JPH08234370A - Silver halide photographic sensitive material and its packaging method - Google Patents

Abstract

PURPOSE: To allow a bright room loading and prevent a photosensitive material having image reproducibility with sharp contrast and high quality from losing these performances in the reservation with the lapse of time. CONSTITUTION: A prescribed silver halide photographic sensitive material is wound in a rolled state on a cylindrical core member. Both side end parts of the core member are covered with closely fitted light shielding flanges 7, and the outer circumference of the photosensitive material is covered with a light shielding leader member 3. When the winding of the leader member 3 has ended, the terminal part of the leader member 3 is fixed onto the photosensitive material with an adhesive sheet 6. Thus, a roll-shaped photosensitive material packaged body is provided. No light is leaked from the space between the leader member 3 and the flange part 7, and even when the packaged body is put on a flat surface, the protruded part of the flange part 7 is fallen down so that the photosensitive material is floated from the surface, and no local excessive force is added to the flange part 7 or the first thermoplastic resin film member 4 of the leader member 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for printing and a method for packaging the same, and more specifically, a silver halide photographic light-sensitive material which has improved storage stability over time and can obtain high-quality image reproduction with high contrast. And its packaging method.

[0002]

2. Description of the Related Art In the past, for printing plate making films and printing papers, there has been a demand for a high-contrast image in which halftone is eliminated as much as possible in order to record halftone dots and line images.

Particularly, high quality is required in each plate-making process. For example, quality such as enlargement (expansion) and reduction (contraction) of a half-tone photograph in a line drawing process, reproducibility of bright paper, and return process. Not only is the character quality high, but the high-definition output exceeding 400 lines / inch, which has been attracting attention in the scanner process in recent years, and the minute Dot output such as the FM screen method, are not only hard, but also from large points to small points. Up to the present, faithful reproducibility is required for the manuscript.

Therefore, as an ultra-high contrast image forming method, a method using a contrast enhancing agent such as a hydrazine derivative, a pyridinium salt derivative or a tetrazolium derivative is well known. For example, a specific method disclosed in US Pat. No. 4,269,929 is known. Of a surface latent image type silver halide photographic light-sensitive material containing a hydrazine derivative of JP-A-63-124045, European Patent 0231850, U.S. Pat. No. 4,975,354. Issue, Japanese Patent Application No. 4-3345
There is known a method of containing a hydrazine derivative as disclosed in No. 1 and including a nucleation accelerator having a specific structure that promotes a hydrazine nucleation reaction. Further, JP-A 1-217337, JP-A 5-53231, and JP-A 6-61009 are known as methods for using a pyridinium salt derivative as a contrast-increasing agent. Other known methods for incorporating a tetrazolium derivative as a contrast-increasing agent are JP-A-57-132137, JP-A-58-173737, and JP-A-61-270745.

As a means for improving the reproducibility faithful to the original, a method of providing an antihalation layer (AHU) between the emulsion layer and the support is known, but it is reduced by diffusion of the dye used for AHU. As a method for reducing the feeling, for example, as disclosed in JP-A-52-92716 and JP-A-2-277045, a dye dispersion which is substantially water-soluble at a pH of 8 or more and is substantially insoluble at a pH of 6 or less. A method of forming an AHU using a material is known.

Further, simply reproducing the optical information faithfully cannot achieve the required quality, and the development of the unexposed area surrounded by the large dots and the blackened area is selectively performed. A method of suppressing is desired, for example, JP-A-61-296138 and JP-A-6-296138.
A method of imagewisely releasing a DIR (Development Inhibiter Releasing) compound as disclosed in 4-88451 and JP-A-4-19647 is known.

Various methods are known as methods for reproducing a high-contrast and faithful image as described above, but materials such as a high-contrast agent, a solid disperse dye, and a DIR compound that greatly change the photographic performance are used. For this reason, there has been a problem that these materials change in the light-sensitive material during storage with time or at high temperature and high humidity, resulting in a large change in performance. In particular, in a roll-shaped photosensitive material obtained by winding a photosensitive material around a cylindrical core member used as one of the usage forms of the photosensitive material, for example, in the longitudinal direction, an outer peripheral portion in contact with the outside air and a portion close to the core portion, and It is often seen that the photographic performance is different near the middle, or in the width direction, in the portions near the ends on both sides of the roll and in the central portion, and improvement thereof has been desired.

As a packaging form of the light-sensitive material, a method of covering the roll-shaped light-sensitive material with a composite material in which polyethylene of about 100 μm containing carbon black or aluminum foil is laminated in consideration of light shielding and storability of the light-sensitive material is used. However, it has not been perfect in terms of storability of the light-sensitive material.

Further, in these packaging forms, when the light-sensitive material is set in the exposure machine or the film magazine, it is necessary to work in a dark room, and workability and installation space of the dark room have been studied. .

As a result, various methods have been tried for packaging forms that can be loaded into a film magazine in a bright room, and light-shielding properties and film protective properties have also been investigated. However, no study has been made on the storability of the packaged light-sensitive material over time, and its improvement has been desired.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to store a silver halide photographic light-sensitive material containing a specific material, capable of being loaded in a bright room, having high contrast and high-quality image reproducibility, with time. The present invention provides a method for packaging a silver halide photographic light-sensitive material that does not impair their performance. Other purposes will be apparent from the following specification.

[0012]

The objects of the present invention have been achieved by the following.

(1) In a method for packaging a silver halide photographic light-sensitive material, which comprises winding a silver halide photographic light-sensitive material containing a tetrazolium salt, a pyridinium salt or a hydrazine derivative around a cylindrical core member in a roll shape, A method for packaging a silver halide photographic light-sensitive material, characterized in that both ends of the member are covered with light-shielding flanges that are in close contact with each other, and the outer periphery of the light-sensitive material is covered with a light-shielding leader.

(2) A silver halide photographic light-sensitive material containing at least one hydrazine derivative and at least one nucleation accelerator is packaged by the packaging method described in the above item (1). Method for packaging silver halide photographic light-sensitive material.

(3) Halogenated containing a solid dispersion of a dye which contains a tetrazolium salt, a pyridinium salt or a hydrazine derivative and is substantially water-insoluble at a pH of 6 or less and substantially water-soluble at a pH of 8 or more. A method for packaging a silver halide photographic light-sensitive material, characterized in that the silver photographic light-sensitive material is packaged by the packaging method described in the above item (1).

(4) A silver halide photograph containing a compound containing a tetrazolium salt, a pyridinium salt or a hydrazine derivative and containing a compound which is oxidized by the oxidation product of a developing agent to release a development inhibitor or is converted into a development inhibitor. A method of packaging a silver halide photographic light-sensitive material, characterized in that the light-sensitive material is packaged by the packaging method described in the above item (1).

(5) At both ends of a cylindrical core member made of a light-shielding material around which a silver halide photographic light-sensitive material is wound,
The roll has a light-shielding flange made of a thermoplastic resin having a light-shielding property and a bending strength of 250 kg / cm ² or more, and the leader covering the outer periphery has a length 1.5 times or more the outer periphery length of the roll. Part of the width of the photosensitive material is wider than that of the photosensitive material, the thickness is 40 to 150 μm, the elastic modulus is 2000 kg or more, and the leader is continuous with the photosensitive material. ) To (4), the method for packaging the silver halide photographic light-sensitive material according to any one of the items.

(6) The silver halide photographic light-sensitive material described in any one of the above items (1) to (4), which is packaged by the method described in the above item (5).

The present invention will be described in detail below.

The packaging material used in the present invention comprises a light-shielding leader and a flange for shielding the outer peripheral portion and the end portion of a roll-shaped light-sensitive material obtained by winding a light-sensitive material around a cylindrical core member. This is achieved by a packaging material that allows the film to be drawn out.

More specifically, in order to provide a sufficient light-shielding property that can be handled even in a bright room, a part of the end flange and the leader covering the outer peripheral portion are sealed with each other.

The light-shielding packaging is in the packaging form described in JP-A-62-172344, Japanese Utility Model Publication No. 4-85438 or Japanese Patent Application No. 6-134368.
The light-shielding flange that covers the end portion and the light-shielding leader that covers the outer periphery of the roll-shaped photosensitive material as described in No. 6, and the width of the light-shielding leader is wider than the width of the roll-shaped photosensitive material This is achieved by a packaging method in which light is wrapped around a flange.

As for the light-shielding flange or the light-shielding leader, the same one as described in Japanese Patent Application No. 6-134360 is preferably used.

It was unexpected that the light-shielding property as well as the storage stability of the light-sensitive material could be improved and improved by providing sufficient light-shielding property even in a bright room.

In the present invention, in order not to be restricted by the size of the film magazine or the function of fixing the film in the magazine, the light-shielding flanges that adhere to both ends are projected from the outer peripheral portion of the rolled photosensitive material, 0.3 mm
1 mm or less and a bending strength of 25 Okg / cm ² or more, preferably 400 kg / cm ² or more, made of a thermoplastic resin, and the light-shielding leader covering the outer periphery is 2 mm wider than the width of the roll-shaped photosensitive material.
Or more, preferably is wider so that a range of 3 mm to 6 mm, and a tensile modulus of 2000 kg / cm ² or more, preferably made of a thermoplastic resin film of ^{2000kg / cm 2 ~5000kg / cm 2} .

Although the use of the above-mentioned packaging form has a great effect on the storage stability of the light-sensitive material, from the viewpoint of productivity and cost of the packaging process, it is described in, for example, Japanese Utility Model Publication No. 4-85438. You can refer to the method.

Next, a particularly preferable form of the packaging form according to the present invention will be described in detail with reference to the drawings.

FIG. 1 is a perspective view showing a state in which a light-shielding leader member is connected to the end of the photosensitive material of the roll portion, FIG. 2 is a perspective view showing a flange member, and FIG. 3 is a flange member attached to the roll portion of FIG. 4 and 5 are perspective views and a plan view of a state in which a light shielding leader member is wound around the photosensitive material roll, and FIG. 6 is a perspective view of a roll-shaped photosensitive material package of the present invention. 7 is a side view of the roll-shaped photosensitive material packaging body of the present invention placed on a plane, and FIG. 8 is a perspective view showing a state in which the roll-shaped photosensitive material packaging body of the present invention is stored in a box,
FIG. 9, FIG. 10 and FIG. 11 are an external view, a partial sectional side view and an internal view of the holder member, respectively.

1 to 7, 1 is a cylindrical core member made of a light-shielding paper tube or the like, 2 is a photosensitive material having a width 2a substantially equal to the width 1a of the cylindrical core member 1, and the cylindrical core member 1
Is rolled to form a roll. 3, the width 4a is the cylindrical core member width 1a and the photosensitive material width 2a (correctly, the width of the roll portion).
Wider with a thickness of 40-100 μm and a tensile modulus of 1800
A first thermoplastic resin film member 4 made of, for example, a polyethylene film having a light-shielding property of up to 5,000 kg / cm ² ,
The width 5a is almost equal to the width 2a of the photosensitive material, and the thickness is 15 to 50 μm.
This is a light-shielding leader member in which a second thermoplastic resin film member 5 made of, for example, a polyethylene terephthalate film having m and a tensile elastic modulus of 20,000 to 45,000 kg / cm ² is laminated and adhered by aligning the width centers. 6 is an adhesive sheet coated with an adhesive on one side, and 7 is a flange made of a thermoplastic resin having a light-shielding property, which is composed of a cylindrical boss portion 7a fitted into the inner diameter of the cylindrical core member 1 and a flange portion 7b. It is a member.

It is effective to form the flange member 7 from a light-shielding thermoplastic resin sheet by a vacuum molding method or a vacuum pressure molding method, or by a light-shielding thermoplastic resin injection molding method. And the flange member 7
Has a bending strength of 250 kg / cm ² or more, preferably 400 kg / c, determined in accordance with JIS K-7203 of the thermoplastic resin that constitutes it.
It is necessary that the thickness of the flange portion 7b is 0.3 to 1 mm, and preferably 0.4 to 0.8 mm, when it is m ² or more. As the thermoplastic resin of the flange member 7, PS, ABS, PC, acrylic, P
A, PE, PP and the like are preferably used.

The above-mentioned bending strength of the thermoplastic resin of the flange member 7 is less than 250 kg / cm ² , or the flange portion 7b
If the thickness is less than 0.3 mm, the flange portion 7b protruding more than the outer circumference of the roll portion may easily fall down, which may make it difficult to cover the protruding flange portion 7b with the light-shielding leader member 3 or may be easily peeled off. Further, when the roll-shaped photosensitive material packaging body is placed on a flat surface, the photosensitive material 2 may be applied with a weight pressure. Also, the flange portion 7
If the thickness of b is more than 1 mm, the productivity of the flange member 7 will be reduced, and it will be difficult to obtain dimensional accuracy.

A photosensitive material 2 is wound around a cylindrical core member 1 in a dark room as shown in FIG.
The light-shielding leader member 3 is connected by. Before or after the light-shielding leader member 3 is connected, the flange members 7 shown in FIG. 2 are provided at both ends of the cylindrical core member 1 with cylindrical boss portions 7a.
Is fitted to the inner diameter of the cylindrical core member 1 and attached as shown in FIG. The present invention is not limited to this, and the photosensitive material 2 may be wound around the cylindrical core member 1 to which the flange member 7 is attached.

The flange portion 7b of the flange member 7 has an outer diameter which projects outward from the outer peripheral surface of the photosensitive material 2 by 2 to 10 mm, preferably 3 to 6 mm. Even if this protrusion height is lower than 2 mm
Flange portion 7b of light-shielding leader member 3 even if higher than 10 mm
It becomes difficult to bend and cover the outer surface.

Next, the light-shielding leader member 3 is wound around the rolled photosensitive material 2 around the cylindrical core member 1 with the flange member 7 as described above. At this time, as shown in FIGS. 4 and 5. Further, it is preferable to use a pressing roller 8 that presses the outer surface of the light-shielding leader member 3 at the winding position near the inside of the flange portion 7b, and a pinching tension roller 9 that applies tension to the light-shielding leader member 3 to be wound.

When tension is applied to the light-shielding leader member 3 and the light-shielding leader member 3 is wound around the light-sensitive material 2, a portion of the first thermoplastic resin film member 4 shown in FIG. However, as shown in FIG. 4 and FIG. 5, the inner surface of the projecting portion projecting from the roll portion of the flange portion 7b to the outer peripheral surface and the outer peripheral surface of the outer peripheral surface extending from the outer diameter to the peripheral portion 2 mm or more inside It comes into close contact with and covers the surface of.

The coating width from the outer diameter with which the first thermoplastic resin film member 4 covers the outer surface of the flange portion 7b is 2
If the width is smaller than mm, light is likely to leak due to peeling of the coating. That is, Smm of the left and right wide portions of the first thermoplastic resin film member 4 shown in FIG. 1 covers the outside diameter of the outer surface of the flange portion 7b from 2 mm or more to the inside, preferably 5 mm or more to the inside. Set to dimensions.

The first thermoplastic resin film member 4 has a thickness of 40 because it is brought into close contact with the flange portion 7b as described above.
～100Myuemu, tensile modulus needs to be made of a thermoplastic resin film 1,500~5,000kg / cm ^2. Thickness is 40
If it is thinner than 100 μm, light leakage due to breakage is likely to occur, and if it is thicker than 100 μm, it becomes difficult to cover the flange portion 7b. Moreover, even if the tensile modulus is less than 1,500 kg / cm ^2, damage due to local extension easily occurs,
Even if it is larger than g / cm ^2, it becomes difficult to cover the flange portion 7b.

The second thermoplastic resin film member 5 bears the rigidity of the light-shielding leader member 3 to improve the close contact with the roll portion around which the photosensitive material 2 is wound, and when the light-shielding leader member 3 is stretched. In order to prevent the first thermoplastic resin film member 4 from extending too much in the longitudinal direction, the width 5a is less than the width 2a of the photosensitive material 2.
It is preferable that the thickness is in the range of 2 mm, and the thickness is 15 to 50 μm,
It must be made of a thermoplastic resin film having a tensile elastic modulus of 20,000 to 45,000 kg / cm ² .

If the thickness of the second thermoplastic resin film member 5 is less than 15 μm or the tensile elastic modulus is less than 20,000 kg / cm ² , the above object cannot be achieved and the thickness is 50.
If it is thicker than μm or the tensile elastic modulus is larger than 45,000 kg / cm ^{2, it} is difficult to apply tension to the first thermoplastic resin film member 4, so that the first thermoplastic resin film member 4 is placed outside the flange portion 7b. It becomes difficult to bend and bend to the side.

As a specific example, the flange member 7 has a light-shielding PS.
The flange portion 7b is formed by vacuum forming the sheet, the thickness of the flange portion 7b is 0.5 mm, the outer diameter of the flange portion 7b projects 6 mm from the outer peripheral surface of the photosensitive material 2, and the first portion of the light shielding leader member 3 is formed.
The thermoplastic resin film member 4 has a width of 332 mm, a thickness of 60 μm,
The second thermoplastic resin film member 5 is a light-shielding polyethylene film having a tensile elastic modulus of 2,800 kg / cm ² and having a width substantially equal to the width of the photosensitive material 2, a width of 310 mm, a thickness of 25 μm, and a tensile elastic modulus of 35,000 kg / In the case of a polyethylene terephthalate film of cm ² , when a tension of about 0.7 kg or more is applied to the light-shielding leader member 3, the first heat is applied from the inner diameter of the protrusion of the flange portions 7b on both sides to the inner diameter of about 8 mm from the outer diameter of the outer surface. The plastic resin film member 4 is covered by adhesion. in this case,
Although the winding deviation occurs when the photosensitive material 2 is wound around the cylindrical core member 1, the cylindrical core is formed so as to make the width of the photosensitive material roll with the flange members 7 fitted at both ends as short as possible. It is desirable that the width of the member 1 be almost the same as the width 2a of the photosensitive material 2 or be 1 to 2 mm shorter with a margin. The width of the photosensitive material roll is the width 2a of the photosensitive material 2.
On the other hand, if the length is too long, it will be difficult to mount the photosensitive material roll on the processing device of the photosensitive material 2 or the like.

When the winding of the light-shielding leader member 3 is completed, the end portion of the light-shielding leader member 3 is attached to the outer peripheral surface of the light-shielding leader member 3 wound on the photosensitive material 2 with an adhesive sheet 6.
And stop as shown in FIG. As a result, the roll-shaped photosensitive material package of the present invention is obtained. The length Lmm of the light-shielding leader member 3 shown in FIG. Set the length to wind more.

The roll-shaped photosensitive material package thus obtained can be placed on a flat surface as shown in FIG. 7 without causing light leakage between the light-shielding leader member 3 and the flange portion 7b. , The protruding portion of the flange portion 7b is elastically tilted so as to float the photosensitive material 2 from the plane, and is locally formed on the flange portion 7b or the first thermoplastic resin film member 4 of the light-shielding leader member 3 covering the flange portion 7b. Since excessive force is not applied, damage to the flange portion 7b and the first thermoplastic resin film member 4 as well as damage to the photosensitive material 2 are of course possible.
There is no pressing tendency or wrinkles, and the coating of the first thermoplastic resin film member 4 does not peel off, so that light leakage does not occur. In particular, in the case where the light-shielding leader member 3 wraps the outer circumference of the photosensitive material 2 three times or more and the first thermoplastic resin film member 4 covers from the outer diameter of the outer surface of the flange portion 7b to the inner side of 5 mm or more. Moreover, damage and peeling of the coating are less likely to occur, and light leakage does not occur.

When the roll-shaped photosensitive material package of the present invention is transported or stacked and stored in a warehouse or the like, it is preferable that the package is stored in a box as shown in FIG. That is, the air cap material 11 is attached to the outer periphery of the portion of the roll-shaped photosensitive material package 10 of the present invention where the photosensitive material is wound, as shown in the figure, and the roll-shaped photosensitive material package 10 is provided.
At both ends of the holder member 12 having a flat plate-shaped base portion 12a and a short cylindrical protrusion portion 12b as shown in detail in FIG. 9, the outer diameter of the short cylindrical protrusion portion 12b is set to the cylindrical boss portion 7 of the flange member 7.
It is attached by fitting it to the inner diameter of a. Then, the roll-shaped photosensitive material packaging body 10 with the holder member 12 is lifted by the air cap material 11 and stored in the box 13.

The air cap material 11 is preferably made of a flexible material such as a commercially available polyethylene film air cap material that is not affected by exerting a local overpressure on the photosensitive material 2. Further, the air cap material 11 preferably has an air cap portion having a thickness of 4 to 15 mm, particularly 8 to 15 mm, so that the photosensitive material 2 can be used even when the roll-shaped photosensitive material package 10 is left on a desk for a long time. Can be protected from damage by external force and good quality can be maintained.

The holder member 12 holds the roll-shaped photosensitive material package 10 in a floating state by its flat plate-shaped base portion 12a, and the light-shielding leader member 3 and the flange portion 7a of the flange member 7 as well as the photosensitive member during transport and storage. It prevents the material 2 from being damaged by an external force. As described above, in the stationary state, the roll portion can be held in a floating state also by the flange member 7, but during transportation or the like, the flange portion 7b can be held.
Is thin, and strength is impossible. The holder member 12 can be manufactured by blow molding, vacuum molding, injection molding, or the like, and it is preferable to manufacture it by blow molding of polyethylene in terms of productivity and cost.

The holder member 12 shown in FIG. 9 has a short cylindrical protrusion 12
b is a cylindrical boss portion 7a of the flange member 7 smoothly up to the root
An annular relief groove 12c is provided at the base of the short cylindrical protrusion 12b so as to enter the inner diameter of the flat base 12a.
A hole 12d for attaching a roll-shaped photosensitive material packaging body lifting handle is provided on the side opposite to the short cylindrical protrusion 12b. The holder member 12 is not limited to the example shown in the figure, and any other means may be used as long as it can prevent the roll-shaped photosensitive material package from moving and being damaged inside the box or the like in which it is stored. , Having a projecting portion projecting more outward than the flange member 7 and having sufficient strength to support the weight of the roll-shaped photosensitive material package, and set on the flange members 7 at both ends of the roll-shaped photosensitive material package. Anything can be used.

In the present invention, it is needless to say that the cylindrical core member is not limited to the paper tube, and the thermoplastic resin of the film of the flange member or the light shielding leader member is not limited to the exemplified resin.

Next, the hydrazine compound used in the present invention can be represented by the following general formula [H].

[0049]

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In the formula, A ₀ represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples include, for example, methyl, ethyl, t-butyl, octyl, cyclohexyl, benzyl group and the like, and these are further suitable substituents (for example, aryl, alkoxy, aryloxy,
(Alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido groups, etc.)
May be replaced with.

The aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic group represented by A ₀ is preferably a monocycle or a condensed ring containing at least one hetero atom selected from nitrogen, sulfur and oxygen atoms, and examples thereof include pyrrolidine, imidazole, tetrahydrofuran, morpholine and pyridine. Pyrimidine, quinoline,
Examples thereof include thiazole, benzothiazole, thiophene and furan ring. Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group of A ₀ may have a substituent. Particularly preferred groups include a substituent having an acidic group having a pKa of 7 or more and 11 or less, and specific examples thereof include a sulfonamide group, a hydroxyl group, and a mercapto group.

A ₀ preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is a photographically inactive group having 8 or more carbon atoms, such as an alkyl group, an alkenyl group or an alkynyl group, Alkoxy group, phenyl group,
Examples thereof include a phenoxy group and an alkylphenoxy group.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group.

G ₀ is a --CO-- group, a --COCO-- group, a --CS-- group,
-C (= NG ₁ D ₁ )-group, -SO- group, -SO ₂ -group or -P (O) (G
₁ D ₁ ) -group. G ₁ is a simple bond, -O- group, -S-
Represents a group or a —N (D ₁ ) — group. D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D _{1 s} are included in the molecule.
, If present, they may be the same or different.

D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group. Preferable G ₀ is —CO— group, and —COCO— group, and particularly preferably —COCO—
Groups. Preferred D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group (ethoxalyl, etc.). Etc.).

Specific examples of the compound represented by the general formula [H] are shown below, but the invention is not limited thereto.

[0059]

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[0060]

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[0061]

[Chemical 4]

[0062]

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[0063]

[Chemical 6]

Next, the pyridinium salt derivative used in the present invention is represented by the following general formula [Pa], [Pb] or [Pc].

[0065]

[Chemical 7]

In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a non-metal atom group for completing the nitrogen-containing heterocycle,
It may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴
And the heterocycle composed of A ⁵ may have a substituent, and they may be the same or different. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an aryloxy group. , Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group,
It represents a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group. As preferred examples, A ¹ , A ² , A ³ , A ⁴ and A ⁵ are 5- or 6-membered rings (for example, pyridine, imidazole, thiazole, oxazole,
Pyrazine, pyrimidine ring, etc.), and a pyridine ring is particularly preferable.

B _P represents a divalent linking group, and examples of the divalent linking group include alkylene, arylene, alkenylene and --SO ₂
-, - SO -, - O -, - S -, - CO -, - N (R 6) -, (R 6
Represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _P include alkylene, alkenylene and alkylene oxide.

R ¹ , R ² and R ⁵ represent a saturated or unsaturated alkyl group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. As the substituents, A ¹ , A ² ,
It has the same meaning as the groups mentioned as the substituents for A ³ , A ⁴ and A ⁵ .

As a preferred example, R ¹ , R ² and R ⁵ each represent an alkyl group having 4 to 10 carbon atoms. Further preferable examples are a substituted or unsubstituted aryl group and a substituted alkyl group. X _P represents a counter ion necessary for balancing the charge of the entire molecule, and represents, for example, chloride ion, bromine ion, iodide ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate. n _P represents the number of counterions required to balance the charge of the entire molecule, and n _P is 0 in the case of an inner salt. Specific compound examples are shown below.

[0070]

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[0071]

[Chemical 9]

[0072]

[Chemical 10]

[0073]

[Chemical 11]

[0074]

[Chemical 12]

In the present invention, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb] in order to effectively promote the contrast enhancement by the hydrazine and pyridinium compounds.

[0076]

[Chemical 13]

In the general formula [Na], R ₁₁ , R ₁₂ , and R ₁₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. A ring can be formed by R ₁₁ , R ₁₂ , and R ₁₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is particularly preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific examples of compounds of these nucleation accelerators [Na] are shown below.

[0079]

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[0080]

[Chemical 15]

[0081]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, but Ar and R ₁₄ may be connected by a connecting group to form a ring. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Further, as a preferable silver halide adsorbing group, a group having the same meaning as the silver halide adsorbing group of the compound represented by the general formula [H] can be mentioned.

Specific examples of the compound of the general formula [Nb] include those shown below.

[0084]

[Chemical 17]

[0085]

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In the present invention, the effect of the present invention was great when a nucleation accelerator having a molecular weight of 500 or less was used.

The tetrazolium compound used in the present invention is represented by the following general formula [T].

[0088]

[Chemical 19]

In the present invention, the substituents R ₁ , R ₂ and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T] are hydrogen atoms or Hammett's sigma value (σP) showing electron withdrawing degree. ) Is preferably negative.

Hammett's sigma value for phenyl substitution is well documented, eg, Journal of Medical Chemistry, Vol. 20,
See, for example, C. Hansch et al., P. 304, 1977, and a particularly preferred group having a negative sigma value is, for example, a methyl group (σ _P = −0.17 or less. Σ _P value) ethyl group (−0.15), cyclopropyl group (−0.21), n-propyl group (−0.13), isopropyl group (−0.15), cyclobutyl group (−0.15), n-butyl group (−
0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-0.66),
Acetylamino group (-0.15), hydroxyl group (-0.3
7), a methoxy group (-0.27), an ethoxy group (-0.24), a propoxy group (-0.25), a butoxy group (-0.32), a pentoxy group (-0.34) and the like. Useful as a substituent of the compound of the formula [T].

N represents 1 or 2, and examples of the anion represented by X _T ^n- are halogen ions such as chloride ion, bromide ion and iodide ion, inorganic acids such as nitric acid, sulfuric acid and perchloric acid. Acid radicals of organic acids such as carboxylic acid, sulfonic acid and carboxylic acid, anionic activators, specifically
Lower alkylbenzene sulfonate anion such as p-toluene sulfonate anion, higher alkylbenzene sulfonate anion such as p-dodecylbenzene sulfonate anion, higher alkyl sulfate ester anion such as lauryl sulfate anion, boric acid anion such as tetraphenylboron, For dialkyl sulfosuccinate anion such as di-2-ethylhexyl sulfosuccinate anion, polyether alcohol sulfate anion such as cetyl polyethenoxysulfate anion, higher aliphatic anion such as stearate anion, and polymer such as polyacrylate anion The thing with an acid radical etc. can be mentioned.

Specific examples of the compound represented by the formula [T] are shown below, but the tetrazolium compound is not limited thereto.

[0093]

[Table 1]

The above-mentioned tetrazolium compound can be obtained, for example, from Chemical Reviews, Volume 55, pp. 335-4.
It can be easily synthesized according to the method described on page 83.

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

The hydrazine derivative, pyridinium salt or tetrazolium salt and the nucleation accelerator used in the present invention are
It may be used in any layer as long as it is on the silver halide emulsion layer side, and is preferably used in the silver halide emulsion layer or its adjacent layer.

The optimum amount of addition is not uniform depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but generally 10 ⁻ per mol of silver halide. The range of ⁶ mol to 10 ^-1 mol is preferable, and the range of 10 ^-5 mol to 10 ^-2 mol is particularly preferable.

The silver halide photographic light-sensitive material of the present invention comprises a dye which is substantially water-insoluble at pH 6 or less and is substantially water-soluble at pH 8 or more in at least one layer on the silver halide emulsion layer side. It may contain a solid dispersion.

As the above solid disperse dye used in the present invention, fine dye particles represented by the following general formulas [1] to [6] are preferably used.

[0100]

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The above-mentioned general formula [1] used in the present invention:
The compound represented by [6] will be described.

Examples of the aryl group represented by Q in the above general formulas [1] and [4] include a phenyl group and a naphthyl group. Moreover, as the heterocycle represented by Q,
For example, pyridine, quinoline, isoquinoline, pyrrole,
Pyrazole, imidazole, indole residues and the like can be mentioned.

The aryl group and the heterocycle include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfamoyl group and a sulfonamide group, and two or more kinds of these substituents may be combined. Preferably,
Alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, 2-hydroxyethyl group, etc.), hydroxy group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, methylenedioxy group, 2-hydroxyethoxy group, n-
Butoxy group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group , Morpholino group, piperidino group, pyrrolidino group etc.), carboxy group, sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), sulfamoyl group (eg sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group) Etc.) and these substituents may be combined.

The acidic nuclei represented by A and A'in the general formulas [1], [2] and [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanin, hydantoin and thiol. Hydantoin, oxazolone,
Examples thereof include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Examples thereof include thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole and indole.

The electron withdrawing groups represented by X and Y in the general formulas [4] and [5] may be the same or different, and for example, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carboxy group, acyl group, alkylsulfonyl group, arylsulfonyl group,
A sulfamoyl group is mentioned.

The heterocycle represented by B'in the general formula [6] is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

L ₁ , L ₂ and L _{3 of the} general formulas [1] to [5]
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isobutyl, etc.),
Aryl groups (eg phenyl, p-tolyl, p-chlorophenyl, etc.), C1-C4 alkoxy groups (eg methoxy, ethoxy, etc.), aryloxy groups (eg phenyl, etc.), aralkyl groups (eg benzyl) Groups, phenethyl groups, etc.), heterocyclic groups (eg pyridyl, furyl,
Thienyl, etc.), substituted amino groups (eg dimethylamino,
Tetramethyleneamino, anilino, etc.) and alkylthio groups (eg, methylthio group, etc.).

Next, specific examples of the dye used in the present invention will be given.

[0110]

[Chemical 21]

[0111]

[Chemical formula 22]

[0112]

[Chemical formula 23]

[0113]

[Chemical formula 24]

[0114]

[Chemical 25]

[0115]

[Chemical formula 26]

[0116]

[Chemical 27]

[0117]

[Chemical 28]

[0118]

[Chemical 29]

[0119]

Embedded image

In the present invention, the above general formulas [1] to
The method of dispersing the dye represented by [6] is not particularly limited, but a known method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied.

The average particle size of the finely dispersed dye fine particles of the present invention may take any value, but preferably 0.01 to 20.
μm, and more preferably 0.03 to 2 μm. Also,
The variation coefficient of the particle diameter of the solid fine particles of the present invention is preferably 60% or less, more preferably 40%.
It is the following.

The fine dye particles of the present invention can be arranged in any layer of the photographic element, and examples of the side of the photosensitive silver halide emulsion layer include, for example, a protective layer above the emulsion layer, an emulsion layer and an undercoat layer. Or between the first emulsion layer and the second emulsion layer. In the case of a backing layer, a protective layer or the like on the backing layer may be mentioned. Further, the addition amount of the dye fine particles of the present invention is not particularly limited, but the effective concentration is 0.3
It is preferable that the addition amount is 2 or more.

The silver halide photographic light-sensitive material of the present invention releases a development inhibitor by being oxidized during development processing.
DIR compounds can be used. Specifically, it can be represented by the following general formula [D].

General Formula [D] A- (Time) _t -X In the formula, A represents a redox mother nucleus, and-(Time) _t -X can be released by being oxidized during development processing. Represents an atomic group that can be trained. As such an atomic group, hydroquinone, catechol, naphthohydroquinone, aminophenol, pyrazolidone, hydrazine, hydroxylamine, reductones and the like are preferably used. Time is 2
It may represent a valence linking group and may have a timing adjustment mechanism.
t represents 0 or 1. X represents a development inhibitor, and is specifically a known development inhibitor having a hetero atom. Preferable specific examples of these A, Time, and X are, for example, JP-A-3-
Examples thereof include those described in Nos. 174143 and 3-29643. The DIR compound particularly preferably used in the present invention includes compounds represented by the following general formula [I] or [II].

[0125]

[Chemical 31]

In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group or oxalyl. Represents a group, a heterocyclic group, an alkoxycarbonyl group, or an aryloxycarbonyl group. R ₄ represents a hydrogen atom. Tm represents a timing group,
n represents 0 or 1. PUG represents a development inhibitor residue. X
Represents O or NH. Z represents an atomic group necessary for constituting a 5- or 6-membered heterocycle.

An alkyl group represented by R ₁ , an aryl group,
Alternatively, the heterocyclic group is preferably a methyl group, a p-methoxyphenyl group, a pyridyl group or the like. Of the acyl groups, carbamoyl groups, cyano groups, nitro groups, sulfonyl groups, aryl groups, oxalyl groups, heterocyclic groups, alkoxycarbonyl groups and aryloxycarbonyl groups represented by R ₂ and R ₃ , preferably an acyl group, A carbamoyl group and a cyano group. The total number of carbon atoms in these groups is preferably 1-20. R _{1 to} R ₃ may further have a substituent, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group). , Methoxymethyl group, trifluoromethyl group, t-
Butyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aralkyl group (eg benzyl group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group, p-tolyl group, p- Chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, n-butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group (eg acetylamino group, propionylamino group) Etc.), alkylthio group (eg methylthio group, ethylthio group, n-butylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido group (eg 3-methylureido group, 3,3-dimethylureido group, 1,3-di Tilureido group etc.), sulfamoylamino group (eg dimethylsulfamoylamino group etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethyl Sulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group etc.) ), An acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), an amino group (eg, methylamino group, ethylamino group, dimethylamino group, etc.), a hydroxyl group, a nitro group, an imide group (eg, phthalyl group). And a heterocyclic group (for example, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group, etc.).

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962, 4,409,323 and 3,674,478.
No. 21228 (December 1981), JP-A-57-56837, JP-A-4-438 and the like.

The 5- or 6-membered heterocycle represented by Z may be a single ring or a condensed ring, and is a 5- or 6-membered heterocycle having at least one O, S, or N atom in the ring. Can be mentioned. These rings may have a substituent, and specific examples thereof include the above-mentioned substituents.

Preferred development inhibitor residues for PUG include, for example, US Pat. No. 4,477,563 and JP-A-60-218644.
No. 60-221750, No. 60-233650, or No. 61-11743. Specific examples of the compound represented by the general formula [I] or the general formula [II] are shown below, but the present invention is not limited thereto.

[0131]

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[0132]

[Chemical 33]

[0133]

Embedded image

[0134]

Embedded image

A fluorinated surfactant can be used in the silver halide photographic light-sensitive material of the present invention. As specific compounds, compounds represented by the general formula [FA] or the general formula [FK] described on pages 14 to 18 of JP-A-5-224328 can be preferably used.

The halogen composition of the silver halide photographic light-sensitive material according to the present invention is not particularly limited, but preferably silver chlorobromide or silver chloroiodobromide emulsion containing silver chloride having a silver chloride content of 60 mol% or more. Is.

The average grain size of silver halide is preferably 0.7 μm or less, and more preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or can be approximated to a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size. CE for details on how to determine the average particle size
“The theory of the photographi” by K. Mees & T.H. James
c process "3rd edition, pp. 36-43 (1966. Published by Mcmillan).

The shape of the silver halide grains is not limited, and may be tabular, spherical, cubic, tetradecahedral, regular octahedral or any other shape. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. or,
A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase where silver halide is formed as a form of the double jet method.
Can be used, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The silver halide grain has a grain size of 8 or more such as a cadmium salt, a zinc salt, a lead salt, a thallium salt, a ruthenium salt, an osmium salt, an iridium salt or a rhodium salt in at least one of the grain forming process and the growing process. It is preferable to add a group transition metal or a complex salt containing these elements.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (RD) N.
17643.22-23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. The preferred chemical sensitization method is sulfur sensitization, and as the sulfur sensitizer, various sulfur compounds other than the sulfur compound contained in gelatin, such as thiosulfates, thioureas, rhodanins, and polysulfide compounds, are used. Can be used.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound, ascorbic acid and the like can be used.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Any of the ring nuclei normally used for cyanine dyes as a basic heterocyclic ring nucleus can be applied to these dyes.

That is, pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole, pyridine ring nuclei, etc., in which an alicyclic hydrocarbon ring is fused to these nuclei or an aromatic hydrocarbon ring Fused nuclei, namely indolenine, benzindolenine, indole, benzoxazole,
Naphtoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, quinoline nucleus and the like can be applied. These ring nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, pyrazoline is used as a nucleus having a ketomethylene structure.
-5-one, thiohydantoin, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic rings such as 4-dione, thiazolidine-2,4-dione, rhodanine and thiobarbituric acid nucleus can be applied. Specifically, (RD) No.17643.23-24 pages, 3
4686 (1993), U.S. Pat. Nos. 4,425,425 and 4,425,426 can be used.

In the present invention, the stabilizing effect was large in the sensitizing dye which is sensitive to light having a relatively long wavelength of 600 nm or more. Examples of dyes having a large effect include JP-A-6-194771, JP-A-6-194774, JP-A-6-242533, and JP-A-5-194533.
Examples include sensitizing dyes described in 119425, 5-158181, and Japanese Patent Application No. 6-195578.

As a method of dissolving or dispersing these sensitizing dyes and adding them to an emulsion, US Pat. No. 3,482,981,
3,585,195, 3,469,987, 3,425,835, 3,3
42,605, British Patents 1,271,329, 1,038,029, 1,
The methods described in 121,174, US Pat. Nos. 3,660,101 and 3,658,546 can be used. Also U.S. Patent 3,485,63
It may be dissolved using ultrasonic vibration described in No. 4.

The sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in (RD) No.17643.23, item IV, section J.

The silver halide photographic light-sensitive material according to the present invention contains various compounds for the purpose of preventing the occurrence of fog during the manufacturing process of the light-sensitive material, during storage or processing and stabilizing the photographic performance. Can be included. That is, azoles, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .;
Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes) , Pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added.

The hydrophilic colloid layer including the emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-
Hexahydro-s-triazine, bis [vinylsulfonyl] methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.) peptide synthesis reagents, active halogen compounds (2,4-dichloro-6- Hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazoles,
Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

Further, the hydrophilic colloid layer contains a coating aid,
Various known surfactants may be used for various purposes such as antistatic, improvement of slipperiness, emulsion dispersion, prevention of adhesion and improvement of photographic characteristics.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

The silver halide photographic emulsion may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

Various other additives are used in the silver halide photographic light-sensitive material of the present invention. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and dyes.

Specific examples of these additives include those described in (RD) No. 17643.22 to 31 (December 1978).

In the silver halide photographic light-sensitive material of the present invention, the emulsion layer and the protective layer may be a single layer or a multi-layer composed of two or more layers. In the case of multiple layers, an intermediate layer may be provided.

The photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Examples of useful materials as the flexible support include films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and polyethylene terephthalate.

The developing agents that can be used in the silver halide photographic light-sensitive material of the present invention include dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone,
Brom hydroquinone, 2,3-dichlorohydroquinone,
Methyl hydroquinone, isopropyl hydroquinone,
2,5-dimethylhydroquinone etc.), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1 -Phenyl-4-ethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diamino) Phenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1
-(p-Methylaminophenyl) -3-aminopyrazoline, 1- (p
-Aminophenyl) -3-aminopyrazoline, 1- (p-amino-N
-Methylphenyl) -3-aminopyrazoline, etc.) and transition metal complex salts (complex salts of transition metals such as Ti, V, Cr, Mn, Fe, C, Ni and Cu), which are used as a developing solution. Any form having reducing power, such as Ti ³⁺ , V ²⁺ , Cr ²⁺ ,
It takes the form of a complex salt such as Fe ^{2+, and} as the ligand, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, phosphorus such as hexametapolyphosphoric acid and tetrapolyphosphoric acid. Examples thereof include acids and salts thereof. ) And the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, a combination of aminophenols and dihydroxybenzenes or 3-
Pyrazolidones and ascorbic acid are preferably used, aminophenols and ascorbic acid are preferably used, 3-pyrazolidones and transition metal complex salts are preferably used, and aminophenols and transition metal complex salts are preferably used. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / liter.

In the present invention, as a silver sludge inhibitor,
62-4702, JP-A-3-51844, 4-26838, 4-36294
The compounds described in Nos. 2 and 1-319031 and the like can be mentioned.

The developing waste liquid can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or semiconductor such as stainless steel wool) is put in the developing waste liquid, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in the electrolyte solution, and the anion exchange membrane is used. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention while energizing. At that time, various additives added to the developer, for example, preservatives, alkali agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developer, are additionally added. You can do it. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added. When the waste developer is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

If necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) may be added to the developer. Dissolution aids (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (for example, US Pat. No. 2,304,025)
Nos. 5,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg glutaraldehyde or its bisulfite adduct), an antifoaming agent and the like can be added. The pH of the developer is preferably adjusted to 8.5-10.5.

As a special form of development processing, an activator processing solution may be used in which a developing agent is contained in a light-sensitive material, for example, an emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution for development. Such a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8 to 5.8.
Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), and pH.
A compound such as a modifier (for example, sulfuric acid), a chelating agent having the ability to soften water, or the like can be included.

The developer may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a semi-kneaded viscous liquid having high viscosity. Further, it may be diluted before use, or may be used as it is.

In the development processing, the development temperature is 20 to 30 ° C.
It can be set to the normal temperature range of 30-40 ° C.
It can also be set within the range of high temperature treatment.

The silver halide photographic light-sensitive material of the present invention is preferably processed using an automatic processor. At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The developing replenishment amount is 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. It is preferably 75 to 200 ml per 1 m ² .

In order to shorten the developing time, the total processing time from when the leading edge of the film is inserted into the automatic developing machine until it comes out of the drying zone (Dry to
Dry) is preferably 10 to 60 seconds. The total processing time mentioned here includes the total process time required for processing the black and white photosensitive material, and specifically, for example, development,
This is the time that includes all the steps of fixing, bleaching, washing, stabilizing, drying, etc., that is, Dry to Dry time. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dr
y) is 15 to 50 seconds.

In the automatic processor, a heat transfer material having a temperature of 90 ° C. or higher (for example, a heat roller at 90 ° C. to 130 ° C.) or 150
Radiant objects above ℃ (for example, tungsten, carbon, nichrome, mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc. to generate heat and radiate heat directly, or heat energy from resistance heating element to copper, stainless steel, nickel, various Those that emit infrared radiation by transmitting heat to a radiator such as ceramic) and those that have a drying zone are included.

[0174]

EXAMPLES The effects of the present invention will be specifically illustrated by the following examples.

Example 1 (Preparation of silver halide emulsion) Silver chloride content 70 mol%,
An aqueous silver nitrate solution and a mixed aqueous solution of NaCl and KBr were mixed by a controlled double jet method so that the silver bromide content was 30 mol% to grow silver halide grains. At this time, mixing was carried out under conditions of 36 ° C., pAg of 7.8 and pH of 3.0, and 2 × 10 ⁻⁷ mol of Na ₃ RhCl ₆ was added per 1 mol of silver during grain formation. After the completion of mixing, 80 mg of the following S-1 was added per mol of silver. After that, desalting was carried out with modified gelatin treated with phenylisocyanate, and the following compound [A],
A bactericide comprising a mixture of [B] and [C] and ossein gelatin were added and redispersed.

The obtained emulsion had an average grain size of 0.2 μm and a coefficient of variation.
The emulsion consisted of 10% cubic grains. To the emulsion thus obtained, 60 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver, and silver 1
Add 5 mg of chloroauric acid and 0.5 mg of sulfur flower per mole to give a pH of 5.
8. Chemical ripening was performed at 60 ° C for 80 minutes under the condition of pAg 6.5.

After aging, 4-hydroxy-6-methyl-1,3,3
900 mg of a, 7-tetrazaindene was added per mol of silver, KI of 300 mg and S-2 of 350 mg were added.

(Preparation of silver halide emulsion) Silver halide grains were prepared by mixing by the controlled double jet method in the same manner as the emulsion so that the composition had a silver chloride content of 70 mol% and a silver bromide content of 30 mol%. Has grown up. At this time, the mixing is 40
℃, pAg7.5, pH3.0 conditions, during the particle formation Na ₃ R
7 × 10 ⁻⁷ mol of hCl ₆ was added per mol of silver. After the mixing was completed, desalting was carried out in the same manner as the emulsion, and a bactericide and ossein gelatin were similarly added and redispersed. The resulting emulsion has an average grain size
The emulsion consisted of cubic grains having a coefficient of variation of 10% and 0.3 μm.

To the emulsion thus obtained, 60 mg of 1-phenyl-5-mercaptotetrazole was added per mol of silver,
Further, add 5 mg of chloroauric acid, 0.2 mg of sulfur flower and 0.3 mg of triphenylphosphine selenide per 1 mol of silver, and add pH.
Chemical aging was performed at 60 ° C for 30 minutes under the conditions of 5.8 and pAg6.5. After the ripening, 900 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver, and 350 mg of S-2 was added.

[0180]

Embedded image

(Preparation of Photosensitive Material) Undercoating layer having a thickness of 0.1 μm (see Example 1 of JP-A-59-19941) is applied on both sides.
The following prescriptions (1) to (5) were simultaneously coated on one undercoat layer of one of 100 μm polyethylene terephthalate film in the order close to the undercoat layer. Also, on the other undercoat layer on the opposite side, a backing layer with a gelatin amount of 3.1 is prepared according to the following prescription (6).
by coating so as to g / m ^2, the amount of gelatin protective layer having the following formulation on (7) to obtain a sample provided by coating so as to 1 g / m ² more.

Formulation (1) Emulsion lower layer gelatin 0.6 g / m ² saponin 100 mg / m ² solid disperse dye Table 2 Amount 1-Phenyl-5-mercaptotetrazole 2 mg / m ² Formulation (2) Silver halide emulsion layer Gelatin 1.7 g / m ² Silver halide emulsion Silver amount 3.3 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² Hardening agent: Compound of Table 1 3 × 10 ^-5 mol / m ² Nucleation accelerator: Compound of Table 1 1 × 10 ⁻⁴ mol / m ² polymer latex 1 0.7 g / m ² colloidal silica 0.5 g / m ² compound K 45 mg / m ² water-soluble polymer V-1 20 mg / m ² saponin 0.1 g / m ² Sodium-isoamyl-N-decyl-sulfosuccinate 8 mg / m ² formulation (3) Intermediate layer Gelatin 0.3 g / m ² Sodium dodecylbenzenesulfonate 50 mg / m ² Polymer latex 2 0.3 g / m ² formulation (4) DIR Layer Silver halide emulsion Table 2 Amount listed Gelatin 0.3 g / m ² Dodecylbenzenesul Sodium phonate 50 mg / m ² DIR compound Table 2 prescribed amount Formulation (5) Emulsion protective layer Gelatin 0.2 g / m ² Polymer latex 2 0.1 g / m ² Matting agent: Silica 20 mg / m ² sodium with average particle diameter 3.5 μm- Di (-2-ethylhexyl) sulfosuccinate 10 mg / m ² F-based surfactant Table 2 Amount promoter Hydroquinone 50 mg / m ² 1-Phenyl-4-hydroxymethyl-4′-methyl-3-pyrazolidone 5 mg / m ² formalin 30mg / m ²

[0183]

Embedded image

Formulation (6) backing layer

[0185]

[Chemical 38]

3.1 g of gelatin
/ M ² Sodium dodecylbenzene sulfonate 50 mg / m ² Colloidal silica 0.5 g / m ² Formulation (7) Backing protective layer Gelatin 1 g / m ² Matting agent: Polymethylmethacrylate 50 mg / m ² Sodium-di with average particle size 4.0 μm (-2-Ethylhexyl) sulfosuccinate 10 mg / m ² glyoxal 25 mg / m ² 2-hydroxy-4,6-dichloro-1,3,5-triazine 35 mg / m ^{2 The} details of the prepared film are shown below.

[0187]

[Table 2]

[0188]

[Chemical Formula 39]

(Packaging process) The film thus obtained is 508 mm wide and 61 m long and is 508 m wide composed of paper.
The emulsion was wound around a core of m, inner diameter of 75 mm, and thickness of 2 mm in a roll shape, and packaged by the following methods A to D.

<Packaging Form> A. Roll black poly wrapping The above roll contains carbon black with a thickness of 60 μm, width 800 mm
A polyethylene film having a length of 1 m was wound and the portions protruding from both ends were folded inside the core.

B. The method described in Japanese Patent Application No. 6-134368. The flange member (7 in FIG. 2) is formed by vacuum forming a light-shielding PS sheet, and the thickness of the flange portion (7b in FIG. 2) is reduced.
0.5 mm, the outer diameter of the flange portion 7b projects 6 mm from the outer peripheral surface of the photosensitive material 2, and the first thermoplastic resin film member 4 of the light-shielding leader member (3 in FIG. 1) has a width of 530 mm and a thickness of 60 mm.
A second thermoplastic resin film member (5 in FIG. 1) which is a light-shielding polyethylene film having a μm and a tensile elastic modulus of 2800 kg / cm ² and having a width substantially equal to the width of the photosensitive material (2 in FIG. 1).
Is a polyester film with a width of 508 mm, a thickness of 25 μm, and a tensile elastic modulus of 3500 kg / cm ² ,
A tension of 0.7 kg or more was applied and the outer circumference of the light-sensitive material was rotated three times.

C. Utility model gazette No. 4-85438 Method described in Examples D. Japanese Patent Application Laid-Open No. 2-72347 Example of packaging form described in FIGS. 5 and 6 The thus packaged product was packed in a cardboard outer box. At this time, the packaged film was fixed with a polyethylene holder shown in FIGS. 9, 10 and 11 so as not to move in the box.

(Temporal Preservation Test of Roll Film) A photosensitive material was subjected to a forced deterioration test under the following conditions.

Storage for 3 days under the conditions of 55 ° C and RH 20% (high temperature and low humidity condition) Storage for 3 days under the conditions of 30 ° C and RH 80% (low temperature and high humidity condition) Samples were taken from the outer periphery and the vicinity of the center of the portion that entered 30 mm inside, and the following evaluations were performed.

(Sensitivity and gamma) The obtained sample was brought into close contact with a step wedge, exposed to 3200 ° K tungsten light for 3 seconds, and treated with a developing solution and a fixing solution having the following composition, and an optical densitometer PDA-65 (Konica Sensitivity was determined by using (manufactured by Co., Ltd.).
The sensitivity is the reciprocal of the exposure amount that gives a fog density + 3.0 transmission density, and was calculated as a relative value when the sensitivity of the fresh sample of Sample No. 1 was 100. Gamma has a transmission density of 1.0 to 3.0.
It was calculated from the slope of the characteristic curve in.

(Fog) The density of the unexposed area of the developed sample was measured with an optical densitometer PDA-65 including the base density. (Black spot) The unexposed area of the developed sample was magnified 40 times to 2 mm. It is expressed by the number of black spots seen in the range of 2 mm.

(Eye enlargement) <Manuscript preparation> Scanner SG-747 (Dainippon Screen)
Co., Ltd. and New RST System Scanner Film RSP
-3 (manufactured by Konica Corporation) was used to create a transparent image of a person consisting of halftone dots and a step wedge in which halftone% was changed stepwise. The number of screen lines at this time was 175 lines / inch.

<Photographing> The above document was set on a Fine Zoom C-880F (manufactured by Dainippon Screen Co., Ltd.) so that the stretching magnification was 120% and exposed. At this time, the exposure was performed so that 95% of the step wedge of the original became 5%. The exposed sample was similarly developed.

<Evaluation method> Gradation reproducibility of the shadow portion of the sample obtained by adjusting the exposure amount and including the halftone dot% on the small dot side (highlight portion) (hardness of dot collapse) The evaluation was carried out in 5 grades in order from the best one. 5 is good and 1 is inferior. The practically usable level was set to 3.

(Developer formulation) Sodium sulfite 50 g 1-phenyl-4-methyl-4′-hydroxymethyl-3-pyrazolidone 0.85 mg Diethylenetriamine-5-acetic acid 1.5 g 1-phenyl-5-mercaptotetrazole 30
mg boric acid
8 g Potassium bromide 4 g Potassium carbonate 55 g 5-Methylbenztriazole 200 mg Hydroquinone 20 g Potassium hydroxide pH 10.4 The amount was adjusted to 1 liter by adding water at the time of use.

(Fixing solution formulation) Ammonium thiosulfate (59.5% w / v aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% w / v aqueous solution) 82 g Citric acid (50% w / v aqueous solution) Aqueous solution) 15.7 g Gluconic acid (50% w / w aqueous solution) 8.55 g Aluminum sulfate (48% aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid Amount to bring pH to 4.6 when used.

The obtained results are shown in Tables 3 and 4 below.

[0203]

[Table 3]

[0204]

[Table 4]

As is clear from the table, the samples of the present invention have stable photographic performance (sensitivity, gamma) even under a severe forced deterioration test, and the generation of black spots does not increase.
The stretchability was also excellent.

Example 2 (Preparation of silver halide emulsion) Samples shown in Table 5 were prepared in the same manner as in Example 1 except that the sensitizing dye was changed to S-3, and the following evaluations were carried out. . Evaluation method (Stability test of roll film) A forced deterioration test was conducted by the same method as in Example 1, and after the forced deterioration, a sample near the center of the outermost circumference and 30 mm inside which are in contact with the packaging material. The following evaluation was performed using.

(Sensitivity and gamma) The obtained sample was adhered to a step wedge and passed through a 633 nm interference filter to
After Xe flash exposure radiation of 0 ^-5 seconds, it was determined sensitivity using an optical densitometer PDA-65 and developed fixing (produced by Konica Corporation). The sensitivity is the reciprocal of the exposure amount that gives a fog density + a transmission density of 3.0, and is shown as a relative value when the fresh sensitivity of Sample No. 51 is 100. Gamma has a transmission density of 1.0 to 3.0.
It was calculated from the slope of the characteristic curve in.

The (fogging) and (black spots) were the same as in Example 1.

[Linearity, real machine test] DOLEV800
(Manufactured by Cytex) 600 W / inch (140 dpm) step wedge with stepwise changed mesh% was output by changing laser intensity. At this time, when the setting of 2% was performed, the reproducibility was represented by the actual measurement value of 50% at the laser intensity reproduced on the halftone dot of 2%. The closer this value is to 50%, the more preferable it is.

The obtained results are shown in Tables 6 and 7 below.

[0211]

[Table 5]

[0212]

[Table 6]

[0213]

[Table 7]

As is apparent from the table, according to the present invention, the samples of the present invention have stable photographic performance (sensitivity, gamma) even in a severe forced deterioration test and increase the generation of black spots. In addition, the linearity and reproducibility of halftone dots in the actual machine test were excellent.

[0215]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material having improved storage stability over time, high contrast and high-quality image reproducibility and a packaging method thereof can be obtained. .

[Brief description of drawings]

FIG. 1 is a perspective view showing a state where a light-shielding leader member is connected to an end portion of a photosensitive material of a roll portion.

FIG. 2 is a perspective view showing a flange member.

FIG. 3 is a perspective view of a photosensitive material winding body in which a flange member is attached to the roll portion of FIG.

FIG. 4 is a perspective view showing a state where a light shielding leader member is wound around a photosensitive material winding body.

FIG. 5 is a plan view showing a state where a light shielding leader member is wound around a photosensitive material winding body.

FIG. 6 is a perspective view of a roll-shaped photosensitive material packaging body of the present invention.

FIG. 7 is a side view showing a state where the rolled photosensitive material packaging body of the present invention is placed on a flat surface.

FIG. 8 is a perspective view showing a situation in which the roll-shaped photosensitive material package of the present invention is housed in a box.

FIG. 9 is an external view of a holder member.

FIG. 10 is a partial sectional side view of a holder member.

FIG. 11 is an inner view of the holder member.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cylindrical core member 2 Photosensitive material 3 Light-shielding leader member 4 1st thermoplastic resin film member 5 2nd thermoplastic resin film member 6 Adhesive sheet 7 Flange member 7a Cylindrical boss portion 7b Flange portion 8 Pressing roller 9 Clamping pressure Tension roller 10 Roll-shaped photosensitive material packaging body 11 Air cap material 12 Holder member 13 Box

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 3/00 560 G03C 3/00 560N 585 585B

Claims (6)

[Claims] 1. A method for packaging a silver halide photographic light-sensitive material, which comprises winding a silver halide photographic light-sensitive material containing a tetrazolium salt, a pyridinium salt or a hydrazine derivative around a cylindrical core member in a roll. A method for packaging a silver halide photographic light-sensitive material, characterized in that both ends of the light-sensitive material are covered with light-shielding flanges that are in close contact with each other, and the outer circumference of the light-sensitive material is covered with a light-shielding leader. 2. A silver halide photographic light-sensitive material containing at least one of each of a hydrazine derivative and a nucleation accelerator, which is packaged by the packaging method according to claim 1. Packaging method for photographic light-sensitive material. 3. A silver halide containing a tetrazolium salt, a pyridinium salt or a hydrazine derivative, and a solid dispersion of a dye which is substantially water-insoluble at a pH of 6 or less and substantially water-soluble at a pH of 8 or more. A method for packaging a silver halide photographic light-sensitive material, characterized in that the photographic light-sensitive material is packaged by the packaging method according to claim 1. 4. A silver halide photographic light-sensitive material containing a tetrazolium salt, a pyridinium salt or a hydrazine derivative and containing a compound which is oxidized by an oxidation product of a developing agent to release a development inhibitor or is converted into a development inhibitor. A method for packaging a silver halide photographic light-sensitive material, characterized in that the material is packaged by the packaging method according to claim 1. 5. A light-shielding flange made of a thermoplastic resin having a light-shielding bending strength of 250 kg / cm ² or more at both ends of a cylindrical core member made of a light-shielding material around which a silver halide photographic light-sensitive material is wound. And, the leader that covers the outer periphery has a length of 1.5 times or more the length of the outer periphery of the roll,
One part is wider than the width of the rolled photosensitive material and the thickness is
The silver halide photographic light-sensitive material according to any one of claims 1 to 4, which is made of a thermoplastic resin having a tensile elastic modulus of 2000 kg or more and having a leader of the light-sensitive material. Packaging method. 6. The silver halide photographic light-sensitive material according to any one of claims 1 to 4, which is packaged by the method according to claim 5.