JPH09218478A - Silver halide photographic sensitive material and method for processing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive material free of occurrence of roller marks and stabilized sensitometric performance even in the case of ultra- highspeed processing reduced in a replenishing rate, and superior in silver tone and free from uneven reflection spots. SOLUTION: This silver halide photographic sensitive material has at least one silver halide emulsion layer and a nonphotosensitive hydrophilic colloidal layer on a support and the silver halide emulsion layer and/or the nonphotosensitive hydrophilic colloidal layer contains flat silica and a fluorinated surfactant. This photosensitive material is processed in the total processing time (Dry to Dry) of 10-45 sec.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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, with respect to the development processing of silver halide photographic light-sensitive materials, it has been desired to shorten the processing time and reduce the processing waste liquid for environmental purification. For example, in the medical field, regular medical examinations, the spread of medical checkups, etc., and the number of examinations including diagnosis in general medical care have increased sharply, which has led to an increase in the number of X-ray photographs taken, further speeding up and processing development after imaging. Demands for further reduction of waste liquid are increasing.

In order to perform development processing in a short time, developability is required.
A light-sensitive material having excellent fixability and capable of being dried in a short time after washing with water is required. As a technology for improving the sensitivity and drying property of X-ray photographic light-sensitive materials, a method of using tabular silver halide grains with high covering power, a method of reducing the amount of gelatin in the emulsion layer, and a method of increasing the hardness and swelling during processing There are known methods for suppressing the drying load.

Many techniques for increasing the sensitivity using tabular silver halide grains have been disclosed and are known.

These tabular silver halide grains are hexahedral,
Compared with so-called normal crystal silver halide grains such as octahedron, the surface area is large in the same volume, so it is possible to increase the adsorption amount of the spectral sensitizing dye on the grain surface, resulting in higher sensitivity. There are advantages.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular silver halide. A technique using particles is disclosed and an effect of increasing sensitivity is shown.

However, if a method of reducing the amount of gelatin as a means for reducing the drying load while using these tabular grains or a method of increasing the hardness and suppressing the swelling during processing, the pressure resistance is deteriorated. Causes a reroller mark, and a difference in the activity of the treatment liquid causes a large variation in the sensitometry performance, making it impossible to obtain a stable image.

Further, the silver tone after development has a yellowish tint,
Medically X
It was difficult to use it as a line photograph luster material. These appear more conspicuously when the treatment liquid replenishment amount is reduced and the treatment is also a problem in promoting reduction of the treatment waste liquid.

[0009]

A silver halide having no roller marks, stable sensitometric performance even in ultra-rapid processing with a reduced replenishment amount, excellent silver tone, and no unevenness in reflection spots. To provide a photographic light-sensitive material and a processing method thereof.

[0010]

DISCLOSURE OF THE INVENTION The inventors of the present invention have developed a halogenated silver halide grain for the purpose of increasing the sensitivity by using hexagonal tabular silver halide grains and reducing the amount of gelatin and increasing the hardness to prevent deterioration of pressure resistance. One of the drawbacks of the generation of roller marks and large fluctuations in sensitometric performance in silver emulsion formulation is that tabular silica and a fluorine-containing surfactant are contained in the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer. They have found that they can be easily solved, and have reached the present invention.

That is, 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, wherein the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer is tabular silica. 1. a silver halide photographic light-sensitive material characterized by containing a fluorine-containing surfactant and A silver halide photographic light-sensitive material according to item 1, wherein the silver halide emulsion layer contains a compound represented by the following general formula (1): Z-SM in the general formula (1): _{SO 3 M 1, -COOR 1,} -OH and -N
Represents a heterocycle directly or indirectly having a substituent selected from HR ₂ , M and M ₁ represent a hydrogen atom, an alkali metal atom or a quaternary ammonium group, and R ₁ represents a hydrogen atom, an alkali metal atom or the number of carbon atoms. 1 to 6 alkyl group, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, —COR ₃ , CO
OR ₃ or —SO ₂ R ₃ represents R ₃ , wherein R ₃ represents a hydrogen atom, an aliphatic group or an aromatic group, and the total treatment in the processing method for processing a silver halide photographic light-sensitive material according to the item 3.1 or 2. Time (Dry to D
3. ry) is 10 seconds or more and less than 45 seconds, a method for processing a silver halide photographic light-sensitive material, The total processing time (Dry to Dry) is 10 seconds or more and less than 45 seconds, and the replenishment amounts of the developing solution and the fixing solution in the processing step are 30 ml / m ² or more and 200 ml / m ² or less, respectively 3. The method for processing a silver halide photographic light-sensitive material as described in the above item.

Hereinafter, the present invention will be described in detail.

The tabular silica of the present invention means a layered silicate containing alkali, alkaline earth metal, aluminum and the like, and examples thereof include kaolin minerals, mica clay minerals and smectites.

Kaolin minerals include kaolinite, dicanite, nacrite, halloysite, and serpentine, and mica clay minerals include pyrophyllite, talc muscovite, swelling synthetic fluoromica, sericite, and chlorite. . Examples of smectite include smectite, vermiculite, and swelling synthetic fluorine vermiculite.

Particularly preferred is smectite having swelling property and ion exchange property.

There are two types of smectites, natural products and synthetic products. Examples of natural products are montmorillonite and beidellite, which are obtained as viscosities called bentonite and acid clay, and these are used as antistatic agents. An example of use in a non-photosensitive hydrophilic colloid layer is JP-A-60-2.
No. 02438 and No. 60-239747. However, synthetic compounds are preferably used because of their excellent transparency.

There is also one containing fluorine for the purpose of further improving heat resistance.

Specific examples of the synthetic smectite include, for example, Lucentite SWN and SW manufactured by Corp Chemical Co., Ltd.
F etc. can be mentioned.

These tabular silicas are preferably tabular silicas having an aspect ratio of 2 or more in 50% or more of the total projected area of all silicas in the emulsion layer used.

The aspect ratio as used herein means the ratio of the diameter of a circle having the same area as the projected area of flat silica and the distance between two parallel planes.

In the present invention, the aspect ratio is 2 or more and 1
It is preferably less than 00, particularly preferably 2 or more and less than 50.
The thickness of the tabular silica of the present invention is preferably 1.0 μm or less, more preferably 0.5 μm or less.

The distribution of tabular silica grains is 30% in terms of the coefficient of variation that is often used (100 times the value s / d obtained by dividing the standard deviation s when the projected area is approximated by a circle by the diameter d).
Hereinafter, it is particularly preferable that the monodisperse is 20% or less, but it is not an essential condition.

The tabular silica of the present invention is preferably used in a dry weight ratio of 0.05 to 1.0, particularly preferably 0.1 to 0, based on gelatin used as a binder for the layer to be added. .6. Further, tabular silica and colloidal silica may be used in combination.

In the present invention, the tabular silica is generally added to the coating solution as an aqueous dispersion, and its preparation method is as follows: a predetermined amount of water and a high-speed stirrer having a sufficient shearing force, for example, a homogenizer. A method is preferred in which tabular silica is added little by little and dispersed while stirring with a mixer, impeller or the like.

When preparing the dispersion liquid, polyphosphates such as sodium pyrophosphate and sodium hexametaphosphate, polyhydric alcohols such as trimethylolpropane, trimethylolethane and trimethylolmethane, and nonionics such as polyethylene glycol alkyl ester. An aqueous dispersion such as a polymer can be added as appropriate.

The coating amount of the hydrophilic binder in the layer containing tabular silica in the present invention is preferably 3.0 g / m ² or less, and particularly preferably 2.0 g / m ² or less per one side of the support. However, the hydrophilic binder in the present invention means gelatin, dextran, dextrin,
It means a hydrophilic colloidal substance such as a natural or synthetic hydrophilic polymer such as polyacrylamide.

As the fluorine-containing surfactant of the present invention,
For example, the exemplified compound 1 described in JP-A-4-362633
6, 1-10, 2-1 to 2-6, 3-1 to 3-4, 4-
1-4-6, exemplary compounds FA-1, FA-2, FA-4 to FA-10, FA- described in JP-A-5-341458.
12-FA-2, FA-31-FA-49, FK-2-
FK-6, FK-8 to FK-11, FK-13 to FK-
20 can be used.

Specific examples of these compounds are shown below.
It is not limited to these.

[0029]

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[0030]

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The fluorinated anionic activator or fluorinated cationic activator of the present invention is described in, for example, the journal of the Chemical Society of England (J.
Chem. Soc. ) 1950, p. 2789, ibid. 195
7 2574 and 2640, American Chemical Society Journal (J.
Amer. Chem. Soc. Vol. 79, page 2549, Oil Chemistry (J. Japan Oil Chemists So.
c. 12: 653, American Society of Organic Chemistry (J. Or.
g. Chem. ) Vol. 30, page 3524 (1965) and the like.

Some of these fluorine-based activators are trade names of Megafax F from Dainippon Ink and Chemicals, Inc., and Fluorad FC from Minnesota Mining and Manufacturing Company. ) Under the trade name of Monflor (Mo from Imperial Chemical Industry).
nflor) under the trade name of E. I. DuPont Nemeras & Co.
s) and sold under the trade name Licowet VPF by Farbeberke Hoechst.

The total amount of the fluorine-based cationic activator and the fluorine-based anionic activator used in the present invention is preferably 0.1 to 1000 mg, preferably 0.5 to 300 mg, per m ² of the photographic light-sensitive material. Preferably 1.0-15
0 mg is good. When used in combination, two or more kinds may be used in combination. Other fluorinated nonionic activators,
A fluorine-based betaine activator and a hydrocarbon-based activator may be used in combination.

The addition ratio of the fluorine-based anionic activator and the fluorine-based cationic activator of the present invention is 1:10 to 1 in a molar ratio.
0: 1 is preferable, and 3: 7 to 7: 3 is more preferable.

The fluorine-based anionic activator and the fluorine-based cationic activator of the present invention are added to the emulsion layer and the emulsion protective layer. Further, the surface of the emulsion protective layer may be further overcoated with the fluorine-based activator according to the present invention.

In the present invention, the compound represented by the following general formula (1) is preferably used.

General formula (1) Z-SM In the above formula (1), Z is -SO ₃ M ₁ , -COOR ₁ , -O.
Heterocyclic groups having a substituent selected directly or indirectly from H and -NHR ₂ , such as oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, pyrimidine ring, Thiazine ring, triazine ring, thiodiazine ring or a ring bonded to other carbon ring or hetero ring, for example, benzothiazole ring, benzotriazole ring, benzimidazole ring, benzoxadiazole ring, benzoselenazole ring, naphthoxazole ring, tria It is a zaindolizine ring, a diazaindolizine ring or a tetraazaindolizine ring (at least one of the above groups is substituted on these rings).

Preferred examples include an imidazole ring, a tetrazole ring, a benzoxazole ring and a triazole ring. Particularly preferred is a tetrazole ring.

M and M ₁ in the general formula (1) represent a hydrogen atom, an alkali metal atom or a quaternary ammonium group,
R ₁ is a hydrogen atom, an alkali metal atom or a carbon number of 1 to 6
Wherein R ₂ is a hydrogen atom, having 1 to 6 carbon atoms.
Alkyl group, -COR _3, -COOR ₃ or -SO ₂ R ₃
R ₃ represents a hydrogen atom, an aliphatic group (for example, having 1 to 1 carbon atoms)
20 alkyl groups, specifically, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, t-butyl group, n-octyl group, dodecyl group, cyclohexyl group and the like, or aromatic group (for example, aryl group having 6 to 20 carbon atoms, specifically phenyl group, naphthyl) And these groups may further have a substituent.

The number of hydrophilic groups in the compound represented by the general formula (1) may be any number as long as it is 1 or more, and compounds having 2 or more hydrophilic groups are also preferably used. Further, the pKa of the hydrophilic groups may be any number, but one having at least one hydrophilic group having a pKa of 7 or more is preferably used. Particularly hydrophilic group -SO ₃ M _1, it shall preferably -COOR _1.

Further, a so-called precursor type compound capable of releasing the compound represented by the general formula (1) with time and / or into the treatment liquid can also be preferably used.

Among the heterocyclic mercapto compounds represented by the general formula (1), particularly preferable compounds are those represented by the following general formula [1a].

[0043]

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In the formula, X and Y are nitrogen atoms or CR ₄ (R ₄
Is a hydrogen atom or a substitutable group. ) And R ₄
Is a substituted or unsubstituted organic group, and the organic group is an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, t-butyl group, n-
An octyl group, a dodecyl group, a cyclohexyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g., phenyl group, naphthyl group, etc.), a heterocyclic group (5 or more containing at least one nitrogen atom, oxygen atom or sulfur atom) A 6-membered ring, a 6-membered ring, or a 7-membered ring, including those that form a condensed ring at an appropriate position, such as a pyridine ring, a quinoline ring, a pyrimidine ring, etc.) or an alkyl group, an aryl group, or a hetero ring group -S -, - O -, - NR 5 -, - CO -, - SO
—, —SO ₂ — represents a group constituted via a linking group composed of, for example. (R ₅ represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms.) The substituent of these alkyl groups, aryl groups and heterocyclic groups or the substitutable group represented by R ₄ has the general formula (1 )
It has the same meaning as the substituent represented by the heterocyclic residue therein, and may be different when there are two or more substituents.

Preferred compounds in the general formula [1a] are
X and Y are nitrogen atoms, and R ₅ is an aryl group having two or more groups selected from an anion group or a group capable of dissociating into an anion. Particularly preferred aryl group is ortho-position to mercaptotetrazole group. Is an aryl group having a hydroxyl group. M ₂ represents a hydrogen atom, an alkyl metal, or a quaternary ammonium group, and at least one of R ₄ and R ₅ has a group selected from an anion group and a group capable of dissociating into an anion.

Below, the general formula (1) and the general formula [1a]
Specific examples of the compound represented by are shown below, but the present invention is not limited to these compounds.

[0047]

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[0048]

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[0049]

[Chemical 6]

[0050]

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[0051]

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The compound represented by the general formula (1) is known, and is described in US Pat. A. Burgess et al., "Journal of Heterocyclic Chemistry" (DA Berges et. Al., Jo.
internal of Heterocyclic Che
Missry, Vol. 15, No. 981 (1978), "The Chemistry of Heterocyclic Compounds," Imidazole and Derivatives, Part 1.
(The Chemistry of Heteroc
iclicound, Imidazole
and Derivatives part 1) 336
~ 339, Chemical Abstracts (Chemic
al Abstract) 58, 7921 (1963)
(Year) According to the method described on page 394 or the like, it can be easily synthesized.

The processing of the silver halide photographic light-sensitive material of the present invention is carried out, for example, by RD-17643, XX-XXI, 29-.
XX to XXI of page 30 or 308119, 1011 to 10
Treatment with a treatment liquid as described on page 12 may be performed.

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

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

The development processing method of the silver halide photographic light-sensitive material of the present invention is carried out by an automatic processor, and the total processing time (Dry
to Dry) 10 seconds or more and less than 45 seconds.

Here, the total processing time (Dry to Dr)
y) means the time from the time when the tip of the light-sensitive material starts to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing step, and more preferably 15 to 30 seconds.

The developing temperature is preferably 25 ° C to 50 ° C and 3
0 ° C to 40 ° C is more preferred. The development time is 5 seconds to 45 seconds, preferably 8 seconds to 30 seconds.

The fixing temperature and time are about 20 ° C to 50 ° C.
6 seconds to 20 seconds is preferable at 30 ° C, 6 seconds to 30 ° C to 40 ° C
15 seconds is more preferable.

The replenishing amounts of the developing solution and the fixing solution in the present invention are each 200 ml / m ² or less, more preferably 30 to 160 ml / m ² , and particularly preferably 30 to 160 ml / m ^2.
100 ml / m ² .

Drying time is usually 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with a far infrared ray heating means may be installed in the automatic processor.

The automatic developing machine is provided with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during the steps of development, fixing and washing with water (Japanese Patent Laid-Open No. 3-2980).
-264953) may be used. Further, a device capable of adjusting a developing solution and a fixing solution may be incorporated.

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
(December 978), page 22-23, 1. Emulsion manufacturing method "E
mulsion preparation and T
types (RD) No. 18
716 (November 1979), p. 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, T.W. H. By James, "T
he Theory of the Photogra
phy Process "4th edition Macmilla
n, published by Company (1977), pp. 38-104,
G. FIG. F. "Photographic Emulsion Chemistry" by Dauffin, "Photo
optic Emulsion Chemist
ry "Focal Press (1966),
P. "The Physics and Chemistry of Photography" by Glafkids, "Ch
imie et Physique Photogra
phique "Paul Montel (196
7 years). L. "Manufacture and Coating of Photographic Emulsions," Zelikman et al., "Making and Coating"
Photographic Emulsion "Foc
It is prepared by the method described in al Press (1964).

That is, the solution method conditions such as the acid method, the ammonia method, the neutral method and the like are mixed under conditions such as a forward mixing method, a reverse mixing method, a double jet method, a controlled double jet method, a conversion method and a core / shell method. And the like, and a combination method thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

The monodisperse emulsion referred to here means an average grain diameter measured from a microscopic photograph of silver halide grains.
At least 95% of the grains by number or weight are silver halide grains within ± 30%, preferably ± 20%, of the average grain size. The term “monodispersity” as used herein refers to a method disclosed in
0-162244, wherein the coefficient of variation with respect to particle size is 20% or less.

The crystal structure of silver halide may have a silver halide composition in which the inside and the outside are different. That is, the core and the core have at least one different silver halide composition.
It has a core / shell structure composed of shells of layers or more. The silver iodide content of the high iodine part is 5 to 40 mol%, particularly preferably 5 to 30 mol%.

Methods for producing such monodisperse emulsions are known,
As a method for obtaining the above-mentioned monodispersed emulsion, for example, a method of using a seed crystal and supplying silver ions and halide ions with the seed crystal as a growth nucleus to perform growth is particularly preferable.

A method for producing a core / shell type emulsion is well known, for example, British Patent 1,027,146, US Patents 3,505,068, 4,444,877 or JP-A-60-143331. The method described in, etc. can be referred to.

The silver halide grains in the silver halide emulsion layer are preferably tabular silver halide grains. Tabular silver halide grains refer to grains having two opposing parallel main planes and have an average aspect ratio of 2 or more and less than 20,
Preferably it is 3 or more and less than 15. The average aspect ratio is represented by the ratio of the average particle diameter to the average particle thickness. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and a diameter corresponding to a circle of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ), And the thickness means the distance between two parallel principal planes forming a tabular silver halide grain.

The tabular silver halide grains have an edge ratio (long side edge length / short side edge length) of 1 to 2, preferably 1 to 1.6, more preferably 1 to 1.2. is there.

In the present invention, the emulsion layer containing tabular silver halide grains has an aspect ratio of 2 or more and an edge ratio (long side edge length / short side edge length) of 50% or more of the total projected area. 1 to 2 of tabular silver halide grains,
It is preferably at least 70%, more preferably at least 90%.

The tabular silver halide grains are silver chloroiodobromide or silver iodobromide and have an average silver iodide content of 0 to
It is preferably less than 2 mol%, more preferably 0.1 to 1.0 mol%.

The tabular silver halide grains have an average grain size of 0.
It is preferably from 15 to 5.0 μm, and from 0.4 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
4 to 2.0 μm.

The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution, specifically, (standard deviation of grain size /
Average particle size) × 100 = 25% or less is preferable when the width of the distribution is defined by the width (%) of the particle size distribution,
It is more preferably 20% or less.

The emulsion may be subjected to a water washing method such as a Noudel water washing method and a flocculation sedimentation method in order to remove soluble salts (desalting treatment step). As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a coagulated polymer agent described in JP-A-2-7037, exemplified by G-
3, a method using G-8 or the like is a particularly preferred desalting method.

The temperature for chemical ripening of the silver halide emulsion is arbitrarily determined, but is in the range of 20 to 90 ° C., preferably 3
It is 0-80 degreeC, More preferably, it is 35-70 degreeC.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention can be spectrally sensitized.

The spectral sensitizing dyes used in the present invention include cyanine, merocyanine or complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes which are usually used. Any of

These sensitizing dyes can be used alone or in combination. Spectral sensitizing dyes
It is preferably added as a solution dissolved in an organic solvent such as methanol.

The addition amount of the spectral sensitizing dye is not uniform depending on the type of dye and the emulsion conditions, but is preferably 10 to 900 mg, and particularly preferably 600 mg, per mol of silver halide.

The spectral sensitizing dye is preferably added before the end of the chemical ripening step, and may be added in several batches before the end of the chemical ripening step. More preferably, it is after the growth step of silver halide grains and before the completion of the chemical ripening step, and especially before the start of chemical ripening.

The emulsion can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978
No.) and the same No. No. 18716 (November 1979) and the same No. 308119 (December 1989).

Table 1 shows the types of compounds and the locations where they are described in these three Research Disclosures.

[0086]

[Table 1]

The silver halide photographic light-sensitive material of the present invention has at least one light-sensitive layer described above on a support and may optionally have an undercoat layer, an antihalation layer, an intermediate layer and a protective layer. Good. As the support, for example, the aforementioned RD-1
7643 and RD-308119, page 1009. As a suitable support, a polyethylene terephthalate film or the like may be used, and an undercoat layer may be provided on the surface of the support to improve the adhesion of the coating layer, or corona discharge, ultraviolet irradiation or the like may be applied.

[0088]

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

(Preparation of Tabular Silver Iodochloride Emulsion Em-1) Using the following five solutions, tabular silver iodochloride emulsion Em- was used.
1 was prepared.

Solution A Low methionine gelatin 214.37 g Sodium chloride 1.995 g Potassium iodide 149.6 mg Water to make 6090 ml Solution B Sodium chloride 10.48 g Potassium iodide 149.4 g Water to make 90 ml Solution C Silver nitrate 30. 58g Water to make 90 ml Solution D Sodium chloride 165.0 g Water to make 5640 ml Solution E Silver nitrate 479.0 g Water to make 5640 ml Solution A was stirred vigorously while keeping it at 40 ° C. The total amount of Solution C was added by the simultaneous mixing method at a flow rate of 180 ml / min over 30 seconds.

Next, after the mixed solution was kept at 40 ° C. for 10 minutes, the solution D and the solution E were added by the simultaneous mixing method at a flow rate of 24 ml per minute over 40 minutes, and then the solution D and the solution were further added. Initial flow rate of 24 ml and final flow rate of 48 m
The flow rate was increased linearly so as to be 1, and the addition was performed by the simultaneous addition method over 130 minutes. During this time, pCl was 2.
I kept it at 35 all the time.

Then, the mixture was adjusted to 1.30 with sodium chloride and desalted by the ultrafiltration method shown in FIG.

That is, the silver halide emulsion after completion of physical ripening was supplied with a pressure of 7.03 kg / cm ² by a pump and fed into an ultrafiltration device, and was passed through an ultrafiltration membrane (cellulose acetate) to give water and an inorganic substance. A part of ions and the like is separated and removed as waste liquid, and desalted.

The ultrafiltration device has a circulation loop formed by a conduit, and the flow of the emulsion in the circulation loop is advanced by a pump, and the desalination degree is increased by repeatedly passing the emulsion through the ultrafiltration device. Go. The outlet pressure of the retentate is 0.703 kg / m ² or less, and the pressure difference across the membrane is 2.
It is 81 kg / m ² .

The obtained silver halide emulsion contains iodine of 0.0
When observed by an electron microscope, the average particle size (in terms of circular diameter) was 1.45 μm, and the average thickness was 0.13 μm.
m, average aspect ratio 11, diameter variation coefficient 18.5%
Was a monodisperse tabular silver halide grain whose main plane was square (adjacent edge ratio 1.2).

Subsequently, the emulsion Em-1 was heated to 55 ° C., and then predetermined amounts of the following spectral sensitizing dyes (A) and (B) were added as a solid fine particle dispersion, followed by ammonium thiocyanate, chloroauric acid, An aqueous solution or a methanol solution of the following sulfur sensitizer and a solid dispersion of triphenylphosphine selenide were added, and aged for a total of 2 hours.

At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The additives and their addition amounts (per mol of silver halide) are shown below.

Spectral sensitizing dye (A) 300 mg Spectral sensitizing dye (B) 375 mg Ammonium thiocyanate 145 mg Chloroauric acid 18.5 mg Sodium thiosulfate (pentahydrate) 15.0 mg 1-Ethyl-3- (2-thiazolyl) ) Thiourea 3.8 mg Simple substance sulfur (sulfur sensitizer) 3.5 mg Triphenylphosphine selenide 3.0 mg Stabilizer (TAI) 1000 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in JP-A-4-994.
Prepared by a method according to the method described in No. 37.

That is, a predetermined amount of the following spectral sensitizing dyes (A) and (B) was added to water whose temperature was previously adjusted to 27 ° C., and the mixture was stirred with a high speed stirrer (dissolver) at 3500 rpm for 30 to 120 minutes. Got by

Spectral sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (3
-Sulfopropyl) oxacarbocyanine sodium salt anhydride Spectral sensitizing dye (B) 5,5'-di (butoxycarbonyl) -1,1'-diethyl 3,3'-di- (4-sulfobutyl) benzimidazo Anhydrous sodium rocarbocyanine salt Next, a sample was prepared by uniformly coating and drying the crossover cut layer, the emulsion layer, and the protective layer on both surfaces of the support in the following manner. At this time, the amount of silver attached to one surface of each sample was 1.8 g / m ² , and the amount of gelatin was 0.4 g / m ² of the protective layer.
m ² , emulsion layer 1.5 g / m ² , transverse light blocking light layer 0.2 /
It was prepared to have a size of m ² .

As the support, a copolymer aqueous solution obtained by diluting a copolymer composed of three monomers of 50% by weight of glycidyl methacrylate, 10% by weight of methyl acrylate and 40% by weight of butyl methacrylate to a concentration of 10% by weight. A polyethylene terephthalate film base colored blue with a concentration of 0.15 for a 175 μm X-ray film using the dispersion as an undercoat liquid was used.

(Preparation of Sample) Various additives described below were added to each emulsion to prepare emulsion coating solutions. At the same time, a dye layer coating solution and a protective layer coating solution described below were also prepared. Using the three coating solutions, using two slide hopper type coaters to form the first dye layer, the second emulsion layer and the third protective layer, both sides on the support at a speed of 80 m / min. Simultaneous application,
After drying for 2 minutes and 20 seconds, sample No. 1 to 11 were obtained.

The additives used for each layer are as follows. The amount of addition is indicated by the amount per 1 m ² of film.

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-Dichloro-6-hydroxy-1,3,5- Sodium triazine salt 5 mg Latex (L) 0.2 g Potassium polystyrene sulfonate 50 mg Second layer (emulsion layer) The following additives were added to the emulsion obtained above.

Potassium tetrachloropalladium (2) ate 100 mg Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butylcatechol 130 mg Polyvinylpyrrolidone (molecular weight 10,000) 35 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenylphosphonium chloride 20 mg 1,3-Dihydroxybenzene-4-sulfonate ammonium 500 mg 2-Mercaptobenzimidazole-5-sulfonate 5 mg Compound _{(H) 0.5mg n-C 4} H 9 OCH 2 CH (OH) CH 2 n (CH 2 COOH) 2 35mg dextran (average molecular weight 40 00) 300 mg Latex (L) 500 mg Example compound of the general formula (1) of the present invention Amount shown in Table 1 Third layer (protective layer) Gelatin 0.4 g 4-hydroxy-6-methyl-1,3,3a, 7 -Tetrazaindene 50 mg Matting agent made of polymethylmethacrylate (area average particle size 4.0 μm) 20 mg Matting agent made of polymethylmethacrylate (area average particle size 1.0 μm) 50 mg Formaldehyde 20 mg Colloidal silica (average particle size 0.014 μm) ) 10 mg formaldehyde 20 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine 10 mg bis-vinylsulfonylmethyl ether 36 mg polyacrylamide (average molecular weight 10000) 0.1 g sodium polyacrylate 30 mg polysiloxane (S1) 20 mg Compound (I) 12 mg Compound (J) 2 mg Compound (K) 15 mg Compound (O) 50 mg Flat silica of the present invention Amount shown in Table 1 Fluorine-containing surfactant of the present invention Amount shown in Table 1

[0107]

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[0108]

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(Evaluation of Processing Stability) A roller transfer type automatic processor SRX-503 (manufactured by Konica Corporation) was modified so that the transfer speed was 25 seconds for the total processing time (Dry to Dry), and the following composition was used. The difference between the sensitivity of each sample when the developing solution and the fixing solution were processed in the fresh solution and the sensitivity when the samples were processed by running the fresh solution to reach the parallel state of the activity was obtained. .

The larger the difference in sensitivity, the poorer the processing stability. However, the replenishing amount of the processing solution during running was 90 ml / m ^{2 for} both the developer fixing solution.

The sensitivity of the sample film was 23 ° C. and 55.
% RH for 3 days, then X-ray fluorescence intensifying screen KO-25
0 (manufactured by Konica Co., Ltd.), and exposed through a penetrometer type B at a tube voltage of 80 kVp and a tube current of 100 mA for 0.05 seconds for X-ray exposure, and the processing speed was (Dry to Dry) It processed in 25 seconds. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog +1.0, and the sample No. It was expressed as relative sensitivity when the value of 1 was 100.

(Evaluation of Roller Mark) After uniformly exposing the obtained four-cut sample (10 × 12 inches) to a blackening degree of 1.0, the following treatment was carried out. It was However, the developing rack and the transition rack from the development to the fixing used at this time were intentionally fatigued.
That is, since the rollers of each rack were fatigued, those having irregularities of about 10 μm on the entire surface were used. Due to the pressure caused by the unevenness in the processed sample, fine speckled density unevenness occurs in the sample film having poor pressure resistance. This level was visually evaluated according to the following evaluation criteria.

Evaluation Criteria 5: No Spots Occurred 4: Slight Spots Occurred, but Practically No Problem Level 3: Small Number of Spots Occurred, but Permissible Limit Level that Does Not Normally Occur in Rack 2: Spots occur and sometimes occur even in normal racks 1: Many spots occur, and always occur in normal racks (Evaluation of developed silver color tone) The prepared sample has a transmission density of 1.2 after development. After being exposed so as to be, the developed sample obtained by processing using the automatic developing machine was observed on a Schaukasten, and the silver tone by transmitted light was visually evaluated according to the following evaluation criteria.

Evaluation Criteria A: Pure Black Tone B: Slightly Reddish Black C: Slightly Yellowish Black D: Yellowish Black (Evaluation of Reflection Spot Mottling) Density becomes 1.0 The sample thus exposed was developed in the same manner as above, and the glossiness of the sample surface was observed to visually evaluate the occurrence of spot unevenness according to the following evaluation criteria.

A: Almost no occurrence B: Some occurrence but no problem C: Many problems D: Occurrence on the entire surface (Developer formulation) Part-A (for 12 liter finish) hydroxide Potassium 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium hydrogen carbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercaptotetrazole 0.2 g 1,4-Dihydroxybenzene 340 g Water was added. Finish to 5000 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 solution formulation (for finishing 1 liter) Glacial acetic acid 120 g Potassium bromide 225 g Water is added to finish to 1000 ml (fixer formulation) Part-A (for 18 liter finish) 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 Add water to finish to 1000 ml Part-B (for 18 liter finish) Aluminum sulfate 800 g Dissolve in 1000 ml of water (Preparation of developer) Preparation: P to about 5 liters of water
Art-A and Part-B were added at the same time, and water was added while stirring and dissolving to make up to 12 liters.
The developer was adjusted to 0.40.

20 ml of the starter solution was added to 1 liter of the developer, and the pH was adjusted to 10.26 to prepare a working solution.

The developing replenisher used was the same as the developing solution.

(Preparation of fixer) To prepare a fixer, Part-A and Part-B were simultaneously added to about 5 liters of water, and water was added while stirring and dissolving to make 18 liters, and sulfuric acid and sodium hydroxide were added. The pH was adjusted to 4.4 using the solutions as the fixer working solution and fixer replenisher.

The results are summarized in Table 2.

[0120]

[Table 2]

From Table 2, the silver halide photographic light-sensitive material and processing method of the present invention can obtain stable sensitometric performance even in an ultra-rapid processing with a reduced replenishing amount, and there is no generation of roller marks or uneven spots of reflection and silver color. You can see that it is excellent in tone.

[0122]

According to the present invention, a stable sensitometric performance can be obtained even in an ultra-rapid processing with a reduced replenishing amount, and a silver halide photographic light-sensitive material excellent in silver tone without generation of roller marks and uneven reflection spots, and the same are provided. A treatment method was obtained.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of an ultrafiltration method according to the present invention.

[Explanation of symbols]

 1 Reaction Tank 2 Valve 3 Pump 4 Conduit 5 Ultrafiltration Device 6 Ultrafiltration Membrane 7 Separation Tank 8 Conduit 9 Conduit 10 Pressure Gauge 11 Pressure Gauge 12 Conductivity Meter 13 Control Valve 14 Stirrer 15 Waste Liquid

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, said silver halide emulsion layer and / or non-photosensitive hydrophilic colloid. A silver halide photographic light-sensitive material characterized in that the layer contains tabular silica and a fluorine-containing surfactant. 2. A silver halide emulsion layer having the following general formula (1)
A compound represented by the formula:
The silver halide photographic light-sensitive material as described above. In the general formula (1) Z-SM formula, Z is _{-SO 3 M 1, -COOR 1,} -OH and -N
Represents a heterocycle directly or indirectly having a substituent selected from HR ₂ , M and M ₁ represent a hydrogen atom, an alkali metal atom or a quaternary ammonium group, and R ₁ represents a hydrogen atom, an alkali metal atom or the number of carbon atoms. 1 to 6 alkyl group, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, —COR ₃ , CO
It represents OR ₃ or —SO ₂ R ₃ , and R ₃ represents a hydrogen atom, an aliphatic group or an aromatic group. 3. A processing method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the total processing time (D
ry to Dry) is 10 seconds or more and less than 45 seconds, a method for processing a silver halide photographic light-sensitive material. 4. The total processing time (Dry to Dry) is 10 seconds or more and less than 45 seconds, and the replenishment amounts of the developing solution and the fixing solution in the processing step are 30 ml / m ² or more and 200 m, respectively.
4. The method for processing a silver halide photographic light-sensitive material according to claim 3, which is 1 / m ² or less.