JPH10239791A - Silver halide photographic sensitive material, and method for processing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material for laser light source superior in processing stability and pressure resistance and purely black in tone of silver image by making the material have specified silver halide grains and incorporating a specified compound in a hydrophilic colloidal layer. SOLUTION: The silver halide grains contained in the silver halide emulsion layer are doped with iridium and have an average particle diameter of 100-250nm and chemically sensitized by a selenium and/or tellurium compound in the presence of a sensitizing dye having a spectral maximum sensitivity in 600-1,200nm. The hydrophilic colloidal layer contains at least one kind of compound represented by the formula in which each of P, Q, and Y represents N atom or CH group and at least one of them is N atom; A is hydroxy, sulfo, or carboxyl, or its salt; and (n) is an integer of 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, images for radiation diagnosis such as MRI (magnetic resonance imaging), X-ray CT (computed tomography), CR (computed radiography), and computer-aided diagnosis systems have been digitally or analogously converted. 2. Description of the Related Art Means have been generalized in which a signal is taken into a processing device such as a computer, scanned with a laser beam, drawn on a silver halide photographic material, and provided as a transmission image for diagnosis.

[0003] Scanning laser exposure apparatuses are used for image recording in these diagnostic apparatuses, and argon, helium-neon, semiconductors, and the like are used as laser light sources.

[0004] Among them, a semiconductor laser has advantages such as being inexpensive, having a long life, being compact, and capable of direct modulation. In particular, the emission wavelength of a semiconductor laser is in the red to infrared region, and a laser having an emission wavelength of near-infrared is particularly important in terms of cost and stability. However, since the life of a semiconductor laser is said to be inversely proportional to the fourth power of its output, a recording material with high sensitivity has been desired in order to extend the life of the apparatus as much as possible.

[0005] As a method for spectrally sensitizing silver halide grains to near-infrared light region, for example, The Theory of
It is also described in The Photographic Process, Vol. 3, pp. 198-201 (Macmillan, 1966), and discloses the use of long-chain cyanine dyes.

It is well known that silver halide photographic materials spectrally sensitized to the near-infrared region or the infrared region generally have poor storage stability over time, and various improved techniques have been disclosed.

On the other hand, with the rapid processing of silver halide photographic light-sensitive materials in recent years, the stability of running processing of the light-sensitive material has become more and more important, and the sensitometric performance has been increased due to the degree of fatigue of the developer during the rapid processing. There is a demand for stable rapid processing performance with no fluctuation.

[0008] The photosensitive material for a laser light source according to the present invention is no exception, and there is a strong demand for processing stability. It was desired to prevent it.

Further, the color tone of the silver image after development processing tends to be yellowish brown, and from the viewpoint of medical diagnostic imaging, an image having a pure black tone and high density has been desired.

A number of proposals have been made on techniques for improving the pressure resistance of light-sensitive materials, and also on toning agents for improving silver tone, but the present invention relates to a laser light source sensitized in the near infrared region. It was insufficient for photosensitive materials.

In recent years, reductones have been regarded as a substitute for hydroquinone as a developing agent in order to reduce environmental burden in the processing of photosensitive materials.

There has been a demand for a silver halide photographic light-sensitive material for a laser light source which has no environmental load, has excellent processing stability, and has an excellent silver tone after processing, and a processing method therefor.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material for a laser light source which is excellent in processing stability and pressure resistance and has a pure black color tone of a silver image, and a processing method therefor. To provide.

[0014]

The object of the present invention has been attained by the following.

In a silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, the silver halide grains in the silver halide emulsion layer may be formed of iridium. Silver halide grains having an average grain size of 0.10 to 0.25 μm doped with
Silver halide grains chemically sensitized with a selenium and / or tellurium compound in the presence of a sensitizing dye having spectral sensitivity in the range of 0 to 1200 nm, and the hydrophilic colloid layer contains the following general formula [ A silver halide photographic material comprising at least one compound represented by the formula (I).

[0016]

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In the formula, P, Q and Y each represent a nitrogen atom or a CH group, and at least one of P, Q and Y is a nitrogen atom. A represents a hydroxy group, a sulfo group, an acylamino group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a sulfoamino group or a salt thereof. n is 1
Or an integer of 2.

The hydrophilic colloid layer has a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, and the non-photosensitive hydrophilic colloid layer contains a compound represented by the above general formula [I]. A silver halide photographic material as described in the above item.

The non-photosensitive hydrophilic colloid layer containing the compound represented by the general formula [I] is preferably located adjacent to the silver halide emulsion layer and farther from the support than the emulsion layer. A silver halide photographic light-sensitive material according to the above item.

A method for processing a silver halide photographic light-sensitive material, characterized by processing the silver halide photographic light-sensitive material according to any one of the above-mentioned items 3 with an automatic developing machine including at least a developing and fixing step. .

2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is performed with a developer containing reductones.

3. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is performed with a developer containing the compound represented by the general formula [I].

Hereinafter, the present invention will be described in detail.

In the silver halide emulsion layer according to the present invention,
Average particle size 0.10 to 0.25 doped with iridium
μm, preferably 0.15 to 0.20 μm.

In the present invention, the iridium compound doped with silver halide grains is preferably selected from a single salt or a metal complex. When selecting from metal complexes, penta-, tetra-, tri- and bi-coordinate complexes are preferred.
The complex may be a mononuclear complex or a polynuclear complex. The term "doping" as used in the present invention means that a substance other than silver ions or halide ions (for example, iridium ions) is contained in silver halide grains.

In the present invention, the iridium compound is usually added at the time of preparing silver halide grains by adding a water-soluble iridium, for example, hexachloroiridium (IV) complex salt in the form of an aqueous solution. As the addition time, it may be added in the form of the same aqueous solution as the halide for grain formation,
Any of before the grain formation, during the grain formation, or after the grain formation and before the chemical sensitization may be used. The doping may be performed only on the inside of the silver halide grains, or may be uniformly performed from the inside to the surface.

In the present invention, the addition amount of the iridium compound may be from 10 ^-9 to 10 ^-4 mol, more preferably from 1 × 10 ^{-7 to} 5 × 10 ^-6 mol, per mol of silver halide.

The above silver halide grains of the present invention containing iridium ions can be mixed with a spectral sensitizing dye in an amount of 600 to 120.
Spectral sensitization is performed so as to have a spectral maximum sensitivity in the 0 nm region. More preferably, it is a silver halide photographic material having a spectral maximum sensitivity in a 600 to 1000 nm region.

The spectral sensitizing dye having a spectral maximum sensitivity in the range of 600 to 1200 nm is not particularly limited, and examples thereof include cyanines such as cyanine, carbocyanine, dicarbocyanine, holographic polar cyanine, and complex cyanine, and merocyanine. And a composite merocyanine can be advantageously used.

The spectral sensitizing dyes that can be preferably used in the present invention are dyes represented by the following general formulas [1], [2] and [3], and at least one selected from these dyes is spectrally sensitized. It is being sensitized.

[0031]

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In the formula, Z ₁ and Z ₂ represent a group of nonmetallic atoms necessary for forming an azole ring which may have a substituent;
R ₁ and R ₂ each represent an alkyl group or a substituted alkyl group.

[0033] X ^- is an ion necessary to neutralize the molecular charge, n is 1 or 2, when forming an intramolecular salt n is 1.

The non-metallic atomic group of Z ₁ and Z ₂ may be the same or different as long as they can complete an azole ring. For example, benzothiazole, benzothiazole, 5-chlorobenzothiazole, 5-methylbenzoyl Thiazole, 5-methoxybenzothiazole, 5-hydroxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5,6-dimethylbenzothiazole,
5-ethoxy-6-methylbenzothiazole, 5-phenylbenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5,6
-Dimethylaminobenzothiazole, 5-acetylaminobenzothiazole and the like.

Examples of the benzoselenazole ring include, for example, benzoselenazole, 5-chlorobenzoselenazole,
-Methylbenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 5,6
-Dimethylbenzoselenazole, 5,6-dimethoxybenzoselenazole, 5-ethoxy-6-methylbenzoselenazole, 5-hydroxy-6-methylbenzoselenazole, 5-phenylbenzoselenazole and the like.

Further, examples of the naphthothiazole ring include β-naphthothiazole, β, β′-naphthothiazole and the like. Examples of the naphthoselenazole ring include β-naphthoselenazole.

Specific examples of the above R ₁ and R ₂ include, for example, an alkyl group such as methyl, ethyl and n-propyl;
Examples include substituted alkyl groups such as carboxyethyl, γ-carboxypropyl, γ-sulfopropyl, γ-sulfobutyl, δ-sulfobutyl, and sulfoethoxyethyl.

[0038] The above X ^- include specific examples of the anion represented by, for example halogen ions, perchlorate ion, thiocyanate ion, benzenesulfonate ion, p- toluenesulfonate ion, and the like methylsulfate ion it can.

[0039]

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In the formula, Z ₃ and Z ₅ represent a benzothiazole, a naphthothiazole, a benzoxazole and a nonmetal atom group necessary for forming a naphthoxazole ring which may have a substituent. Z ₄ represents a 5- or 6-membered carbon atom ring which may have a substituent, and R ₃ and R ₄ each represent an alkyl group or a substituted alkyl group. X ⁻ represents an ion necessary for neutralizing the intramolecular charge, n represents 1 or 2, and n is 1 when an internal salt is formed.

In the formula (2), benzothiazole rings and naphthothiazole rings represented by Z ₃ and Z ₅ (for example, naphthothiazole rings of [1,2d], [2,1d] and [2,3d]) Benzoxazole ring and naphthoxazole ring (eg, naphthothiazole rings of [1,2d], [2,1d] and [2,3d]) each may have a substituent, for example, Examples thereof include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a halogen atom (for example, a chlorine atom and a bromo atom).

R ₃ and R ₄ are an alkyl group which may have a substituent having 1 to ₄ carbon atoms (eg, methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-acetoxyethyl, carboxymethyl, -Carboxyethyl, 3-
Carboxypropyl, 4-carboxybutyl, 2-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, vinylmethyl, benzyl, phenethyl, P-sulfophenethyl, n-propyl, isopropyl, n-butyl group, etc.)
It is.

When Z _{4 in the} general formula [2] of the present invention is a 5-membered carbon atom ring, it can be specifically expressed by the following general formula [2-a].

[0044]

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In the formula, R ₈ and R ₉ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
R ₁₀ and R ₁₁ each represent a halogen atom (eg, a chlor or brom atom), and R ₁₀ and R ₁₁ each may be an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent (eg, a phenyl group, an m-tolyl group, -A tolyl group, an m-chlorophenyl group, a p-chlorophenyl group, a substituted alkoxy group having 1 to 4 carbon atoms such as a p-methoxyphenyl group, and an alkoxycarbonylalkyl group having 1 to 4 carbon atoms (such as an ethoxycarbonylmethyl group). Etc.).

R ₁₂ represents an alkyl group having 1 to ₁₂ carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, or a phenyl group. Z ₃ , Z ₅ , R ₃ ,
R ₄ has the same meaning as in the general formula [2], and X ⁻ and n represent the general formula [2]
Is synonymous with

When Z _{4 in the} general formula [2] of the present invention is a 6-membered carbon atom ring, it can be specifically expressed by the following general formula [2-b].

[0048]

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In the formula, R ₁₃ and R ₁₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Z ₃ ,
Z ₅ , R ₃ , R _4, X ⁻ and n have the same meanings as in the general formula [2].

Next, the compound of the general formula [3] according to the present invention will be described.

[0051]

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In the formula, R ₅ and R ₆ represent an alkyl group or a substituted alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. Examples of the substituent that may be substituted on these alkyl groups include a carboxyl group, a sulfone group, a cyano group,
Halogen atom (for example, chlor atom, bromo atom, fluorine atom, etc.), hydroxyl group, alkoxycarbonyl group (preferably having 8 or less carbon atoms), alkoxy group (preferably having 7 or less carbon atoms), aryloxy group, acyloxy group (preferably An acyl group (preferably having 8 or less carbon atoms), a carbamoyl group, a sulfamoyl group,
An aryl group and the like can be mentioned.

R ₇ is a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group, preferably an alkyl group having 1 to 4 carbon atoms or a benzyl group. Y is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or a halogen atom, and the alkyl group may have a substituent. Examples of the substituent include a carboxymethyl group, a trifluoromethyl group, and an alkoxy group. And the like. The nitrogen-containing heterocyclic 5-6 membered represented by Z _6, for example a thiazole ring include selenazole ring, an oxazole ring, 3,3-alkyl indolenine ring, and imidazole ring.

Of these, a thiazole ring is preferred,
The oxazole ring is more preferably a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring, a naphthoxazole ring, or the like. X ⁻ and n have the same meanings as in the general formula [1], and m and p represent 1 or 2.

Next, specific examples of the compounds represented by the general formulas [1], [2] and [3] are shown, but the present invention is not limited to these.

[0056]

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[0057]

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[0058]

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Examples of the dye represented by the general formula [1] include the specific examples (1) described in JP-A-3-200953, including the above.
To (32) can be used.

The dyes of the general formula [2] include the dyes of the general formula [1] described in JP-A-4-251839 including the above.
1-1 to 1-16 can be used.

Further, as the dye of the general formula [3], the dye represented by the general formula [2] described in JP-A-4-251839 is similar to the above.
2-1 to 2-10 can be used.

The dyes represented by the general formulas [1], [2] and [3] according to the present invention include, for example, F.I. M. Hamer, The Chemistry of Heteroc
The compound can be synthesized according to the method described in “Cyclic Compound”, Vol.

The use amount of these spectral sensitizing dyes is preferably from 0.003 g to 0.3 g per mol of silver halide.
And more preferably 0.005 g to 0.15
g. These dyes may be added directly to the emulsion, but may be any suitable hydrophilic solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone,
It may be dissolved in water or a mixed solution thereof and added.
Further, an ultrasonic method may be used as a dissolution method.

As a method of adding to an emulsion, for example, US Pat. Nos. 3,469,987 and 3,822,135
No., JP-B-46-24185, JP-A-50-8082
6, No. 51-74624, and the like.

The silver halide grains of the present invention may further contain selenium and / or selenium in the presence of the above-described spectral sensitizing dye.
Alternatively, it is chemically sensitized with a tellurium compound. The selenium and tellurium compounds used include a wide variety of compounds.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), and selenoureas (eg, N, N-dimethylselenourea, triethyl N, N, N′-seleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N '
-Trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and seleno Esters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (triphenylphosphine selenide, diethyl selenide) , Diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenides, selenoureas,
Selenoamides and selenoketones.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 ^-4 per mol of silver halide.
Used in the molar range.

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The emulsion pH was 4-9, pAg
Is preferably in the range of 6.0 to 9.5.

In the spectral sensitization method for color sensitization in the near infrared region and the chemical sensitization method using selenium and / or tellurium compounds in the present invention, each of them may be chemically ripened simultaneously.
The ripening time may be staggered.

Next, useful examples of tellurium sensitizers used in the present invention include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyl). Tellurourea, N, N'-
Dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides (eg, Telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer. In the present invention, chemical sensitization may be performed by combining selenium sensitization and tellurium sensitization.

The hydrophilic colloid layer containing the silver halide photographic light-sensitive material of the present invention contains at least one compound represented by the above general formula [1].

The hydrophilic colloid layer referred to in the present invention comprises:
It has a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, and the non-photosensitive hydrophilic colloid layer here is:
A layer having no sensitivity substantially contributing to image formation, for example, a protective layer, an intermediate layer, a dye layer, an undercoat layer, an antistatic layer or a non-photosensitive silver halide emulsion layer; Refers to a non-photosensitive hydrophilic colloid layer.

In the general formula [I], P, Q,
Y represents a nitrogen atom or a CH group, and at least one of P, Q, and Y is a nitrogen atom. Specific heterocycles include tetrazole, triazole, imidazole, pyrazole and the like, and preferably a tetrazole ring.

R ₁ represents a linear or branched alkylene group having 1 to 8 carbon atoms, A represents a hydroxy group, an acylamino group,
Carboxyl group or a salt thereof, sulfo group or a salt thereof,
Represents a sulfoamino group or a salt thereof. The salt mentioned here is an alkali metal atom (for example, Na, K or the like). Z represents a hydrogen atom or an SM group, and M represents a hydrogen atom, an alkali metal atom (eg, Na, K, etc.) or an ammonium group. n represents an integer of 1 to 2.

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

[0077]

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The above-mentioned compounds are compounds known as photographic fogging inhibitors and can be easily synthesized using, for example, isothiocyanate as a starting material.

The addition amount of the compound represented by the above general formula [I] of the present invention is optional, but when it is used in a silver halide emulsion layer, it is usually 1 × 10 ^-8 per mol of silver halide.
To 1 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁷ to
It is 1 × 10 ^-3 mol. The compound may be added at any time, but may be added to the silver halide emulsion at any time from immediately before chemical ripening to preparation of the emulsion coating solution. Upon addition, it may be added by dissolving in water or a hydrophilic solvent such as methanol, ethanol, or the like, or may be added as a solid dispersion in fine particles.

The compound represented by the above general formula [I] of the present invention may be used alone or in combination of two or more. Further, it may be used in combination with a known fog inhibitor outside the present invention.

The compound represented by the above general formula [I] of the present invention is preferably added to a non-photosensitive hydrophilic colloid layer of the silver halide photographic material of the present invention, for example, a protective layer on an emulsion layer. .

That is, the non-photosensitive hydrophilic colloid layer of the present invention containing the compound represented by the above formula [I] is a hydrophilic colloid layer adjacent to the photosensitive silver halide emulsion layer. The layer is preferably located farther from the support than the photosensitive silver halide emulsion layer. The amount of addition is in accordance with the case of the silver halide emulsion layer.

The silver halide emulsion used in the present invention may have any silver halide composition, for example, silver chloride, silver bromide,
Any silver halide such as silver iodobromide and silver chloroiodobromide may be used. A preferred silver halide composition is a silver iodobromide emulsion containing 30 mol% or less of silver iodide.

The silver halide grains may be of any crystal type as long as they have the constitution of the present invention, and may be, for example, single crystals such as cubic, octahedral, and tetrahedral. The polytwinned particles may be used.

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 (1
Emulsion, December 978), pp. 22-23.
Preparation and Types ”, or the method described in (RD) No. 18716 (November 1979), page 648.

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.

The average grain size of the silver halide grains used in the present invention is preferably 0.10 to 0.25 μm, more preferably 0.15 to 0.20 μm.

The tabular silver halide grains preferably used in the present invention have a ratio of the grain size to the grain thickness (hereinafter referred to as aspect ratio) of 2 or more, preferably 2.0 or more and less than 15.0. It is. In particular, 3 or more and less than 10 are preferable. Here, the grain size is an average projected area diameter (hereinafter, referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (of a circle having the same projected area as the silver halide grains). (Diameter), and thickness refers to the distance between two parallel major planes forming tabular silver halide grains. The silver halide photographic light-sensitive material of the present invention can be chemically sensitized with a noble metal salt such as a sulfur compound or a gold salt, and sensitized by combining these sensitization methods with the above-described chemical sensitization method using a selenium and / or tellurium compound. I can feel it.

Specific examples of the sulfur sensitizer applicable to the present invention include thiosulfate and 1,3-diphenylthiourea.
Preferred examples include thiourea derivatives such as triethylthiourea, 1-ethyl, 3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. still,
As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As gold sensitizers, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-9 mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 1
^0-8 mol.

The sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols or other inorganic or organic solvents and adding them in the form of a solution. It may be added in the form of a dispersion obtained by emulsifying and dispersing using such a medium. Both sulfur sensitization and gold sensitization may be performed simultaneously or separately and stepwise.

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.

Compounds used in such a step include, for example, Research Disclosure (RD) N
o. 17643 (December 1978), (RD) No.
18716 (November 1979) and (RD) No. 3
Various compounds described in 08119 (December 1989) can be used. These three (RD)
The types and locations of the compounds described in are described below.

[0095]

[Table 1]

The support used in the silver halide photographic light-sensitive material of the present invention includes those described in the above RD. A suitable support is a polyethylene terephthalate film or the like, and the surface of the support is coated. In order to improve the adhesiveness of the layer, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

The silver halide photographic material of the present invention is processed by an automatic developing machine including at least a developing step and a fixing step. Preferably, the processing method is completed through the steps of development, fixing, washing and drying.

The silver halide photographic material of the present invention is preferably processed with a developer containing reductones. The reductones used in the treatment method of the present invention include an enediol type, an enaminol type, an enediamine type, a thiol enol type and an enamine thiol type. Preferably, a compound represented by the following general formula [II] is specifically exemplified.

[0099]

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In the formula, R ₁ represents a hydrogen atom or a hydroxyl group;
l represents an integer of 1 to 4. As the compound represented by the general formula [II], typical examples of the compound are shown below.

[0101]

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[0102]

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The reductones used in the present invention can be used in the form of alkali metal salts such as lithium salts, sodium salts and potassium salts. The most preferred reductones in the present invention include ascorbic acid and erythorbic acid represented by II-1 above.

These reductones are used in an amount of 1 to 100 g, preferably 5 to 50 g, per liter of the developing solution.

The silver halide photographic light-sensitive material of the present invention is preferably processed with a developer containing the compound represented by the above general formula [I]. The compound represented by the above general formula [I] has the effects of improving the processing stability of the light-sensitive material of the present invention at the time of development, improving silver tone, and reducing roller marks.

The compound represented by formula (I) preferably used in the processing method of the present invention is used in an amount of 1 to 1000 mg, preferably 50 to 500 mg, per liter of a developing solution.
Used. The compounds may be used alone or in combination, and can be used by directly adding to the developer.

In the developing solution in the processing method of the present invention, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, , 3-Dibromohydroquinone, 2,5-dimethylhydroquinone,
Potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, catechol, etc.), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1
-Phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4 -Dimethyl-
3-pyrazolidone, 1- (2-benzothiazolyl) -3
-Pyrazolidone, 3-acetoxy-1-phenyl-3-
Pyrazolidone, etc.), 3-aminopyrazolines (for example,
1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl)-
3-aminopyrazoline and the like and phenylenediamines (for example, 4-amino-N, N-diethylaniline, 3
-Methyl-4-amino-N, N-diethylaniline, 4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methoxyethylaniline, etc.) can be added in combination.

Further, even when an aminophenol is used as an auxiliary developing agent, a high contrast image can be obtained. 4-aminophenol as an aminophenol developing agent,
4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,4-diaminophenol,
N- (4-hydroxyphenyl) glycine, N- (2 '
-Hydroxyethyl) -2-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, and hydrochlorides and sulfates of these compounds. .

The addition amount of these compounds is from 0.2 g to 40 g, preferably from 0.5 g to 2 g per liter of developer.
5 g.

The developer of the present invention contains known materials such as preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants, defoamers, colorants, 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.

[0112]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 (Preparation of emulsion EM-1) 60 ° C., pAg = 8, pH =
While controlling at 2.0, a monodispersed cubic seed emulsion of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.13 μm was obtained by a double jet method. From the electron micrograph of this emulsion, the incidence of twinning was 1% or less in number. This seed emulsion was grown as follows.

That is, 8.5 liters of a solution containing protective gelatin kept at 40 ° C. and, if necessary, ammonia was dispersed in the seed crystal, and the pH was adjusted with acetic acid. Using this solution as a mother liquor, the pH was maintained at 8.0 and the pAg was maintained at 8.5.
A 3.2 N aqueous solution of ammonium silver nitrate and an aqueous solution of potassium bromide were added by a double jet method to grow.

Thereafter, the potassium bromide solution was added by a nozzle over 8 minutes to raise the pAg to 9.7, and the mixing was terminated 10 minutes after the addition of the potassium bromide solution.

The obtained emulsion had an average particle size of 0.20 μm.
Was a tetrahedral monodispersed emulsion having a rounded apex, and the average silver iodide content of the whole grains was 0.2 mol%.

Next, desalting was performed to remove excess soluble salts. That is, while keeping the emulsion at 40 ° C., a formaldehyde condensate of sodium naphthalene sulfonate and magnesium sulfate were added, and the mixture was allowed to stand with stirring, and excess salts were removed by decantation.

(Preparation of Emulsions EM-2 to EM-4) Potassium hexachloroiridium (IV) salt in the amount shown in Table 2 below was
Emulsions EM-2 to EM-4 were prepared in the same manner as for emulsion EM-1 except that they were added to a 3.2 N potassium bromide solution. The average particle size was 0.20 μm in each case.

(Preparation of emulsion EM-5) Emulsion EM-5 was prepared in the same manner as described above, except that potassium hexachloroiridium (IV) salt was doped within 70% by volume of silver halide grains. 5 was prepared. The average particle size was 0.20 μm.

(Preparation of emulsion EM-6) Emulsion EM-6 was prepared in the same manner as described above except that potassium hexachloroiridium (IV) salt was doped within 35% by volume of silver halide grains. 6 was prepared. The average particle size was 0.20 μm.

(Preparation of Emulsions EM-7, 8) Emulsion EM-1
In the same manner as in the above emulsions EM-2 to -4, except that the used amount of the monodispersed cubic seed emulsion prepared in
7, 8 were prepared. The average particle size is 0.25 μm and 0.30
μm.

[0122]

[Table 2]

Next, the emulsion after desalting dispersed in gelatin was heated to 55 ° C., and then 1-5 of the exemplified sensitizing dyes according to the present invention.
Was added in an amount of 140 mg per mol of silver halide. Next, triphenylphosphine selenide was added as a selenium compound as shown in Table 3.

Further, appropriate amounts of ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added for chemical sensitization.

When the highest sensitivity is reached, 4-hydroxy-
6-Methyl-1,3,3a, 7-tetrazaindene was stabilized by adding an appropriate amount per mole of silver halide.

The EM-1 to EM obtained as described above
Using -8, the following coating liquid was prepared to prepare a sample.

(Backing Layer Lower Layer Coating Solution) Gelatin 400 g i-amyl-n-decylsulfosuccinate sodium salt 0.4 g Antihalation dye 10 g Potassium polystyrene sulfonate (average molecular weight 150,000) 50 g Diethylene glycol 5 g Glyoxal 2 g Dye emulsion dispersion (The following content) 33g

[0128]

Embedded image

Make up to 7 liters with water.

Preparation of Dye Emulsion Dispersion 10 kg of the above dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate. This is an oil-based solution. On the other hand, 9.3 containing 1.35 kg of the following anionic surfactant (AS)
A 270 liter% gelatin solution was prepared. This was used as an aqueous solution. Next, the oil-based solution and the aqueous-based solution were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the mixture was made up to 240 kg with water.

[0131]

Embedded image

(Coating solution for upper layer of backing layer) Gelatin 400 g i-Amyl-n-decyl sulfosuccinate sodium salt 10 g Antihalation dye 10 g Polymethyl methacrylate (average particle size: 6 μm) 12 g SAM-1 3 g C ₈ F ₁₇ SO ₃ K 0.3 g Glyoxal 13.6 g Dye emulsified dispersion (as described above) 33 g

[0133]

Embedded image

Finishing to 7 liters with water (Red-Sensitive Silver Halide Emulsion Layer Coating Solution) The following was added to the obtained emulsion per mole of silver halide to prepare a red-sensitive silver halide emulsion layer coating solution.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1, 1-dimethylol-1-bromo-nitromethane 10 mg potassium polystyrene sulfonate (average molecular weight 150,000) 10 g

[0136]

Embedded image

[0137] (protective layer coating solution for the emulsion layer side) amount below is a film 1 m ² per.

Lime-treated inert gelatin 0.8 g i-amyl-n-decylsulfosuccinate sodium salt 27 mg polymethyl methacrylate (matting agent having an area average particle diameter of 3 μm) 28 mg silicon dioxide particles (area average particle diameter 1.2 μm) 10 mg Ludox AM (Colloidal silica (manufactured by DuPont)) 50 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt (2% aqueous solution) 5 mg Formalin (35%) 10 mg Glyoxal (40%) 40 mg Side 300 (manufactured by Permchem Asia Ltd) 1 mg SAM-1 20 mg C ₈ F ₁₇ SO ₃ K 2 mg

[0139]

Embedded image

The compound represented by the general formula [I] of the present invention was added to the coating solution for the emulsion layer and the coating solution for the protective layer as shown in Table 3.

After the biaxial stretching heat setting on both sides as a support,
JP-A-59-18945 on a polyethylene terephthalate film (175 μm thickness) subjected to a corona discharge treatment.
Latex for undercoating described in Example 1 (compound of Synthesis Example 1) was applied. Next, the following antistatic layer was applied to both surfaces.

(1) Water-soluble conductive polymer (P-1 below) 0.6 g / m ² Hydrophobic polymer (P-2 below) 0.5 g / m ² Curing agent (H-1 below) 2 × 10 ^{− 3} / dm ²

[0143]

Embedded image

[0144] The resulting silver amount of the silver halide emulsion layer on a support is 2.5 g / m ^2, the emulsion layer is 1.5 g / m ² gelatin amount, the protective layer is 0.8 g / m ² Was applied.

On the other side, the lower layer and the upper layer were coated. Amount of gelatin backing lower layer and upper layer were simultaneously coated by such a slide hopper to be 1.5 g / m ² and 0.9 g / m ^2, respectively.

The following are evaluated for each of the obtained samples.

<Sensitometry> Each sample was evaluated with a semiconductor laser beam having a wavelength of 670 nm and a wedge image printed on a 14 × 17 cm film. The sensitivities in the table are comparative sample Nos. This is a relative sensitivity where 1 is set to 100.

<Evaluation of processing stability> Automatic developing machine SRX-
701 (manufactured by Konica Corporation) and a developing solution and a fixing solution having the following compositions were processed under the condition of Dry to Dry (all processing steps) for 25 seconds.

However, the difference between the sensitivity when the treatment was carried out in the state of the new solution and the sensitivity when the samples were run from the new solution and the activity of the treatment solution was brought to an equilibrium state was determined. That is, the larger the sensitivity difference in the table, the lower the processing stability. However, the replenishment of the processing solution during the running process was 90 ml per 1 m ² of the film for both the developing solution and the fixing solution.

(Formulation of developer) <Part A> (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriaminepentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 140 mg 1- Phenyl-5-mercaptotetrazole 250 mg 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 102 g Hydroquinone 390 g Diethylene glycol 550 g Water is added to make up to 6000 ml.

<Part B> (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0.4 g (starter formulation) Glacial acetic acid 120 g KBr 225 g 1 ml after adding water To finish.

(Fixing solution formulation for 18.3 liter finishing) <Part A> Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N) -Dimethylamino) -ethyl-5-mercaptotetrazole 18 g <Part B> 800 g of aluminum sulfate To prepare a developer, add parts A and B simultaneously to about 5 liters of water, add water while stirring and dissolving, and finish to 12 liters. The pH was adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher. 20 ml of the above-mentioned starter is added to 1 liter of the replenisher to adjust the pH to 10.26, and this is used as a used solution.

The fixing solution was prepared by simultaneously adding parts A and B to about 5 liters of water, adding water while stirring and dissolving to make up to 18.3 liters, and adjusting the pH to 4.4 using sulfuric acid and NaOH. Is a fixer replenisher.

The processing temperature was 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, and 50 ° C. for drying, and the processing time was 25 seconds dry to dry.

<Evaluation of Roller Mark> The obtained sample was exposed to a semiconductor laser beam having a wavelength of 670 nm so that the blackening density after the development processing became 1.0.
Inch films were processed as described above. However, the development rack and the transition rack from development to fixing used at this time were those that were intentionally fatigued and damaged. Therefore, a large number of fine spot-like density unevenness occurs in a sample having poor pressure resistance due to the pressure caused by the unevenness of the rollers of the rack in the processed film sample, which is suitable as a method for evaluating roller marks. The evaluation was visually evaluated in the following five stages.

5: No spots are generated 4: Spots are slightly generated, but there is no problem in practical use 3: Acceptable limit level where small spots are generated but not generated in a normal rack 2: Spots are generated Occurred occasionally even in a normal rack 1: Spots frequently occurred and always occurred in a normal rack <Evaluation of silver tone> The roller mark evaluation sample was visually observed, and the silver tone was evaluated as follows. It was evaluated by rank.

A: Pure black tone B: Slightly reddish black C: Slightly yellowish black D: Yellowish black The results obtained are shown below.

[0158]

[Table 3]

As is clear from Table 3, the sample according to the present invention has high sensitivity and stable running processing performance with little processing fluctuation, and exhibits silver tone of pure black tone. Further, generation of roller marks indicating pressure resistance was hardly observed in the sample of the present invention.

Example 2 Sample No. 1 of Example 1 1, 4, 13 to 15 and 17 were developed with the following processing solutions, and evaluated in the same manner as in Example 1.

(Developer composition for finishing 1 liter) <Part A> Reductones (Exemplified Compound 4-1) 30 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.0 g 50% potassium sulfite 195 g Boric acid 20 g Sodium bicarbonate 20 g 5-methylbenzotriazole 0.03 g 1-phenyl-5-mercaptotetrazole 0.05 g Diethylene glycol 70 g 50% potassium hydroxide 110 g Finished to 550 ml with pure water and adjusted to pH 11.30.

<Part B> Acetic acid (90%) 22 g Triethylene glycol 5.0 g 1-phenyl-3-pyrazolidone 3.0 g 5-Nitroindazole 0.03 g n-acetyl-D, L-penicillamine 0.2 g The present invention (Amount shown in Table 3) <Part C> Glutaraldehyde (50%) 7.0 g Sodium bisulfite 8.0 g Pure water 20 ml (Fixing solution composition for finishing 1 liter) Ammonium thiosulfate (70 wt / vol%) 250 g Sodium sulfite 25 g Sodium thiosulfate 20 g Acetic acid (90%) 25 g β-alanine 40 g Aluminum sulfate 30 g Finished to 500 ml with pure water, and adjusted to pH 4.45.

(Developer Starter Composition) Acetic Acid (90%) 195 g HO (CH ₂ ) ₂ —S— (CH ₂ ) ₂ OH 1.5 g Potassium Bromide 225 g 5-Methylbenzotriazole 1.5 g Compound A CH ₃ N (CH ₂ CH ₂ CH ₂ NHCONHCH ₂ CH ₂ SC ₂ H ₅ ) ₂ 1.0 g Finish up to 1000 ml with pure water.

The pH of the working solution was 10.56 for the developing solution and 4.50 for the fixing solution, and was adjusted with KOH and sulfuric acid, respectively. After adding 20 ml per 1 liter of the developing solution, the pH of the developing starter is adjusted to 10.30 using KOH or acetic acid.
To make a development start solution.

The above processing solution was dried to dry using an automatic developing machine SRX-503 modified machine [manufactured by Konica Corporation].
(Developing temperature 35 ° C, so that (total processing time) is 25 seconds)
Fixing temperature 33 ° C, washing water 18 ° C, 4.0 liters / minute
The treatment was carried out at a temperature of 55 ° C. in a feeding and drying step. Two pairs of heat rollers having a temperature of 70 ° C. were provided in the drying unit. The results obtained are shown in Table 4 below.

[0166]

[Table 4]

As shown in Table 4, also in the processing method according to the constitution of the present invention, there was little processing fluctuation, high sensitivity, stable running processing performance, and silver tone of pure black tone. Also, roller marks were hardly recognized in the samples of the present invention.

[0168]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material having excellent running processing stability and a pure black tone in the processed image, and a method for processing the same are obtained. Was done. Further, according to the present invention, it was possible to prevent the occurrence of roller marks during the development processing.

Claims (6)

[Claims] In a silver halide photographic material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, silver halide grains in the silver halide emulsion layer are Iridium-doped silver halide grains having an average grain size of 0.10 to 0.25 μm;
Silver halide grains chemically sensitized with a selenium and / or tellurium compound in the presence of a sensitizing dye having a spectral maximum sensitivity in the range of ~ 1200 nm, and in the hydrophilic colloid layer, At least one of the compounds represented by the formula:
A silver halide photographic light-sensitive material comprising a seed. Embedded image In the formula, P, Q, and Y each represent a nitrogen atom or a CH group, and at least one of P, Q, and Y is a nitrogen atom. A represents a hydroxy group, a sulfo group, an acylamino group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a sulfoamino group or a salt thereof. n represents an integer of 1 or 2. 2. The hydrophilic colloid layer has a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, and the compound represented by the general formula [I] is contained in the non-photosensitive hydrophilic colloid layer. The silver halide photographic light-sensitive material according to claim 1, further comprising: 3. A non-photosensitive hydrophilic colloid layer containing the compound represented by the formula [I] is adjacent to the silver halide emulsion layer and located farther from the support than the emulsion layer. The silver halide photographic light-sensitive material according to claim 2, wherein 4. A silver halide photographic light-sensitive material characterized in that the silver halide photographic light-sensitive material according to claim 1 is processed by an automatic developing machine including at least a developing and fixing step. Processing method. 5. The method for processing a silver halide photographic material according to claim 4, wherein the processing is performed with a developer containing reductones. 6. The method for processing a silver halide photographic material according to claim 4, wherein the processing is performed with a developer containing the compound represented by the general formula [I].