JP2001235827A - Silver halide photographic sensitive material and processing method for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material which ensures improved antistatic property, scuffing resistance and sticking property and suppresses the contamination of a processing solution under low replenishment and a processing method for the photosensitive material. SOLUTION: In the silver halide photographic sensitive material with a silver halide emulsion layer and a non-photosensitive colloidal layer on each of both faces of the base, a compound of formula 1 and a polyalkylene oxide type nonionic surfactant of the formula R21-A-(B)n21-R20 are contained in at least one of the layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter simply referred to as a "light-sensitive material") and a processing method therefor. More specifically, the present invention has improved antistatic properties, abrasion resistance, anti-stickiness, and processing solution stain. The present invention relates to a photosensitive material and a processing method thereof.

[0002]

2. Description of the Related Art Photosensitive materials are liable to be charged with static electricity under low humidity. When the photosensitive material discharges, static marks are formed, and foreign substances such as dust are liable to adhere, thereby causing pinholes and uneven development. However, the quality of the photographic image is significantly degraded. Therefore, many antistatic techniques have been proposed in the past, and for example, various methods using various surfactants, inorganic salts, conductive metal oxides, ionic polymers, and the like for the surface protective layer have been disclosed.

[0003] However, these conventional techniques have a problem that the conductive performance is deteriorated due to a decrease in the water content in an atmosphere of low humidity which needs to provide conductivity.
Therefore, if the amount of the conductive compound is increased in order to avoid such a drawback, this results in excessive water retention in a high-temperature atmosphere, which causes a serious obstacle that light-sensitive materials may be sticky or sticky. become.

Further, the use of a large amount of a conductive compound results in the accumulation of the compound in a developing and fixing processing solution, and the development of the compound due to the deposition of the compound from the processing solution on the photosensitive material surface. Inhibition and fixation inhibition occur.

In recent years, from the viewpoint of environmental protection, the amount of replenishment tends to be reduced more and more in order to reduce the amount of processing solution waste, and the importance of an antistatic method free of processing solution contamination is increasing.

More recently, films have been transported at a high speed, such as a film transport device using an automatic feeder for sheet films used for medical photosensitive materials, or a film transport mechanism of an automatic photographing device. Therefore, a photosensitive material which has high anti-static property and abrasion resistance and is free from cracks is strongly desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a light-sensitive material having improved antistatic properties, abrasion resistance, dustiness, and low contamination of a processing solution at low replenishment, and a processing method therefor.

[0008]

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

1. In a silver halide photographic material having a silver halide emulsion layer and a non-photosensitive colloid layer on both sides of a support, at least one layer selected from a silver halide emulsion layer and a non-photosensitive colloid layer contains A silver halide photographic material comprising a compound represented by formula (1) and a polyalkylene oxide nonionic activator represented by formula (2).

[0010] 2. In a silver halide photographic material having a silver halide emulsion layer and a non-photosensitive colloid layer on both sides of a support, at least one layer selected from a silver halide emulsion layer and a non-photosensitive colloid layer contains A silver halide photographic material comprising a compound represented by formula (3) and a polyalkylene oxide nonionic activator represented by formula (2).

3. In a silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-light-sensitive colloid layer on both sides of a support, the non-light-sensitive colloid layer has a matte degree of 2.00 × 10 ⁴ Pa to 3.33 × 10 3 ^A silver halide emulsion layer or a non-photosensitive colloid layer, and a compound represented by the formula (1). Silver halide photographic light-sensitive material.

4. In a silver halide photographic material having a silver halide emulsion layer and a non-photosensitive colloid layer on both sides of a support, the non-photosensitive colloid layer has a matte degree of 2.00 × 10 ⁴ Pa to 3.33 × 10 3 ^A matting agent that gives ⁴ Pa; and a compound represented by the general formula (3) in at least one layer selected from a silver halide emulsion layer and a non-photosensitive colloid layer. Silver halide photographic light-sensitive material.

5. 5. The silver halide photograph described in the above item 3 or 4, wherein the silver halide emulsion layer and the non-photosensitive colloid layer contain a polyalkylene oxide-based nonionic activator represented by the general formula (2). Photosensitive material.

6. 6. The silver halide photographic light-sensitive material according to any one of the above 1 to 5, wherein a replenishment amount of a developing solution or a fixing solution is 50 to 150 ml per m ^{2 of the} silver halide photographic light-sensitive material.
A method for processing a silver halide photographic light-sensitive material, comprising:

Hereinafter, the present invention will be described in more detail. The compound of the present invention represented by the general formula (1) will be described.

In the general formula (1), among the substituents represented by R ₁ and R ₂ , examples of the alkyl group include methyl, ethyl and
It is each group such as hexyl and octyl, and examples of the aryl group include a phenyl group.

The alkoxy group represented by at least one of R ₁ and R ₂ is methoxy, butoxy, hexyloxy, octoxy or the like, and the aryloxy group is propoxy or phenoxy. . These groups may be linear, branched or cyclic, and may be further substituted by other substituents. Further, a plurality of substituents may be bonded to each other to form a ring.

Examples of the halogen atom represented by X ₁ and X ₂ include a fluorine atom, a chlorine atom and a bromine atom.

Next, typical compounds represented by the general formula (1) of the present invention will be described, but the present invention is not limited thereto.

[0020]

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[0021]

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The compounds represented by the general formula (1) of the present invention include all compounds such as water-soluble, oil-soluble or latex-based compounds. Alternatively, the compound is dissolved in an organic solvent such as methanol, ethanol, acetone, dimethylacetone, dioxane, methyl ethyl ketone, acetonitrile, methyl acetate, ethyl acetate, or a mixed solvent of water and the organic solvent, and then added to the emulsion. In some cases, the following surfactant for dispersion may be used in combination.

When the compound of the present invention is oil-soluble,
The low-boiling organic solvent and the water-soluble and high-boiling organic solvent (for example, butyl phthalate, dioctyl phthalate, tricresyl phosphate, trihexyl phosphate,
Trioctyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, dioctyl phenyl phosphate, hexyl oleate, dihexyl glutarate, butyl citrate, butyl myristate, butanediol dibenzoate, N, N-diethyl lauryl amide, behen Acid, octadecyl alcohol,
Chlorinated polyethylene, etc.), and a dispersing surfactant (for example, anionic, nonionic, cationic, amphoteric surfactant such as sulfonic acid type, sulfate type, carboxylic acid type, malic acid type, boric acid type boric acid type). An alkylene oxide type, polyglycerin type, carboxybetaine type, sulfobetaine type, ammonium type, pyridinium type, etc.) may be used for solubilization or emulsification and then added to the emulsion.

The compound represented by the general formula (1) of the present invention is contained in the hydrophilic colloid layer farther from the support than the silver halide emulsion layer. Layers, intermediate layers, filter layers, etc., but are preferably contained in a protective layer farthest from the support.

The amount of addition is not particularly limited, but is preferably 0.01 to 10 g per 1 m ^{2 on} one side of the photosensitive material.
More preferably, from 0.05 to 1 m ² per side of the photosensitive material.
2 g.

Next, the polyalkylene oxide nonionic activator represented by the general formula (2) of the present invention will be described.

In the general formula (2), R ₂₀ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a hydroxyethyl group, an isopropyl group) and an alkylcarbonyl having 1 to 5 carbon atoms. Groups (eg acetyl groups,
Chloroacetyl group, carboxymethylcarbonyl group, etc.)
Represents R ₂₁ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms, and A represents —O
-, - S -, - COO -, - CON (R 22) -, - N
(R ₂₂ ) —, —SO ₂ N (R ₂₂ ) —, R ₂₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, and B represents an oxyalkylene group (for example, an oxyethylene group, an oxypropylene group, Oxyhydroxypropylene group, oxybutylene group, etc.). Preferred are an oxyethylene group and an oxyhydroxypropylene group.

N21 represents the average degree of polymerization of the oxyalkylene group, and is a natural number of 2 to 50. Next, representative compounds of the polyalkylene oxide-based nonionic activator represented by the general formula (2) of the present invention will be described, but the present invention is not limited thereto.

2-1: C₈H₁₇O (CH_TwoCH_TwoO)₇H2-2: C₁₁H_{twenty three}O (CH_TwoCH_TwoO)₈H 2-3: C₁₂H_{twenty five}O (CH_TwoCH_TwoO)_TenH 2-4: C₁₆H₃₃O (CH_TwoCH_TwoO)₁₂H 2-5: C₂₀H₄₁O (CH_TwoCH_TwoO)₂₀H 2-6: C₁₈H₃₇O (CH_TwoCH (OH) CH_TwoO)
_Two(CH_TwoCH_TwoO)_TenH 2-7: C₁₆H₃₃O (CH_TwoCH_TwoO)_Four(CH_TwoCH (O
H) CH_TwoO)_Two(CH _TwoCH_TwoO)_FourH 2-8: C₁₁H_{twenty three}COO (CH_TwoCH_TwoO)₈H 2-9: C_FifteenH₃₁COO (CH_TwoCH_TwoO)₁₃H 2-10: C₁₆H₃₃COO (CH_TwoCH_TwoO)_FifteenH 2-11: C₁₈H₃₇COO (CH_TwoCH_TwoO)_FifteenH 2-12: C₁₂H_{twenty five}S (CH_TwoCH_TwoO)_FifteenH

[0030]

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[0031]

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The addition amount of the nonionic activator having a polyoxyalkylene group represented by the general formula (2) of the present invention is preferably 1 to 500 mg per 1 m ² per side of the photographic material, and more preferably 1 m ² per side per photographic material. 5 to 25 per ²
0 mg.

Next, the compound represented by formula (3) of the present invention will be described. In the general formula (3), R ₃₁ ,
The alkyl group represented by R ₃₂ preferably has 1 to 18 carbon atoms, and may be linear, branched, or cyclic. The alkoxy group preferably has 1 to 18 carbon atoms, and may be linear, branched, or cyclic.

The aryl group is preferably a phenyl group, and the aryloxy group is preferably a phenoxy group.

These alkyl, alkoxy, aryl and aryloxy groups may be substituted with other substituents. It is particularly preferred that at least one of R ₃₁ and R ₃₂ contains a 2-hydroxyphenyl group. The alkoxy group represented by R ₃₃ may be linear, branched, or cyclic. The alkoxy group and the aryloxy group represented by R ₃₃ may be substituted with another substituent.

Next, typical compounds represented by the general formula (3) of the present invention will be described, but the present invention is not limited thereto.

[0037]

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The compounds represented by the general formula (3) of the present invention include water-soluble, oil-soluble and latex-type compounds. The addition amount and the addition method are as described in the general formula (1).
Are exactly the same as the compounds represented by

The light-sensitive material of the present invention has a mat degree of 2.00 × 10 ^{4 to} Pa to 3.33 × 10 ^{4 in the} non-photosensitive colloid layer.
Contains a matting agent of Pa.

In the present invention, the term "mat degree" refers to a value obtained by expressing the amount of inflow of air, which varies with the smoothness (mat degree) of the photosensitive material surface, as a change in pressure using a vacuum air micrometer. A value obtained by measuring a suction pressure under the same conditions of an unexposed photosensitive material (so-called raw film) that has been conditioned for 3 hours under the condition of 48% RH.
It is a value obtained by converting g to the international unit Pa. That is, the larger the value, the higher the matte degree.

The measurement of the suction pressure in the embodiment of the present invention is as follows.
A smoother (manufactured by Toei Electronics Industry Co., Ltd.) was used.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material, a layer functioning as the outermost surface layer or a layer close to the outer surface, and a layer acting as a so-called protective layer. Is more preferably contained. The content of the matting agent is 100 to 6 per side of the photosensitive material.
The amount is preferably from 00 to 400 mg, more preferably from 150 to 400 mg per one side of the photosensitive material, more preferably from 150 to 300 mg per side of the photosensitive material.

The average particle size of the matting agent is preferably 0.5 to 20 μm, more preferably 1 to 10 μm. In general, the desired matte degree can be obtained in a large amount when a material having a small average particle size is used, and in a small amount when a material having a large average particle size is used.

Further, it is well known that the matting agent may be deformed such as sinking or crushing due to pressure from a conveying roller or the like during coating and drying, and the matting agent is adjusted to an optimum amount according to manufacturing conditions.

The same or different type of matting agent may be contained in two or more layers. In this case, the layer to which the matting agent is added may be an emulsion layer, a protective layer, an undercoat layer provided as necessary,
Any of the intermediate layers may be used.

The particle size distribution of the matting agent preferably used in the present invention may be narrow or wide, but it is preferable to use a monodisperse matting agent. Monodisperse matting agent means that the number of particles having a particle size within ± 20% of the average particle size is 90% of the total number of particles.
This is what is described above.

The kind of the matting agent is arbitrary, and for example, a known matting agent can be appropriately used.

Specifically, fine particles of a water-insoluble organic or inorganic compound are used. Examples of the organic compound include water-dispersible vinyl polymers such as polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, and polyvinyl acetate. Examples of cellulose derivatives such as polyethylene carbonate and polytetrafluoroethylene include:
For example, methylcellulose, ethylcellulose / cellulose acetate, cellulose acetate propionate, etc., as examples of starch derivatives, for example, carboxy starch,
Gelatin hardened with a known hardener, such as carboxynitrophenyl starch and urea-formaldehyde-starch reactant, and hardened gelatin obtained by coacervate hardening into microcapsule hollow granules can be preferably used.

Examples of inorganic compounds include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide,
Barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, diatomaceous earth and the like can be preferably used.

The above matting agent can be used by mixing different kinds of substances as necessary.

The silver halide grains preferably used in the present invention may have any shape, for example, cubic, octahedral, tetradecahedral, spherical, tabular, potato-like and the like. Particularly preferred are tabular silver halide grains.

Tabular silver halide grains are crystallographically classified as twins. Twins are crystals having one or more twin planes in one grain. Classification of twin morphology in silver halide grains is based on a report by Klein and Moiser in "Photographhishhe Korrespon."
denz, Vol. 99, p. 99, and Vol. 100, p. 57.

The tabular silver halide grains have one or two or more twin planes parallel to each other in the grains, and these twin planes are in the plane forming the surface of the tabular grains. Exists almost parallel to a plane having the largest area (also referred to as a main plane). The most preferable form in the present invention is a case having two parallel twin planes.

In the silver halide emulsion, 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion has an average aspect ratio (hereinafter, also simply referred to as aspect ratio) of 1.5 to 300. The silver halide grains are preferably tabular silver halide grains, more preferably 50% or more of the total projected area are tabular silver halide grains having an aspect ratio of 3 to 50, and particularly preferably tabular silver halide grains having an aspect ratio of 5 to 25. Silver particles are preferred. Further, it is preferable that 80% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is the tabular silver halide grains used in the present invention.

As used herein, the term “aspect ratio” refers to the ratio of the area-converted particle diameter to the particle thickness (equivalent diameter / thickness). The area-converted particle size means the diameter of a circle having an area equal to the area when the particle is projected perpendicular to the main plane.

On the other hand, the volume-converted grain size means the diameter of a sphere having the same volume as each silver halide grain. Grain thickness is the thickness of a grain in a direction perpendicular to the major plane and generally corresponds to the distance between the two major planes.

The average equivalent circle diameter of the tabular silver halide grains is preferably 0.1 to 10.0 μm, more preferably 0.2 to 5.0.
μm is preferable, and particularly preferably 0.3 to 2.0 μm.

The average grain thickness of the tabular silver halide grains is preferably from 0.01 to 0.3 μm, more preferably from 0.05 to 0.3 μm.
25 μm is preferable, and particularly preferably 0.07 to 0.2 μm.

The projected area and thickness of the particles for calculating the area-converted particle diameter and the volume-converted particle diameter can be obtained by the following methods.

A sample was prepared by coating a support with a latex ball having a known particle size as an internal standard and silver halide particles so that the main plane was oriented parallel to the substrate, and shadowed by carbon deposition from a certain angle. , A replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the length of the internal standard and the shadow of the particle.

Aspect ratio, area-converted particle size, particle thickness,
The average value of the volume-converted particle size is determined by arbitrarily setting the silver halide grains contained in the silver halide emulsion to 50% by the replica method.
A value obtained by measuring zero or more pieces and obtaining an arithmetic average thereof.

The coefficient of variation of the silver halide grain in terms of volume is a value defined by the following equation using the value obtained from the above measurement.

Coefficient of variation of volume-converted particle size = (standard deviation of volume-converted particle size / average value of volume-converted particle size) The coefficient of variation of the volume-converted particle size of silver halide grains is preferably 0.2 or less. It is more preferably at most 15 and particularly preferably at most 0.1.

Similarly, the coefficient of variation of the area-converted grain size of silver halide grains can be determined from the above measurement. Here, the variation coefficient of the area-converted particle diameter is a value defined by the following equation.

Coefficient of variation of area-converted grain size = (standard deviation of area-converted grain size / average value of area-converted grain size) The variation coefficient of the area-converted grain size of silver halide grains is preferably 0.2 or less. It is more preferably at most 15 and particularly preferably at most 0.1.

The tabular silver halide grains have one or two or more twin planes parallel to each other in the grains, but 50% or more of the tabular silver halide grains have two parallel planes in the grains. It is preferably a tabular grain having a twin plane, more preferably 80% or more. These twin planes can be observed with a transmission electron microscope.
The specific method is as follows.

First, a silver halide emulsion is coated on a substrate such that the main plane of the tabular grains contained therein is oriented substantially parallel to the substrate to prepare a sample. This is continuously cut perpendicular to the substrate using a diamond cutter to obtain a continuous thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the existence and position of the twin plane can be confirmed.

The preferred composition of silver halide grains in the present invention is silver iodobromide, silver bromide, silver chlorobromide, and silver chloroiodobromide. It is particularly preferred that the silver halide emulsion is silver iodobromide having an average silver iodide content of 2 mol% or less, more preferably an average silver iodide content of 1 mol% or less. Molar% or less is particularly preferred. The composition of the silver halide grains can be determined by a composition analysis method such as an EPMA method and an X-ray diffraction method.

The average silver iodide content of the surface phase of silver halide grains is preferably 3 mol% or less, more preferably 0.1 mol% to 2 mol%, and more preferably 0.2 mol%. ~ 1 mol% is more preferred. The average silver iodide content of the surface phase of the silver halide grains as used herein may be determined by an XPS method or an IS method.
This is a value obtained by using the S method.

For example, the surface silver iodide content by the XPS method can be obtained as follows. The sample was 1.33 × 10 ^-2 P
The sample is cooled to −155 ° C. or lower in an ultra-high vacuum equal to or lower than a and irradiated with MgKa as an X-ray for a probe at an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the composition such as the silver iodide content of the silver halide surface phase is determined from these intensity ratios.

Further, in the silver halide emulsion, the silver iodide content between silver halide grains is preferably more uniform. That is, the coefficient of variation of the silver iodide content in the silver halide emulsion is preferably 30% or less, and more preferably 20% or less.

Here, the coefficient of variation is a value obtained by dividing the standard deviation of the silver iodide content by the average of the silver iodide content and multiplying by 100, and is included in the silver halide emulsion. A value obtained by arbitrarily measuring 500 or more silver halide grains.

The silver halide grains are fine crystals composed of silver chloride, silver bromide, silver iodide, or a solid solution thereof.
Two or more phases having different silver halide compositions can be formed inside the crystal. As a grain having such a structure, a grain composed of an inner core phase and an outer surface phase having mutually different silver halide compositions is known, and is generally called a core / shell type grain.

The silver halide grains of the light-sensitive material of the present invention include:
The outer surface phase preferably has a core / shell type grain structure having a higher silver iodide content than the inner core phase.

The silver halide emulsion preferably has dislocation lines. The dislocation lines are preferably located near the outer periphery, near the ridge or near the top of the tabular silver halide grains. In terms of the positional relationship of dislocation line introduction in each grain, it is preferably introduced after 50% of the silver content of the whole grain, more preferably between 60% and 95%, more preferably between 70% and 95%. Most preferably, it is introduced between 90%.

As a method for introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jetting, or a method of introducing silver iodide fine grains. Addition method, method of adding only a solution containing iodide ions, Japanese Patent Application Laid-Open No. HEI 6-11781
A known method such as a method using an iodide ion releasing agent as described in No. 1 can be used to form a dislocation originating a dislocation line at a desired position.

Further, by using a production method in which an aqueous solution containing a salt is appropriately extracted from the reaction solution by an ultrafiltration apparatus, the efficiency of introducing dislocation lines into a silver halide emulsion can be drastically increased. For example, the average intergranular distance at the time of dislocation line introduction in the growth process of silver halide grains,
It is preferable to control the average distance between grains at the start of growth to 0.60 to 1.00, and more preferably to 0.60 to 0.80. Specifically, the value of the average interparticle distance when dislocation lines are introduced is preferably controlled to 3.2 μm or less, more preferably to 2.8 μm or less, and more preferably to 0.90 μm to 2.0 μm. Is particularly preferred.

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. E
ng. 11 (1967) 57 and T.I. Shiozaw
a, J. et al. Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature.

That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are put on a mesh for an electron microscope, and damage (printout or the like) by an electron beam is caused. Observation is performed by a transmission method in a state where the sample is cooled so as to prevent it.

At this time, the thicker the particle, the more difficult it is for an electron beam to pass through, so that a method using a high-pressure electron microscope can observe more clearly. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined.

As a preparation form of the silver halide emulsion, a method known in the art can be appropriately applied. For example, a so-called controlled double jet method or controlled triple jet method for controlling pAg of a reaction solution at the time of forming silver halide grains can be used.

A silver halide solvent can be used if necessary. Examples of useful silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, US Pat. No. 3,271,
No. 151, No. 3,790,387, No. 3,57
No. 4,626 can be referred to. The method for preparing the grains is not particularly limited, and an ammonia method, a neutral method using no ammonia, an acidic method, and the like can be used.From the viewpoint of suppressing fog during silver halide grain formation, it is preferable. The particles are preferably formed in an environment having a pH of 5.5 or less, more preferably 4.5 or less.

The silver halide emulsion contains a dispersion medium together with silver halide grains. The dispersion medium is a compound having a protective colloid property for silver halide grains, and is preferably present from the nucleation step to the end of grain growth. The dispersion medium that can be preferably used in the present invention includes:
There are gelatin and protective colloid polymers. As gelatin, alkali-treated gelatin or acid-treated gelatin having a molecular weight of about 100,000, or low-molecular gelatin or oxidized gelatin having a molecular weight of about 5,000 to 30,000 can be preferably used. In particular, at the time of nucleation, oxidized gelatin, low molecular weight gelatin, and oxidized low molecular weight gelatin can be suitably used.

In order to more precisely control the silver halide composition between silver halide grains and inside the grains, at least a part of the formation of the silver iodide-containing phase of the silver halide grains is controlled by 1
It can be formed by supplying only silver halide fine particles of more than one kind.

For the same reason, at least a part of the formation of the silver iodide-containing phase of the silver halide grains can be carried out in the presence of silver halide grains having a lower solubility than the silver halide grains. It is desirable to use silver iodide fine grain emulsions as silver halide grains having low solubility.

The silver halide emulsion was manufactured by Research Disclosure (hereinafter abbreviated as RD) No. 30811
The technique described in No. 9 can be used.

At least one of a layer containing the photosensitive silver halide emulsion and a layer other than the layer containing the photosensitive silver halide emulsion is decolorized and / or decolorized during development.
Alternatively, when a dye capable of being discharged is contained, a photosensitive material having high sensitivity, high sharpness, and little dye stain can be obtained.

The dye used in the light-sensitive material is appropriately selected from dyes which can improve the sharpness by absorbing a desired wavelength and eliminating the influence of the wavelength according to the light-sensitive material. You can do it.

It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed.

The dye preferably used in the light-sensitive material of the present invention is substantially insoluble in water at a pH of 7 or less, and substantially water-soluble at a pH of 8 or more.

Here, “substantially insoluble in water at pH 7 or less” means that 100 g of water at 20 ° C. adjusted to pH 7.0 or less.
Has a solubility of 0.001 g or less in
The term “substantially water-soluble at H8 or more” means that the compound has a solubility of 0.01 g or more in 100 g of water at 20 ° C. adjusted to pH 8.0 or more.

The addition amount can be changed according to the purpose of sharpness, and the preferable addition amount is 0.1 to ² per m ² of the light-sensitive material.
The amount is ² mg to ²⁰ mg, more preferably 0.8 mg to 15 mg per m ² of the light-sensitive material.

Known dyes can be used as these dyes. Various photographic additives can be used in the silver halide photosensitive material.

Known additives include, for example, RD-
17643 (December 1978) and 18716 (19
November 1979) and 308119 (December 1989)
Month).

Examples of the support which can be used in the light-sensitive material of the present invention include those described on page 28 of RD-17643 and page 1009 of RD-308119. A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The undercoat layer preferably contains an antistatic improver such as tin oxide sol.

The light-sensitive material of the present invention is preferably provided with a silver halide emulsion layer and a crossover cut layer on both sides of a support, whereby a light-sensitive material having high sensitivity, high sharpness and excellent processability can be obtained. can get.

The total amount of gelatin in the silver halide emulsion layer, the surface protective layer and the other layers is preferably in the range of 0.5 to 3.5 g per 1 m ² on one side of the support, and particularly preferably on one side of the support. The total amount is preferably in the range of 1.0 to 3.0 g per 1 m ² .

It is preferable to use latex in the light-sensitive material of the present invention. As the latex, it is preferable that the latex has no or very little adverse effect on the following points when used in a silver halide photographic element. That is, it is preferred that the latex surface is photographically inert and has very little interaction with various photographic additives.

As specific examples, preferred are those which hardly adsorb dyes and dyes and hardly contaminate photographic elements, and those which hardly adsorb development accelerators and inhibitors, and hardly affect sensitivity and fog.

In the production of a photographic element, it is desirable that the pH of a layer solution of a light-sensitive material in which a latex is dispersed is low and that it is not easily influenced by ionic strength and hardly aggregates and precipitates. If the glass transition point of the latex is too high, it is hard and unsuitable as a buffer, but if it is low, it generally tends to interact with photographic performance and may have an adverse effect. For this reason, considering the photographic characteristics, the selection of the composition and its use amount are not simple.

Latexes using monomers such as styrene, butadiene, and vinylidene are well known.

It is said that the introduction of a monomer having a carboxylic acid group such as acrylic acid, itaconic acid or maleic acid during the synthesis of latex has less influence on the photographic properties.

Further, by including a methacrylate unit in the latex obtained by such a combination, the glass transition point can be appropriately set according to the photosensitive material. As a specific example, see Japanese Patent Application Laid-Open No. 2-135335.
JP-A-6-308670 and JP-A-6-3086
No. 58, etc.

A preferred developer used in the method for processing a light-sensitive material of the present invention is described in JP-A-4-4-1 as a developing agent.
No. 5641, JP-A-4-16841, 3-pyrazolidones such as hydroquinone, paraaminophenols such as p-aminophenol, N-methyl-p-aminophenol and 2,4-diaminophenol. As 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like, and ascorbic acids, which are preferably used in combination. Further, dihydroxybenzenes, para-aminophenols, 3
The total molar number of pyrazolidones and ascorbic acids is 0.
It is preferably at least 1 mol / liter.

The preservative may include sulfites, for example, potassium sulfite, sodium sulfite, and reductones, for example, piperidinohexose reductatone.
These are preferably used in an amount of 0.2 to 1 mol / l, more preferably 0.3 to 0.6 mol / l. Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate can be contained, and further, a borate described in JP-A-61-28708 and JP-A-60-93439. Buffers such as saccharose, acetoxime, 5-sulfosalicylic acid, phosphates, carbonates and the like described in No. 1 may be used. The content of these agents is selected so that the pH of the developer is 8.5 to 11.5, preferably pH 9.5 to 10.5.

Examples of the dissolution aid include diethylene glycol, triethylene glycols and esters thereof, and examples of the sensitizer include quaternary ammonium salts.
A development accelerator, a surfactant and the like can be contained.

The silver sludge inhibitor is described in JP-A-56-1981.
No. 106244, silver stain inhibitor, JP-A-3-518
The sulfides and disulfide compounds described in JP-A No. 44, and the cysteine derivatives or triazine compounds described in JP-A-5-289255 are preferably used.

Examples of the organic inhibitor include azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benztriazole, tetrazole, thiadiazole and mercaptoazole (eg, 1-phenyl-5). -Mercaptotetrazole) compound and the like are preferably used.

As the inorganic inhibitor, sodium bromide, potassium bromide, potassium iodide and the like can be contained.

In addition, L. F. A. Mason, "Photographic Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364.
And those described in JP-A-48-64933. As a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant with iron of 8 or more described in JP-A-1-193853 as an organic chelating agent is preferably used. Can be Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

In the processing method according to the sixth aspect of the present invention,
The replenishment amount of the developing solution is 1 m ^Two50 to 15
0 ml, preferably 65-130 ml.

Preferred fixing solutions in the processing method of the present invention may include fixing materials generally used in the art.

As the fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l.

The pH of the fixing solution is preferably 3.8 or more, more preferably 4.2 or more.

The fixing solution of the present invention may be one that forms an acidic hardening film. In this case, an aluminum compound is preferably used as a hardener. For example, aluminum sulfate,
It is preferably added in the form of aluminum chloride, potassium alum and the like. In addition, the fixing solution may optionally contain a sulfite,
Preservatives such as bisulfite, acetic acid, pH buffer such as boric acid,
PH adjusters such as mineral acids (sulfuric acid, nitric acid), organic acids (citric acid, oxalic acid, malic acid, etc.), hydrochloric acid, etc., metal hydroxides (potassium hydroxide, sodium hydroxide) and hard water softening ability. Chelating agents can be included.

As the fixing accelerator, for example, Japanese Patent Publication No.
No. 35754, No. 58-122535, No. 58-12
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459.

In the processing method according to the sixth aspect of the present invention,
The replenishment rate of the fixing solution is 1 m ^Two50 to 15
0 ml, more preferably 65-130 ml.
You.

As the processing method of the present invention, a method using a solid processing agent is preferable. To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. Any means such as forming a coating layer can be adopted (see JP-A-4-29136 and JP-A-4-29136).
No. 85535, No. 4-85536, No. 4-85533
Means described in JP-A Nos. 4-85534 and 4-172341).

A preferred tablet production method is a method in which a solid processing agent in the form of powder is granulated and then subjected to a tableting step. Compared to a solid processing agent formed by simply mixing a solid processing agent component and passing through a tableting process, there is an advantage that solubility and storage stability are improved, and as a result, photographic performance is stabilized.

The granulation method for tablet formation is to use a known method such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be done.

For tablet formation, the average particle size of the obtained granules is preferably 100% because the components are not made uniform, that is, so-called segregation hardly occurs when the granules are mixed and compressed.
It is preferable to use one having a thickness of from 800 to 800 μm, more preferably from 200 to 750 μm. Further, the particle size distribution is preferably such that 60% or more of the granulated particles have a deviation of ± 100 to 150 μm.

When the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine may be used. Wear.

The solid processing agent obtained by pressurizing and compression can take any shape. However, from the viewpoints of productivity and handling, and the problem of dust when used on the user side, a cylindrical type, so-called tablet, is used. Is preferred.

More preferably, at the time of granulation, the above effect is further remarkable by separately granulating an alkali agent, a reducing agent, a preservative and the like for each component.

The method for producing a tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method.
For example, Japanese Unexamined Patent Publication Nos.
No. 3, 3-39735, 3-39939, and the like. Furthermore, powder processing agents can be produced by a general method described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. it can.

The bulk density of the solid processing agent is preferably 1.0 to 2.5 g / cm ³ in the case of a tablet, from the viewpoint of its solubility and the effect of the present invention is more exhibited. 1.0g
/ Cm ³ or more, in terms of the strength of the obtained solid,
When the content is 2.5 g / cm ³ or less, the solubility of the obtained solid is more preferable. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

As the automatic developing machine used in the processing method of the present invention, a known roller conveying type automatic developing machine is preferably used. Total processing time (Dry to
(dry) is preferably processed in 10 to 45 seconds,
More preferably, the treatment is performed in 15 to 30 seconds.

Here, the total processing time (Dry to dr)
y) is the development time, which is the time from when the leading edge of the photosensitive material to be processed is immersed in the developing solution of the automatic developing machine to when it comes into contact with the fixing solution in the next step, similarly immersed in the fixing solution, and then washed with the washing bath solution. The time until contact with (stabilizing bath liquid) is the fixing time, the time of dipping in the washing bath liquid (stabilizing bath liquid) is the washing time, and the time in the drying zone of the automatic developing machine is the drying time. This is the time from when the tip of the photosensitive material is immersed in the developing solution of the automatic developing machine to when it leaves the drying zone.

The preferred development time is 3 to 15 seconds, more preferably 5 to 10 seconds, and the development temperature is preferably 25 seconds.
To 50 ° C, more preferably 30 to 40 ° C. The fixing time is preferably 2 to 12 seconds, more preferably 2 to 10 seconds. The fixing temperature is preferably from 20 to 50 ° C, and from 30 to 40 ° C.
C is more preferred. The washing (stabilization) time is preferably 2 to 15 seconds, more preferably 2 to 8 seconds. The washing (stabilization) temperature is preferably 0 to 50 ° C, more preferably 15 to 40 ° C.
Is preferred. The drying time is preferably 3 to 12 seconds, more preferably 3 to 8 seconds. The drying temperature is preferably from 35 to 100 ° C, more preferably from 40 to 80 ° C.

In the processing method of the present invention, it is preferable that after development, fixing and washing (or stabilization), the water is squeezed by a squeeze roller and then dried.

[0133]

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

Example 1 All emulsions shown below were prepared in a reaction vessel having a volume of 32 liters. The ultrafiltration unit is SIP
-1013 (manufactured by Asahi Kasei Co., Ltd.).
AIDO Rotary Pump was used. The volume of the emulsion circulation part of the ultrafiltration step is 1.2 liters,
The emulsion was circulated at a constant flow rate of 15 liter / min. Thus, the residence time of the reactant solution was 4.8 seconds, and the volume of the emulsion circulation portion of the ultrafiltration step was 3.8% of the volume of the reaction vessel. The control of the distance between particles in the particle growth process was performed by appropriately controlling the permeation flux in the ultrafiltration step.

FIG. 1 is a schematic view showing an example of a silver halide emulsion manufacturing apparatus applicable to the present invention. The control of the distance between grains is performed by adjusting a flow control valve 19 shown in FIG. The reactant solution in the reaction vessel is circulated to the ultrafiltration apparatus so as to maintain the average distance between the particles at the start of the particle growth step-1 over the entire area of the growth step-1 and the particle growth step-2, thereby performing concentration. Carried out.

(Em-1: Preparation of Ultrafiltered Emulsion) [Nucleation Step] The following gelatin solution B-10 in a reaction vessel
1 was maintained at 30 ° C., and the pH was adjusted to 1.96 with 1 mol / L sulfuric acid while stirring at 450 rpm using the mixing and stirring apparatus in FIG. Thereafter, the S-101 solution and the X-101 solution were added using the double jet method.
Nucleation was performed by addition at a flow rate of 0 ml / sec.

(B-101) Low molecular weight gelatin (average molecular weight: 20,000) 32.4 g Potassium bromide 9.92 g H ₂ O 12938.0 ml (S-101) Silver nitrate 50.43 g H ₂ O 225.9 ml (X- 101) 35.33 g of potassium bromide 224.7 ml of H ₂ O [Aging step] After the completion of the above addition, the following G-101 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. After heating, 60
The stirring was maintained for 20 minutes while maintaining the temperature. Subsequently, the pH was adjusted to 9.5 by adding a 28% aqueous ammonia solution, and the mixture was maintained for 7 minutes. A 1 mol / L nitric acid aqueous solution is added thereto and p
H was adjusted to 5.8. During this time, the silver potential of the solution (saturated silver-
Measured with silver ion selective electrode using silver chloride electrode as reference electrode)
Was controlled to 14 mV using a 1 mol / L potassium bromide solution.

(G-101) Alkali-treated inert gelatin (average molecular weight 100,000) 139.1 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by mass methanol solution of [Compound A] 4.64 ml H ₂ O 3266.0 ml [Particle growth step-1] After completion of ripening, the S-102 solution was subsequently prepared by using a double jet method. And X-102 solution while accelerating the flow rate (the ratio of the addition flow rate at the end to the addition at the start is about 12 times)
Added in 38 minutes. After the addition was completed, the G-102 solution was added, the stirring speed was adjusted to 550 rpm, and then the S-103 solution and the X-103 solution were accelerated while increasing the flow rate (the ratio of the addition flow rate at the end to the start was about (2x) added in 40 minutes. During this time, the silver potential of the solution was controlled to 14 mV using a 1 mol / L potassium bromide solution.

(S-102) 639.8 g of silver nitrate 2866.2 ml of H ₂ O (X-102) 448.3 g of potassium bromide 2850.7 ml of H ₂ O (G-102) alkali-treated inert gelatin (average molecular weight 100,000) ) 203.4 g the 10 wt% methanol [compound a] solution _{6.20ml H 2 O 1867.0ml (S-} 103) Silver nitrate _{989.8g H 2 O 1437.2ml (X-} 103) potassium bromide 679.6g Potassium iodide 19.35 g H ₂ O 1412.0 ml [Grain growth step-2] After completion of the addition, the temperature of the solution in the reaction vessel was lowered to 40 ° C. over 20 minutes. afterwards,
After adjusting the silver potential in the reaction vessel to -32 mV using a 3.5 mol / L aqueous potassium bromide solution, the following silver iodide fine grain emulsion a was added in an amount corresponding to 71.2 g of silver nitrate, and S-1 was added.
Liquid 04 and liquid X-104 were added for 7 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was 1.2 times).

(S-104) Silver nitrate 672.0 g H ₂ O 975.8 ml (X-104) Potassium bromide 470.8 g H ₂ O 959.4 ml The entire area of the grain growing step 1 and the grain growing step 2 was
The reaction solution in the reaction vessel was circulated to the ultrafiltration device so as to maintain the average interparticle distance at the start of the particle growth step 1, and concentration was performed.

(Preparation of silver iodide fine grain emulsion a) Gelatin 3
2000 ml of an aqueous solution containing 5 g was kept at 40 ° C. and stirred. After adjusting the silver potential to -150 mV with respect to the saturated calomel electrode using a KI aqueous solution, a 178 g aqueous solution of AgNO ₃ and a 174 g aqueous solution of KI were added over 13 minutes while accelerating the flow rate by a double jet method. After desalting, gelatin was added and the pH was adjusted to 6.8 and pAg9 at 50 ° C. This silver iodide fine grain emulsion has an average circle equivalent diameter of 0.05 μm.
m.

After completion of the growth, desalting and washing are carried out according to a conventional method, and gelatin is added and dispersed well.
H was adjusted to 5.8 and pAg to 8.1. The resulting emulsion had an average grain thickness of 0.18 microns and an average grain diameter of 1.
16, hexagonal tabular grains having an average aspect ratio of 6.4. When dislocation lines were observed, an average of 16 dislocation lines were observed in the particle fringe portion. This emulsion was designated as Em-1.

After the above emulsion was heated to 60 ° C., the following spectral sensitizing dyes (A) and (B) were added as a dispersion in the form of solid fine particles, and 10 minutes after the addition, adenine, ammonium thiocyanate, and chloride were added. A mixed aqueous solution of gold acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added, and 30 minutes later, silver iodide fine grain emulsion a was added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-
A predetermined amount of tetrazaindene was added.

The amount added per mole of AgX is shown below. Spectral sensitizing dye (A) 5,5-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous 270 mg Spectral sensitizing dye (B) 5,5-di- (Trifluoromethyl) -1-methyl-1'-ethyl-3,3'-di- (sulfopropyl) -benzimidazolocarbocyanine sodium salt anhydride 100 mg adenine 10 mg potassium thiocyanate 90 mg chloroauric acid 20 mg ammonium thiosulfate 2 0.0 mg triphenylphosphine selenide 0.2 mg silver iodide fine particles a 0.3 mol equivalent 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 500 mg spectral sensitizing dye (A), ( The solid particulate dispersion of B) was prepared by a known method.

That is, predetermined amounts of the above-mentioned spectral sensitizing dyes (A) and (B) are added to water whose temperature has been previously adjusted to 27 ° C., and high-speed stirring (dissolver) is performed at 3,500 rpm at 30 to 120 rpm.
Obtained by stirring for minutes.

The dispersion of the selenium sensitizer triphenylphosphine selenide was prepared as follows.

That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C.
Stir to dissolve completely. On the other hand, photographic gelatin 3.8k
g was dissolved in 38 kg of pure water, and 93 g of a 25% by mass aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than mass%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above Examples.

<Preparation of Emulsion Layer Coating Solution> The following various additives were added to each emulsion obtained above.

1,1-dimethylol-1-bromo-1-nitromethane 70 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / M ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 150 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² sodium 1,3-dihydroxybenzene-4-sulfonate 400 mg / m ² 2-mercaptobenz Sodium imidazole-5-sulfonate 6 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² Colloidal silica (Rudox AM: manufactured by DuPont, particle size 0.013 μm) ) 0.5g / m ² Zera Down 1.2 g / m ² (protective layer coating solution Preparation) Gelatin 0.8 g / m ² of polymethyl methacrylate having matting agent (area average particle diameter 6.0 .mu.m) (average particle number of particles within ± 20% of the diameter Was 98% of all particles.) Hardening agent (CH ₂ = CHSO ₂ CH ₂ CONHCH _2- ) ₂ Addition amount was adjusted such that the swelling ratio was 150%. (S-1) 7 mg / m ² Polyalkylene oxide-based nonionic activator represented by the general formula (2) (Exemplary compound) Amount shown in Table 1 Compound represented by the general formula (1) or (3) (Exemplary) Compound) Amount shown in Table 1 The amount of the material applied was 1 m ² per side, and the amount of silver applied was adjusted to 1.5 g / m ² per side.

(Preparation of Filter Layer) Glycidyl methacrylate 50% by mass, methyl acrylate 10% by mass,
A copolymer dispersion obtained by diluting a copolymer having three types of monomers of 40% by mass of butyl methacrylate and 10% by mass was coated as a subbing liquid to a thickness of 17%.
On both sides of 5μm blue colored polyethylene terephthalate support to prepare a support sample coating amount per surface 1 m ² was coated with a filter layer so that the following composition.

Solid fine particle dispersion dye (AH) 50 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 2 mg Compound (I) 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Potassium polystyrene sulfonate 50 mg

[0152]

Embedded image

(Coating) Using these coating solutions, two slide hopper type coaters were used at a speed of 120 m / min using two slide hopper coaters so that the coating amount was 1.5 g / m ² per side. Simultaneous application on both sides of body sample for 2 minutes 2
It dried in 0 second and the application sample was produced.

<Preparation of Solid Developer> Granules (A) 1050 g of sodium metabisulfite, 1-phenyl-3
-450 g of pyrazolidone, 7200 g of sodium erysorbate monohydrate, 810 g of binder D-sorbit, N
After mixing 7 g of acetyl-DL-penicillamine in a commercially available stirring granulator at room temperature for about 3 minutes and adding 150 ml of water over 1 minute to granulate, the granulated product is dried with a fluid bed dryer. At 50 ° C. for 2 hours to remove almost completely the water content of the granulated material.

Granulated product (B) 9500 g of potassium carbonate and 6.0 g of potassium iodide are each pulverized in a commercially available bantam mill to an average of 10 μm. These fine powders and diethylene triamine pentaacetic acid 5
Na (DTPA-5Na) 170 g, sodium sulfite 425 g, 5-mercapto- (1H) -tetrazolylacetic acid Na salt 8.3 g, 1- (3-sulfophenyl) -5-
40 g of tetrazole-Na salt, 15 mannitol binder
00g and 600g of D-Sorbit were added, mixed at room temperature for about 3 minutes in a commercially available stirring granulator, and granulated by adding 125 ml of water over 1 minute. After drying at 40 ° C. for 2 hours, the water content of the granules is almost completely removed.

The granulated product (A) thus obtained was added with 1
1.0% of the total mass of sodium octanesulfonate,
Methyl-β-cyclodextrin was added at 3% of the total mass, 25%.
C., and added and mixed in a room conditioned at 40% RH or less. Further, the granulated product (B) contains sodium 1-octanesulfonate at 1.2% of the total mass and methyl-β-cyclodextrin at the total mass. In a room conditioned at 25 ° C. and 40% RH or less, and mixed with Kikusui Seisakusho's Tough Press Collect 1
527HU was subjected to compression tableting using a modified tableting machine to produce each of the developed tablets (A) and (B). The filling amount per tablet was (A) 8.45 g and (B) 12.4 g. (A) 60 pieces, (B) 50 pieces (volume after dissolution is 5.
The tablets were sealed and packaged using a packaging material having the following layer structure for moisture prevention.

The packaging material is biaxially stretched nylon (ONY)
15 μm thickness / aluminum oxide deposited PET 12 μm thickness /
A bag made of a laminated material having a thickness of 25 μm of biaxially oriented polypropylene (OPP) / a thickness of 40 μm of low density polyethylene (LLDP). The effective surface area of the packaging material on the side (inside) in contact with the tablet was 1300 cm ² . .

<Preparation of Solid Fixing Agent> Granulated product (C) Ammonium thiosulfate / sodium thiosulfate (90/1
(0 mass ratio) is pulverized in a commercially available bantam mill to an average of 10 μm. The compound HO-
_{CH 2 CH 2 -S-CH 2} CH 2 -S-CH 2 CH 2 -OH1
000 g, sodium metabisulfite 920 g, 5-mercapto-tetrazole 50 g, binder pine flow 90
0 g was added, mixed in a commercially available stirring granulator at room temperature for about 3 minutes, and granulated by adding 150 ml of water over 1 minute. Dry to remove water almost completely.

Granulated product (D) Boric acid 250 g, aluminum sulfate octahydrate 1500 g, succinic acid 1150 g, tartaric acid 250 g, mannitol 208 g,
After adding 100 g of D-sorbit, mixing at room temperature for about 3 minutes in a commercially available stirring granulator, and granulating by adding 150 ml of water over 1 minute, the granulated product is dried with a fluid bed dryer. Dry at 40 ° C. to remove water almost completely.

The granulated product (C) thus obtained, 1400 g of sodium acetate and sodium 1-hexanesulfonate in a room conditioned at 2.5% of the total mass, 25 ° C. and 40% RH or less. 1400 g of sodium acetate was added to the granulated product (D), and sodium 1-hexanesulfonate was further added to 3.0% of the total mass at 25 ° C and 40% R.
The mixture was added and mixed in a room humidified to not more than H, and compressed and compressed by a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to produce respective fixing tablets (C) and (D). The filling amount per tablet is (C) 10.5 g, (D)
8.95 g. Using the packaging material used in developing tablets (A) and (B) for moisture proofing, 92 (C) and 28 (D) (the amount after dissolution becomes 5.0 liters) were used as tablets. Was packaged.

Development starter formulation (addition amount per liter of developer) N-acetyl-DL-penicillamine 0.11 g diethylene glycol 48.5 g 5-mercapto- (1H) -tetrazolylacetic acid Na 0.12 g acetic acid 90% 11.5 g KBr 8.0 g Finished with pure water 67 ml As an automatic developing machine, TCX-701 (manufactured by Konica Corporation) was used. At the start, 7.8 liters of the developing solution in which the developing tablet was dissolved was added to the developing solution in the developing tank, a developing starter solution was added, and the developing tank was filled as a developing start solution to start processing. The development starter solution was added in an amount corresponding to a developing tank capacity of 7.8 liters at a rate of 67 ml / liter of the developer. As a fixing solution, 5.6 liters of the fixing solution prepared in the same manner was placed in a fixing processing tank of TCX-701 to be used as a fixing start solution.

In each of the developing and fixing steps, the one in which each packaging bag was opened by hand was set at the inlet of each solid agent, and the tablets were dropped into the built-in chemical mixer, and simultaneously with warm water (25 to 25).
(30 ° C), and the mixture is adjusted to 5.0 liters with a dissolution time of 25 minutes while stirring and dissolving. This was used as a developing and fixing replenisher.

When the developer is dissolved, the pH of the developer is 1
0.15, and the pH when the starter was added was 9.90. The pH at the time of dissolution of the fixing solution was 4.25.

The built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank. The capacity of the liquid preparation tank is 5.0 liters and the capacity of the spare tank is 5.0 liters. The film is produced in the liquid preparation tank during the running process. A spare tank is provided to supply the replenisher so that the replenisher does not enter the non-replenished state during the stirring and dissolving time (about 25 minutes) even if the replenisher runs out.

Development temperature 35 ° C. (replenishment rate is 100 ml / m
² ) The evaluation was performed at a fixing temperature of 35 ° C. (replenishment rate was 100 ml / m ² ), water at 18 ° C. (5 liter / min), a drying temperature of 55 ° C., and a processing time of 30 seconds.

<Evaluation of Sensitometry> The prepared sample was sandwiched between two fluorescent intensifying screens XG-S (manufactured by Konica Corporation), and X was measured under the conditions of a tube voltage of 90 kVp, a current of 100 mA and a time of 0.05 second. After irradiating with light and developing, a sensitometric curve was prepared by a distance method, and sensitivity and fog were determined. The value of the sensitivity was determined as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0, and the sample No. The value of 1 is 10
The relative sensitivity was evaluated as 0.

<Evaluation of Scratch Resistance> The unexposed sample photosensitive material was allowed to stand at 23 ° C. and a relative humidity of 40% for 2 hours.
Under the same conditions, 9.8 × 10
After rubbing with a load of ³ Pa, processing was performed with an automatic developing machine under the above conditions, and the evaluation was made by visual observation.

A: Almost no scratches B: Level of practically no problem, but some scratches C: Scratch occurs to the extent of being noticeable and is a problem in practical use D: Very many scratches <Evaluation of processing liquid stain> 500 pieces of a quarter-sized sample, which was entirely exposed to a density of 1.0, were continuously processed under the above-described processing conditions, and 500 pieces were processed from the 491th sheet. The ten samples were evaluated for film contamination by sludge-like deposits, and the average rank was given. Each time the sample was changed, the treatment liquid was exchanged, and running from a new liquid was performed.

A: No deposits B: Small spot-like deposits are slightly observed C: Small spot-like deposits are observed, and a decrease in density is caused by the suppression of development at the deposits D: Large or small A large number of fixed-form deposits were observed, and the concentration was remarkably reduced. <Evaluation of anti-cutting property> The same sample conditioned for 12 hours under the air-conditioning conditions of 23 ° C. and 80% RH was superposed 1.96 × 1.
Apply a load so that a pressure of 0 ³ Pa is applied and leave it for 3 days.
The degree of tightness between the films was determined as follows:
It was rated on a scale.

A: No dustiness B: Less than 5% area C: Less than 15% area D: More than 15% area <Evaluation of antistatic performance> Regarding antistatic performance, unexposed samples were measured at 23 ° C. and 20%. % RH for 2 hours, rub the sample with a rubber roller and a nylon roller in a dark room under the same air-conditioning conditions, and then develop with an automatic developing machine SRX-502 (manufactured by Konica Corporation) for an X-ray automatic developing machine. Liquid XD-S
R, fixer XF-SR (both manufactured by Konica Corporation)
The treatment was performed for 45 seconds, and the generated static mark was evaluated.

The evaluation of the degree of occurrence of the stitch marks was visually determined. The evaluation criteria are as follows.

A: No occurrence B: Less than 3% by area C: 3% or more and less than 10% by area D: 10% or more by area <Evaluation of transportability> Auto feeder KDA-500 (Konica [ Co., Ltd.), and five sets were transported in 100 pieces each of four cut sizes, and the number of occurrences of transport troubles such as two transports was measured.

The sample was conditioned at 23 ° C., 20% RH and 80% RH for 2 hours, and evaluated for transportability under the same conditions. Tables 1 and 2 summarize these results.

[0174]

[Table 1]

[0175]

[Table 2]

From Tables 1 and 2, it can be seen that the light-sensitive material of the present invention and the processing method thereof are excellent without antistatic properties, abrasion resistance, dustiness, and no processing solution stain at low replenishment.

[0177]

According to the present invention, the antistatic property of a film
A light-sensitive material which is excellent in abrasion resistance and dustiness and has improved processing solution stains at low replenishment, and a processing method therefor were obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a silver halide emulsion manufacturing apparatus applicable to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring mechanism 3 Dispersion medium 4 Silver addition line 5 Halide addition line 6 Dispersion medium addition line 7 Addition line 8 Liquid take-out line 9 Liquid return line 10 Permeate discharge line 11 Permeate return line 12 Ultrafiltration unit 13 Circulation Pump 14 Flow meter 15, 16, 17 Pressure gauge 18 Pressure adjusting valve 19 Flow adjusting valve 20 Silver addition valve 21 Halide addition valve 22 Liquid extraction valve 23, 24, 25 Valve 26 Ultrafiltration permeate 27 Permeate receiver 28 Scale 29,30 Silver halide fine grain emulsion addition line 31,32 Fine grain addition valve

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/95 G03C 1/95 5/31 5/31 5/395 5/395

Claims (6)

[Claims] 1. A silver halide photographic material having a silver halide emulsion layer and a non-light-sensitive colloid layer on both sides of a support, wherein at least one layer selected from a silver halide emulsion layer and a non-light-sensitive colloid layer is provided. A silver halide photographic material comprising a compound represented by the following general formula (1) and a polyalkylene oxide nonionic activator represented by the following general formula (2). Embedded image [In the formula, R ₁ and R ₂ each represent a substituent. Where R ₁ ,
At least one of R ₂ represents an alkoxy group or an aryloxy group; X ₁ and X ₂ each represent a halogen atom;
n, p, and q each represent an integer of 0-4. Where m and n
And the sum of p and q is an integer of 0 to 4, and both m and n are not 0. When m, n, p or q is 2 or more, a plurality of R ₁ , R ₂ , X ₁ or X ₂ may be the same or different. General formula (2) R ₂₁ -A- (B) _n21 -R ₂₀ wherein R ₂₀ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
R ₂₁ represents a substituted or unsubstituted alkyl, alkenyl or aryl group having 1 to 30 carbon atoms; A represents -O-, -S-, -C
_{OO -, - CON (R 22} ) -, - N (R 22) -, - SO
₂ N (R ₂₂₎ - represents, R ₂₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, B represents an oxyalkylene group.
n21 represents an average degree of polymerization of the oxyalkylene group;
It is an integer of 50. ] 2. In a silver halide photographic material having a silver halide emulsion layer and a non-light-sensitive colloid layer on both sides of a support, at least one layer selected from a silver halide emulsion layer and a non-light-sensitive colloid layer. A silver halide photographic material comprising a compound represented by the following general formula (3) and a polyalkylene oxide nonionic activator represented by the general formula (2). Embedded image Wherein R ₃₁ and R ₃₂ each represent an alkyl group, an aryl group,
R ₃₃ represents an alkoxy group or an aryloxy group; ] 3. A silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-light-sensitive colloid layer on both sides of a support, wherein the non-light-sensitive colloid layer has a matte degree of 2.00 × 10 ⁴ Pa or more. Contains a matting agent that gives 3.33 × 10 ⁴ Pa, and contains the compound represented by the general formula (1) in at least one layer selected from a silver halide emulsion layer and a non-photosensitive colloid layer. A silver halide photographic material. 4. A silver halide photographic material having a silver halide emulsion layer and a non-photosensitive colloid layer on both sides of a support, wherein the non-photosensitive colloid layer has a matte degree of 2.00 × 10 ⁴ Pa or more. It contains a matting agent that gives 3.33 × 10 ⁴ Pa, and at least one layer selected from a silver halide emulsion layer and a non-photosensitive colloid layer contains the compound represented by the general formula (3). A silver halide photographic material. 5. The polyalkylene oxide-based nonionic activator represented by the general formula (2) is contained in the silver halide emulsion layer and the non-photosensitive colloid layer. The silver halide photographic light-sensitive material as described above. 6. The silver halide photographic light-sensitive material according to claim 1, wherein a replenishment amount of a developing solution or a fixing solution is 50 to 150 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material.
A method for processing a silver halide photographic light-sensitive material, comprising: