgX at a ratio of 20: 1, add 4-hydroxy-6-
2.5 g / Ag of methyl-1,3,3a, 7-tetrazaindene was added.

[0146]

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Next, the exemplified compounds of the general formula [1] according to the present invention were added as shown in Table 4. Further, the following additives were added to each emulsion as emulsion liquid additives.
The amount of addition is shown in an amount per mole of silver halide.

Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane 10 g Diethylene glycol 5 g Nitrophenyl-triphenyl-phosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 4 g 2 -Sodium mercaptobenzimidazole-5-sulfonate 1.5mg

[0149]

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1,1-Dimethylol-1-bromo-1-nitromethane 10 mg

[0151]

Embedded image

Was added. Further, as shown in Table 4, an antifoggant was added as an inclusion compound.

The inclusion method was the same as in Example 2.

The following compounds were added to gelatin as additives for a protective layer to prepare a coating solution for forming a protective layer. The additives used in the coating solution are as follows. The amount of addition is shown in an amount per 1 g of gelatin.

[0155]

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Matting agent composed of polymethyl methacrylate having an average particle size of 7 μm 7 mg Colloidal silica (average particle size 0.013 μm) 70 mg Further, as a hardener, the following compound was added in different amounts to change the swelling ratio.

CH ₂ CHCHSO ₂ OCH ₂ SO ₂ CH = CH ₂ A solution obtained by adding gelatin and a protective film solution to change the film thickness of the emulsion to which the additive was added were colored blue.
On a polyethylene terephthalate film base having a subbing treatment of 0 μm, both sides were uniformly coated and dried to obtain a double-sided emulsion sheet-like photosensitive material.

At this time, the amount of silver applied was 1.9 g / m ² as one side.
In, 2.5 g / m ² as a gelatin emulsion layer, and 4g / m ^2, was applied so that the protective film of gelatin 1.5 g / m ^2.

The obtained sample was processed as follows. In addition, sensitometry, preservability, and scuffing of each sample were evaluated.

(Processing step) The obtained sample was developed with the following developer containing a silver halide solvent shown in Table 4 using an ultra-rapid automatic developing machine SRX-501 (manufactured by Konica Corporation).
Processed in 45 seconds.

The following developing solutions and fixing solutions were used.

<Developer> Potassium sulfite 70 g Hydroxyethylethylenediamine trisodium triacetate 8 g Hydroquinone 28 g Boric acid 10 g 5-Methylbenzotriazole 0.04 g 1-Phenyl-5-mercaptotetrazole 0.01 g Sodium metasulfite 5 g Acetic acid (90%) 13 g Tri Ethylene glycol 15 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Nitroindazole 0.2 g Glutaraldehyde 4 g Ethylenediaminetetraacetic acid disodium 2 g Potassium bromide 4 g 5-Nitrobenzimidazole 1 g Silver halide solvent described in Table 1 Make 1 liter aqueous solution, pH 10.50 with sodium hydroxide
Solution.

<Fixing solution> Sodium thiosulfate pentahydrate 45 g Sodium ethylenediaminetetraacetate 0.5 g Ammonium thiosulfate 150 g Anhydrous sodium sulfite 8 g Potassium acetate 16 g Aluminum sulfate 10-18 hydrate 27 g Sulfuric acid (50 wt%) 6 g Citric acid 1 g Boric acid 7 g Glacial acetic acid 5 g A 1 liter aqueous solution was added with glacial acetic acid to give a pH 4.0 solution.

Evaluation Method (Sensitometry) The obtained sample film was stored at 23 ° C. and 50%, and the tube voltage was set to 90 KVP, 20 mA, 0.05 using a fluorescent intensifying screen KO-250 for X-ray photography (Konica Corporation). Irradiate X-rays according to the distance method according to the conventional method in seconds and develop, fix,
Washing and drying were performed to create a sensitometric curve. The value obtained by subtracting the support concentration from the highest concentration in this curve is multiplied by 0.4, and the reciprocal of the X-ray dose required to obtain a value obtained by adding the support concentration is calculated. did.

(Preservability) The obtained sample was stored at 55 ° C. and 50% for 3 days, and the same sensitometric evaluation was performed.

(Scratch test) The same test as in Example 3 was performed, but the treatment was the same as in sensitometry.
45 seconds processing with SRX-501.

[0167]

[Table 4]

As described above, it is found that the sample containing the clathrate compound of the present invention is excellent in storage stability and also excellent in scratch resistance during processing in an automatic developing machine.

[0169]

According to the present invention, a silver halide photographic material having high sensitivity, low fog, and excellent preservability without impairing coatability is provided. In addition, in a high contrast processing system using a tetrazolium compound, Thus, it was possible to provide a silver halide photographic material in which the sensitivity was not reduced and the contrast enhancement ability was improved.

Continuation of the front page (56) References JP-A-61-20940 (JP, A) JP-A-64-15731 (JP, A) JP-A-1-128066 (JP, A) JP-A-2-100048 (JP) , A) JP-A-5-216162 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/34

Claims (3)

(57) [Claims] 1. A silver halide photographic material having a hydrophilic colloid containing at least one layer of a photosensitive silver halide photographic emulsion on at least one side of a support,
A silver halide photographic light-sensitive material characterized in that the silver halide photographic light-sensitive material contains at least one compound containing at least one antifoggant or at least one stabilizer. 2. A support having at least one silver halide emulsion layer on a support, wherein said emulsion layer or another hydrophilic colloid layer contains a tetrazolium compound, and has the following general formula [1] or [2]: ] Or a silver halide photographic light-sensitive material comprising at least one compound which includes the compound represented by [3]. Embedded image [In the formula, Y ₁ represents a hydrogen atom, an alkali metal or a mercapto group, and R ₁ and Y ₂ each represent a hydrogen atom, a halogen atom,
Nitro group, amino group, cyano group, hydroxyl group, mercapto group, sulfo group, substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a hydroxycarbonyl group, an alkylcarbonyl group or an alkoxycarbonyl group;
Represents an integer of 4. ] 3. The silver halide photographic material according to claim 2, wherein the compound to be included is a cyclodextrin compound.