JP2005148492A - Silver halide photographic sensitive material and its package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in suitability to passing through an automatic film transport machine and less liable to cause pressure fog (black spots) due to dust generated during packaging of the sensitive material. <P>SOLUTION: In the silver halide photographic sensitive material, (i) silver halide grains contained in an emulsion layer have a halogen composition containing on average ≥40 mol% of silver bromide, (ii) a total amount of gelatin per unit area on a side with the emulsion layer is 1.0-5.0 g/m<SP>2</SP>and smaller than that on a side with a back layer, and (iii) a flatness is -10.0 to +2.0 mm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide photographic light-sensitive material that has excellent passability in an automatic film feeder and is less susceptible to pressure fog (black spots) due to dust generated during packaging of the light-sensitive material. The present invention also relates to a package in which the silver halide photographic light-sensitive material is packaged.

Silver halide light-sensitive materials used for industrial applications have super high contrast photographic characteristics that can clearly distinguish between image areas and non-image areas in order to improve the reproducibility of characters, line drawings, and point images. Has been demanded. Such ultra-high photographic characteristics are likely to cause pressure fog (black spots) due to dust in the packaging material of the photosensitive material.
Conventionally, a sheet-shaped photosensitive material is generally packaged by sandwiching or wrapping the sheet-shaped photosensitive material between paper or plastic called a protective plate, and then placing the sheet-shaped photosensitive material in a light-proof moisture-proof bag and placing it in a mating form box. It is.
The photosensitive material used for industrial use is required to have a small dimensional change of the film, so that the thickness of the support is thick, and the film size is large, so that the weight is considerably heavy. For this reason, when the curl of the sheet-like photosensitive material is large, the four sides of the film are rubbed during product processing, packaging, and conveyance after packaging, and fine film scraps are easily generated. Further, if the product moves in the box or bag during transportation, scratches and pressure fog are generated, and there is a problem that the line is missing when a thin line is exposed.
In addition, when the sheet-like photosensitive material has a large curl, there has been a problem that, during exposure / development with a film plotter, the sheet is caught in the plotter device during conveyance, causing a conveyance failure.

  In view of the above problems, the problem of the present invention is that the silver halide is excellent in passage through an automatic film transporter such as a film plotter and is less prone to pressure fog (black spots) due to dust generated during packaging of photosensitive materials. The object is to provide a photographic material.

The above problems have been solved by the following means of the present invention.
[1] A silver halide photographic material having at least one silver halide emulsion layer containing silver halide grains on one side of a polyester film support and a back layer on the other side. The flatness of the silver photographic light-sensitive material is in the range of -10.0 to +2.0 mm, the silver halide grains contained in the emulsion layer have a halogen composition containing an average of 40 mol% or more of silver bromide, and The total gelatin amount per unit area on the side having the silver halide emulsion layer is 1.0 to 5.0 g / m ² , and the total gelatin amount per unit area on the side having the back layer is silver halide emulsion. A silver halide photographic light-sensitive material characterized by being larger than the total amount of gelatin per unit area on the side having the layer.
[2] The silver halide photographic light-sensitive material according to [1], wherein the flatness is in a range of −5.0 to 0 mm.
[3] The silver halide photographic light-sensitive material according to [1] or [2], wherein the polyester film support has a thickness of 160 μm to 200 μm.
[4] Any one of [1] to [3], wherein the silver halide grains contained in the silver halide emulsion layer have a halogen composition containing 45 mol% to 75 mol% of silver bromide on average. The silver halide photographic light-sensitive material described in 1.
[5] The silver halide according to any one of [1] to [4], wherein a silver halide emulsion layer is coated on the outer surface of the polyester film support wound in a roll shape. Photosensitive material.
[6] The silver halide photographic light-sensitive material as described in any one of [1] to [5], which is in a sheet form.
[7] The silver halide photographic light-sensitive material described in [6] is stored in a storage mating box in which the front, back, and cross section of the paperboard constituting the inner box and the lid are all covered with plastic. A package of silver halide photographic light-sensitive material characterized by the above.

  The silver halide photographic light-sensitive material of the present invention has characteristics that it is excellent in passage through a film plotter and that pressure fog (black spots) due to dust generated at the time of packaging hardly occurs.

  The silver halide photographic light-sensitive material of the present invention will be specifically described below. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

The silver halide photographic light-sensitive material of the present invention has a flatness in the range of -10.0 to +2.0 mm. In this specification, “flatness” means that a silver halide photographic light-sensitive material is cut into 30 cm × 25 cm, and the emulsion surface is horizontal with 25 ° C. and a relative humidity of 55% (after conditioning for 24 hours). It is the average value (mm) measured on the surface and measured from the bottom surface of the four corners. When the curl of the film is in the reverse direction, the measurement is performed in the same manner with the emulsion surface facing downward, and the minus sign is given. The smaller the absolute value of flatness, the better the flatness of the film. The flatness of the silver halide photographic light-sensitive material of the present invention is preferably in the range of -7.5 to +1.0 mm, preferably in the range of -5.0 to 0 mm, and -3.0 to Even more preferably within the range of 0 mm. If the flatness is within the range of the present invention, the silver halide photographic light-sensitive material can be passed through the automatic transport machine, and transport troubles are unlikely to occur.
The method for adjusting the flatness of the silver halide photographic light-sensitive material within the range of -10.0 to +2.0 mm is not particularly limited. As a preferred adjustment method, a method of adjusting the total gelatin amount per unit area on the side having the silver halide emulsion layer of the silver halide photographic material and the total gelatin amount per unit area on the side having the back layer, The method of using the curl of the support body wound around can be mentioned.

The silver halide photographic light-sensitive material of the present invention contains gelatin on both the side having a silver halide emulsion layer and the side having a back layer. The total amount of gelatin per unit area on the side having the silver halide emulsion layer is 1.0 to 5.0 g / m ² , preferably 2.0 to 4.0 g / m ² , more preferably 2. 5 to 3.5 g / m ² . On the side having the silver halide emulsion layer, an undercoat layer, a protective layer and the like may be provided in addition to the silver halide emulsion layer. When a plurality of layers are provided on the side having the silver halide emulsion layer, gelatin may be contained in all of the layers, or gelatin may be contained in only a part of the layers. In addition to the back layer, a conductive layer or the like may be provided on the side having the back layer. Even when a plurality of layers are provided on the side having the back layer, gelatin may be included in all of the layers, or gelatin may be included in only a part of the layers.
In the silver halide photographic light-sensitive material of the present invention, the total gelatin amount per unit area on the side having the back layer is larger than the total gelatin amount per unit area on the side having the silver halide emulsion layer. The difference in total gelatin amount is preferably 0.1 to 3.0 g / m ² , more preferably 0.3 to 2.0 g / m ² , and particularly preferably 0.6 to 1.5 g / m 2. ² .

  The silver halide photographic light-sensitive material of the present invention is provided with a silver halide emulsion layer containing silver halide grains. The silver halide grains contained in the silver halide emulsion layer contain an average of 40 mol% or more of silver bromide. In particular, it is preferable to use one having a halogen composition containing 45 mol% to 75 mol% of silver bromide. Specifically, it is preferable to use silver chlorobromide or silver iodochlorobromide containing 40 mol% or more of silver bromide. Furthermore, it is preferable to use silver chlorobromide or silver iodochlorobromide containing 45 to 75 mol% of silver bromide. The shape of the silver halide grains may be any of a cube, a tetrahedron, an octahedron, an indeterminate shape, and a plate shape, but a shape having an aspect ratio (equivalent circle diameter / thickness) of 2 or less is preferred, and most preferably a cube. It is. The average grain size of silver halide is preferably 0.1 μm to 0.3 μm, more preferably 0.15 to 0.22 μm, and further preferably 0.17 to 0.2 μm. Further, the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is preferably 15% or less, more preferably 10% or less and a narrow particle size distribution. The silver halide grains may be composed of a single phase having a uniform inner layer and surface layer, or may be composed of phases different from each other. Moreover, you may have the localized layer from which a halogen composition differs in the inside or the surface of a particle | grain.

The photographic emulsions used in the present invention are P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967), GF Dufin, Photographic Emulsion Chemistry (The Forcal Press, 1966), VL Zelikman et al, Making and It can be prepared using a method described in Coating Photographic Emulsion (published by The Forcal Press, 1964).
That is, either an acidic method or a neutral method may be used. In addition, as a method for reversing the soluble silver salt and the soluble halogen salt, any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. A method (so-called back mixing method) in which grains are formed in the presence of excess silver ions can also be used.

As one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase in which silver halide is generated, that is, a so-called controlled double jet method can be used. In particular, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether or tetrasubstituted thiourea. More preferred as a silver halide solvent is a tetrasubstituted thiourea compound, which is described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

  In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal type and a narrow grain size distribution. The silver halide used in the present invention It is a useful tool for making emulsions. Further, in order to make the grain size uniform, as described in British Patent No. 1,535,016, Japanese Patent Publication No. 48-36890, No. 52-16364, silver nitrate or halogenated A method of changing the alkali addition rate according to the particle growth rate, or a method of changing the concentration of the aqueous solution as described in British Patent No. 4,242,445 and JP-A-55-158124 It is preferable to grow quickly in a range not exceeding the critical saturation.

The silver halide emulsion used in the present invention preferably contains a metal complex containing at least one cyanide ligand in an amount of 1 × 10 ⁻⁶ mol or more per mol of silver in the silver halide. The metal complex is preferably contained in the silver halide in an amount of 5 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver. Furthermore, it is particularly preferable that the silver halide contains 5 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol per 1 mol of silver.
When a metal complex containing one or more cyanide ligands is used, it is generally added in the form of a water-soluble complex salt. Particularly preferred is a hexacoordination complex represented by the following formula.
[M (CN) _n1 L _6-n1 ] ^n-
Here, M represents a metal belonging to Group V to Group VIII, and Ru, Re, Os, and Fe are particularly preferable. L represents a ligand other than a cyanide compound, and a halide ligand, a nitrosyl ligand, a thionitrosyl ligand and the like are preferable. n1 represents 1 to 6, and n represents 0, 1, 2, 3 or 4. n1 is preferably 6. In this case, the counter ion has no significance and ammonium or alkali metal ions are used.
Specific examples of the complex used in the present invention are shown below, but the complex that can be used in the present invention is not limited to these.

[Re (NO) (CN) ₅ ] ^2- [Re (O) ₂ (CN) ₄ ] ^3-
[Os (NO) (CN) ₅ ] ^2- [Os (CN) ₆ ] ^4-
[Os (O) ₂ (CN) ₄ ] ^4- [Os (CN) ₆ ] ^4-
[Ru (CN) ₆ ] ^4- [Fe (CN) ₆ ] ^4-

  The metal complex used in the present invention may be present anywhere in the silver halide grains, but is preferably present inside the silver halide crystal. Most preferably, the silver halide crystals are present in the interior containing 99 mol% or less, preferably 95 mol% or less, and more preferably 0 to 95 mol% of silver in each silver halide crystal. For this purpose, it is preferable to form photosensitive silver halide grains in multiple layers.

  In order to achieve high contrast and low fog in addition to a metal complex containing one or more cyanide ligands, the silver halide emulsion used in the present invention is composed of rhodium compounds, iridium compounds, rhenium compounds, ruthenium compounds. It is preferable to contain an osmium compound or the like.

  As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a halogen, amines, oxalato, aco, etc. as a ligand, such as hexachlororhodium (III) complex salt, pentachloroacorodium complex salt, tetrachlorodiaco salt Examples thereof include rhodium complex salts, hexabromorhodium (III) complex salts, hexaamine rhodium (III) complex salts, and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving in water or an appropriate solvent, and are generally used in order to stabilize the rhodium compound solution, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, hydrofluoric acid). Or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add another silver halide grain previously doped with rhodium and dissolve it at the time of silver halide preparation.

Rhenium, ruthenium, and osmium used in the present invention are water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855, and the like. Added in the form. Particularly preferred is a hexacoordination complex represented by the following formula.
[ML ₆ ] ^n-
Here, M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4. In this case, the counter ion has no significance and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, nitrosyl ligands, thionitrosyl ligands and the like.
Specific examples of the complex used in the present invention are shown below, but the complex that can be used in the present invention is not limited to these.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3-
[ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2-
[RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^1-
[RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2-
[Ru (CO) ₃ Cl ₃ ] ^2- [Ru (CO) Cl ₅ ] ^2-
[Ru (CO) Br ₅ ] ^2- [OsCl ₆ ] ^3-
[OsCl ₅ (NO)] ^2- [Os (NS) Br ₅ ] ^2-

The amount of these compounds added is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, particularly preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁶ mol, per mol of silver halide.
Examples of the iridium compound used in the present invention include hexachloroiridium, hexabromoiridium, hexaammineiridium, and pentachloronitrosyliridium.

  The silver halide emulsion used in the present invention is preferably chemically sensitized. Known methods such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, and a noble metal sensitizing method can be used, and they can be used alone or in combination. When used in combination, for example, sulfur sensitizing method and gold sensitizing method, sulfur sensitizing method and selenium sensitizing method and gold sensitizing method, sulfur sensitizing method and tellurium sensitizing method and gold sensitizing method, etc. Is preferred.

The sulfur sensitization used in the present invention is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. Known compounds can be used as the sulfur sensitizer, for example, various sulfur compounds such as thiosulfate, thioureas, thiazoles, rhodanines, etc. in addition to sulfur compounds contained in gelatin. be able to. Preferred sulfur compounds are thiosulfate and thiourea compounds. As the thiourea compound, a specific tetra-substituted thiourea compound described in US Pat. No. 4,810,626 is particularly preferable. The amount of sulfur sensitizer added varies depending on various conditions such as pH, temperature, and size of silver halide grains during chemical ripening, but is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. More preferably, it is 10 ^<-5 > ^-10 < ^-3 > mol.

  A known selenium compound can be used as the selenium sensitizer used in the present invention. That is, it is usually carried out by adding unstable and / or non-labile selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the unstable selenium compound, compounds described in JP-B Nos. 44-15748, 43-13489, JP-A-4-109240, and JP-A-4-324855 can be used. In particular, it is preferable to use compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound that forms silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide grain. The silver telluride formation rate in the silver halide emulsion can be tested by the method described in JP-A-5-313284.
Specifically, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640, 4-271341, 4-3333043, 5-303157, Journal of Chemical Society, Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (1979), ibid 645 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2191 (1 80), S. The compounds described in S. Patai, The Chemistry of Organic Serenium and Tellunium Compounds, Vol 1 (1986), Vol 2 (1987) are used. be able to. Particularly preferred are compounds represented by the general formulas (II), (III) and (IV) in JP-A-4-324855.

The amount of selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, etc., but is generally 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide, preferably 10 ^{−. About 7} to 10 ⁻³ mol is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and the like, and about 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. Can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of silver halide grain formation or physical ripening.

  In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion used in the present invention by the method described in EP 293,917A. In the silver halide photographic light-sensitive material of the present invention, 1 to 3 types of silver halide emulsions are preferably used. When two or more kinds are used in combination, those having different average particle sizes, those having different halogen compositions, those containing different amounts and types of metal complexes, those having different crystal habits, those having different chemical sensitization conditions, sensitivity It is preferable to use a combination of different ones. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.

  At least one of the silver halide emulsion layers constituting the silver halide photographic light-sensitive material of the present invention has the following general formulas (I), (II), (III), (IV), (V), (VIa) and It is preferable to contain at least one spectral sensitizing dye represented by the general formula (VIb).

（式中、Ｙ¹¹、Ｙ¹²、Ｙ¹³およびＹ¹⁴は、各々独立に＝Ｎ（Ｒ¹）、酸素原子、硫黄原子、セレン原子またはテルル原子を表す。ただし、Ｙ¹³およびＹ¹⁴のいずれか一方は＝Ｎ（Ｒ¹）であり、Ｙ¹¹、Ｙ¹²およびＹ¹³あるいはＹ¹¹、Ｙ¹²およびＹ¹⁴は同時に硫黄原子であることはない。Ｒ¹¹は、水可溶化基を有する炭素数８以下の脂肪族基を表し、Ｒ¹、Ｒ¹²およびＲ¹³は、各々独立に脂肪族基、アリール基または複素環基を表す。ただし、Ｒ¹、Ｒ¹²およびＲ¹³の内の少なくとも２つは水可溶化基を有している。Ｚ¹¹は、５員または６員の含窒素複素環を形成するのに必要な非金属原子群を表す。ただし、Ｚ¹¹によって形成される５員または６員の含窒素複素環はさらに縮合環を有していてもよい。Ｗ¹は、酸素原子、硫黄原子、＝Ｎ（Ｒ¹）、または＝Ｃ（Ｅ¹¹）（Ｅ¹²）を表す。Ｅ¹¹、Ｅ¹²は、各々独立に電子吸引性の基を表す。これらは互いに結合してケト環または酸性の複素環を形成してもよい。Ｌ¹¹およびＬ¹²は、各々独立に置換あるいは無置換のメチン基を表し、ｌ¹¹は、０または１を表す。Ｍ¹は、分子の電荷を相殺するのに必要なイオンを表す。ｎ¹¹は、分子の総電荷を中和させるのに必要な数を表す。ただし、分子内塩を形成しているときは０である。）

(Wherein Y ¹¹ , Y ¹² , Y ¹³ and Y ¹⁴ each independently represent ═N (R ¹ ), an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, provided that any of Y ¹³ and Y ¹⁴ One of them is = N (R ¹ ), and Y ¹¹ , Y ¹² and Y ¹³ or Y ¹¹ , Y ¹² and Y ¹⁴ are not simultaneously sulfur atoms, and R ¹¹ is a carbon having a water-solubilizing group. R ¹ , R ¹² and R ¹³ each independently represents an aliphatic group, an aryl group or a heterocyclic group, provided that at least ^one of R ¹ , R ¹² and R ¹³ two has a water solubilizing group .Z ¹¹ represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic 5- or 6-membered. However, 5 formed by Z ¹¹ nitrogen-containing heterocyclic ring may .W ¹ further have a condensed ring membered or 6-membered, oxygen atom, sulfur atom, = N ( ^1), or = C (.E ^11, E ¹² representing the E ¹¹⁾ (E ¹²⁾ represents an electron-withdrawing group independently. They form a heterocyclic keto ring or acidic bonded to each other L ¹¹ and L ¹² each independently represent a substituted or unsubstituted methine group, and l ¹¹ represents 0 or 1. M ¹ is an ion necessary to cancel the charge of the molecule. N ¹¹ represents the number necessary to neutralize the total charge of the molecule, provided that it is 0 when forming an inner salt.)

（式中、Ｚ²¹は、５員または６員の含窒素複素環を形成するのに必要な非金属原子群を表す。ただし、Ｚ²¹によって形成される５員または６員の含窒素複素環はさらに縮合環を有していてもよい。Ｙ²¹およびＹ²²は、各々独立に＝Ｎ（Ｒ²）、酸素原子、硫黄原子、セレン原子またはテルル原子を表す。Ｗ²は、＝Ｎ（Ａｒ）、酸素原子、硫黄原子、または＝Ｃ（Ｅ²¹）（Ｅ²²）を表す。Ｅ²¹、Ｅ²²は、各々独立に電子吸引性の基、あるいは、Ｅ²¹およびＥ²²が互いに結合して酸性の複素環を形成する非金属原子群を表し、Ａｒは芳香族基または芳香族性の複素環基を表す。Ｒ²¹は、水可溶化基を有する炭素数８以下の脂肪族基を表し、Ｒ²、Ｒ²²およびＲ²³は、各々独立に脂肪族基、アリール基または複素環基を表す。ただし、Ｒ²、Ｒ²²およびＲ²³の内の少なくとも２つは水可溶化基を有している。Ｌ²¹、Ｌ²²、Ｌ²³およびＬ²⁴は、各々独立に置換あるいは無置換のメチン基を表し、ｍ²¹は、０または１を表す。Ｍ²は、分子の電荷を相殺するのに必要なイオンを表す。ｎ²¹は、分子の総電荷を中和させるのに必要な数を表す。ただし、分子内塩を形成しているときは０である。）

(In the formula, Z ²¹ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, provided that the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ²¹ is used. May further have a condensed ring, Y ²¹ and Y ²² each independently represent ═N (R ² ), an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, and W ² represents ═N ( Ar), an oxygen atom, a sulfur atom, or ═C (E ²¹ ) (E ²² ), where E ²¹ and E ²² are each independently an electron-withdrawing group, or E ²¹ and E ²² are bonded to each other. And Ar represents an aromatic group or an aromatic heterocyclic group, and R ²¹ represents an aliphatic group having 8 or less carbon atoms having a water-solubilizing group. R ² , R ²² and R ²³ each independently represents an aliphatic group, an aryl group or a heterocyclic group, provided that R ² , R ^{2 At} least two of ² and R ²³ have a water-solubilizing group, L ²¹ , L ²² , L ²³ and L ²⁴ each independently represent a substituted or unsubstituted methine group, and m ²¹ represents , 0 or 1. M ² represents an ion necessary to cancel the charge of the molecule, and n ²¹ represents a number necessary to neutralize the total charge of the molecule, provided that an inner salt 0 when forming.)

（式中、Ｒ³¹、Ｒ³²は、各々独立にアルキル基を表す。ただし、少なくとも一方のアルキル基は水溶性基を有する。Ｖ³¹、Ｖ³²、Ｖ³³およびＶ³⁴は、水素原子または１価の置換基を表す。ただし、該置換基（Ｖ³¹、Ｖ³²、Ｖ³³、Ｖ³⁴）の分子量の合計は５０以下である。Ｌ³¹、Ｌ³²、Ｌ³³およびＬ³⁴は、各々独立に置換あるいは無置換のメチン基を表す。Ｍ³は、分子の電荷を相殺するのに必要なイオンを表す。ｎ³¹は、分子の総電荷を中和させるのに必要な数を表す。ただし、分子内塩を形成しているときは０である。）

(In the formula, R ³¹ and R ³² each independently represents an alkyl group, provided that at least one alkyl group has a water-soluble group. V ³¹ , V ³² , V ³³ and V ³⁴ are each a hydrogen atom or 1 The total molecular weight of the substituents (V ³¹ , V ³² , V ³³ , V ³⁴ ) is not more than 50. L ³¹ , L ³² , L ³³ and L ³⁴ are each independently Represents a substituted or unsubstituted methine group, M ³ represents an ion necessary to cancel the charge of the molecule, and n ³¹ represents a number necessary to neutralize the total charge of the molecule. , 0 when forming an inner salt.)

（式中、Ｒ⁴¹は、アルキル基、アルケニル基またはアリール基であり、Ｒ⁴²およびＲ⁴³は、各々独立に水素、アルキル基、アルケニル基またはアリール基を表し、Ｒ⁴⁴、Ｒ⁴⁵およびＲ⁴⁶は、各々独立にアルキル基、アルケニル基、アリール基または水素原子を表す。Ｌ⁴¹、Ｌ⁴²は、各々独立に置換あるいは無置換のメチン基を表し、ｐは、０また１を表す。Ｚ⁴¹は、５員または６員の複素環を完成するのに必要な原子団を表す。ただし、Ｚ⁴¹によって形成される５員または６員の複素環式基はさらに縮合環を有していてもよい。Ｍ⁴は、分子の電荷を相殺するのに必要なイオンを表す。ｎ⁴¹は、分子の総電荷を中和させるのに必要な数を表す。ただし、分子内塩を形成しているときは０である。一般式（IV）で表される分光増感色素は少なくとも３個の水可溶化基を有する。）

(In the formula, R ⁴¹ represents an alkyl group, an alkenyl group or an aryl group; R ⁴² and R ⁴³ each independently represents hydrogen, an alkyl group, an alkenyl group or an aryl group; R ⁴⁴ , R ⁴⁵ and R ⁴⁶⁾ Each independently represents an alkyl group, an alkenyl group, an aryl group or a hydrogen atom, L ⁴¹ and L ⁴² each independently represent a substituted or unsubstituted methine group, and p represents 0 or 1. Z ⁴¹ Represents an atomic group necessary for completing a 5-membered or 6-membered heterocyclic ring, provided that the 5-membered or 6-membered heterocyclic group formed by Z ⁴¹ may further have a condensed ring. M ⁴ represents an ion necessary to cancel the charge of the molecule n ⁴¹ represents a number necessary to neutralize the total charge of the molecule, provided that an inner salt is formed Sometimes it is 0. There are few spectral sensitizing dyes represented by the general formula (IV). Also has three water-solubilizing group.)

（式中、Ｚ⁵¹およびＺ⁵²は、各々独立に５員または６員の含窒素複素環を形成するのに必要な非金属原子群を表す。ただし、Ｚ⁵¹およびＺ⁵²によって形成される５員または６員の含窒素複素環はさらに縮合環を有していてもよい。Ｒ⁵およびＲ⁵²は、各々独立にアルキル基、置換アルキル基またはアリール基を表す。Ｑ⁵¹およびＱ⁵²は、協同してチアゾリジノン環またはイミダゾリジノン環を形成するのに必要な非金属原子群を表す。Ｌ⁵¹、Ｌ⁵²およびＬ⁵³は、各々独立にメチン基または置換メチン基を表す。ｎ⁵¹、ｎ⁵²は、各々独立に０または１を表す。Ｍ⁵は、分子の電荷を相殺するのに必要なイオンを表す。ｎ⁵³は、分子の総電荷を中和させるのに必要な数を表す。ただし、分子内塩を形成しているときは０である。）

(In the formula, Z ⁵¹ and Z ⁵² each independently represent a group of non-metallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, provided that 5 formed by Z ⁵¹ and Z ⁵² The membered or six-membered nitrogen-containing heterocyclic ring may further have a condensed ring, R ⁵ and R ⁵² each independently represents an alkyl group, a substituted alkyl group or an aryl group, Q ⁵¹ and Q ⁵² are L ⁵¹ , L ⁵² and L ⁵³ each independently represents a methine group or a substituted methine group, each representing a nonmetallic atom group necessary for forming a thiazolidinone ring or an imidazolidinone ring in cooperation with each other, n ⁵¹ , n ⁵² each independently represents 0 or 1. M ⁵ represents an ion necessary to cancel the charge of the molecule, and n ⁵³ represents a number necessary to neutralize the total charge of the molecule. However, it is 0 when an intramolecular salt is formed.)

（式中、Ｒ⁶¹およびＲ⁶²は、各々独立にアルキル基を表す。Ｒ⁶³は、水素原子、低級アルキル基、低級アルコキシ基、フェニル基、ベンジル基またはフェネチル基を表す。Ｖ⁶は、水素原子、低級アルキル基、アルコキシ基、ハロゲン原子または置換アルキル基を表し、ｐ⁶は、１または２を表す。Ｚ⁶¹は、５員または６員の含窒素複素環を形成するのに必要な原子群を表す。ただし、Ｚ⁶¹によって形成される５員または６員の含窒素複素環はさらに縮合環を有していてもよい。ｍ⁶¹は、０または１を表す。Ｍ⁶¹は、分子の電荷を相殺するのに必要なイオンを表す。ｎ⁶¹は、分子の総電荷を中和させるのに必要な数を表す。ただし、分子内塩を形成しているときは０である。）

(In the formula, R ⁶¹ and R ⁶² each independently represents an alkyl group. R ⁶³ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. V ⁶ represents hydrogen. Represents an atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group, and p ⁶ represents 1 or 2. Z ⁶¹ represents an atom necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. Wherein the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ⁶¹ may further have a condensed ring, m ⁶¹ represents 0 or 1. M ⁶¹ represents a molecule of Represents the ion required to cancel the charge, n ⁶¹ represents the number necessary to neutralize the total charge of the molecule (provided zero when forming an inner salt).

（式中、Ｒ⁶⁴およびＲ⁶⁵は、各々独立にアルキル基を表す。Ｒ⁶⁶およびＲ⁶⁷は、各々独立に水素原子、低級アルキル基、低級アルコキシ基、フェニル基、ベンジル基またはフェネチル基を表す。Ｒ⁶⁸、Ｒ⁶⁹は、それぞれ水素原子を表す。また、Ｒ⁶⁸とＲ⁶⁹は、互いに連結してアルキレン基を形成してもよい。Ｒ⁷⁰は、水素原子、低級アルキル基、低級アルコキシ基、フェニル基、ベンジル基または−Ｎ（Ｗ⁶¹）（Ｗ⁶²）〔Ｗ⁶¹とＷ⁶²は、各々独立にアルキル基またはアール基を表す。また、Ｗ⁶¹とＷ⁶²は、互いに連結して５員または６員の含窒素複素環を形成するものであってもよい。〕を表す。また、Ｒ⁶⁶とＲ⁷⁰またはＲ⁶⁷とＲ⁷⁰は、互いに連結してアルキレン基を形成するものであってもよい。Ｚ⁶²およびＺ⁶³は、各々独立に５員または６員の含窒素複素環を形成するのに必要な非金属原子群を表す。ただしＺ⁶²およびＺ⁶³によって形成される５員または６員の含窒素複素環はさらに縮合環を有していてもよい。Ｍ⁶²は、分子の電荷を相殺するのに必要なイオンを表す。ｎ⁶²は、分子の総電荷を中和させるのに必要な数を表す。ただし、分子内塩を形成しているときは０である。）

(In the formula, R ⁶⁴ and R ⁶⁵ each independently represents an alkyl group. R ⁶⁶ and R ⁶⁷ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or a phenethyl group. R ⁶⁸ and R ⁶⁹ each represent a hydrogen atom, and R ⁶⁸ and R ⁶⁹ may combine with each other to form an alkylene group, and R ⁷⁰ represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group. , phenyl group, benzyl group, or ^{-N (W 61) (W 62} ) [W ⁶¹ and W ⁶² each independently represent an alkyl group or Earl group. also, W ⁶¹ and W ⁶² is 5 connected to each other R ⁶⁶ and R ⁷⁰ or R ⁶⁷ and R ⁷⁰ may be bonded to each other to form an alkylene group. good .Z ⁶² and Z ⁶³ may be also each independently a 5- Represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic 6-membered. However 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ⁶² and Z ⁶³ are further have a condensed ring M ⁶² represents an ion necessary to cancel the charge of the molecule, and n ⁶² represents a number necessary to neutralize the total charge of the molecule, provided that an inner salt is formed. When it is, it is 0.)

  In the following, typical examples of the compound represented by the general formula (III) are shown, but the compounds that can be used in the present invention are not limited to these specific examples.

  The compound represented by the general formula (III) is "FM Hemer", "Heterocyclic Compounds-Cyanine Dyes and Related Compounds" (John Willy and Sons John Wiley & Sons-New York, London, 1964., DM Sturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry ( Heterocyclic Compounds--Special topics in cyclic chemistry--) "Chapter 18, Section 14, 482-515, John Wiley & Sons, New York, London, (1977). “Rods Chemistry of Carbon Compounds (Ro dd's Chemistry of Carbon Compounds), (2nd. Ed. vol. IV, part B, 1977), Chapter 15, pages 369-422; (2nd. Ed. vol. IV, part B, 1985), 15 Chapter 267-296, Elsevier Science Publishing Company Inc., New York, etc. can be used for the synthesis.

These spectral sensitizing dyes may be used alone or in combination. Spectral sensitizing dye combinations are often used for the purpose of supersensitization. In addition to the spectral sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization.
Useful spectral sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (issued December 1978), page 23, item IV, Alternatively, they are described in the aforementioned Japanese Patent Publication Nos. 49-25500, 43-4933, JP-A 59-19032, 59-192242 and the like.

  Two or more kinds of spectral sensitizing dyes may be used in combination in the silver halide photographic light-sensitive material of the present invention. In order to add spectral sensitizing dyes to the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2, 2, 3, Of solvents such as 3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide It may be added to the emulsion alone or dissolved in a mixed solvent. Further, as disclosed in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. As disclosed in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22091, etc., a dye is dissolved in an acid and the solution is added to the emulsion. As disclosed in US Pat. Nos. 3,822,135, 4,006,025, and the like. A method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to the emulsion, as disclosed in JP-A-53-102733 and 58-105141, in a hydrophilic colloid. Dye A method of adding the dispersion into the emulsion, and dissolving the dye using a compound that shifts red as disclosed in JP-A-51-74624, and adding the solution to the emulsion It is also possible to use a method of In addition, ultrasonic waves can be used for the solution.

  The time when the spectral sensitizing dye used in the present invention is added to the silver halide emulsion may be during any step of emulsion preparation that has been found to be useful so far. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58. As disclosed in JP-A-184142, JP-A-60-196749, etc., chemical ripening is performed during the silver halide grain formation step or / and before the desalting, during and / or after the desalting step. As long as it is before the start of the emulsion, as disclosed in Japanese Patent Application Laid-Open No. 58-11939, etc., immediately before chemical ripening or during the process, after chemical ripening and before coating, the emulsion is not coated. It may be added in the process at any time. Further, as disclosed in US Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound can be used alone or in combination with a compound having a different structure, for example, a particle forming step. It may be added separately during the chemical ripening process or after completion of chemical ripening, or may be added separately before or during chemical ripening or after completion of chemical ripening. You may change and add the kind of compound combination.

In the present invention, the amount of spectral sensitizing dye added varies depending on the shape, size, halogen composition, method and degree of chemical sensitization of silver halide grains, the type of antifoggant, etc., but is 4 × per 1 mol of silver halide. It can be used at 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, an addition amount of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grain is preferable. The addition amount of 5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The silver halide photographic light-sensitive material of the present invention preferably has a characteristic curve having a gamma of 4.0 or more, more preferably 5.0 to 100, still more preferably 5.0 to 30. In the present invention, “gamma” is an optical density of 0.1 and 1 in a characteristic curve shown on an orthogonal coordinate axis having the same unit length represented by an optical density (y-axis) and a common logarithmic exposure (x-axis). 5 is a gradient when a straight line is drawn at two points. That is, tan θ is expressed as θ where the angle formed by the straight line and the x axis is θ.
In the present invention, in order to obtain a characteristic curve, a silver halide is used by using a developer (manufactured by Fuji Photo Film Co., Ltd., QR-D ¹ ) and a fixing solution (manufactured by Fuji Photo Film Co., Ltd., NF-1). The photographic light-sensitive material is processed with an automatic developing machine (manufactured by Fuji Photo Film Co., Ltd., FG-680AG) under development conditions of 35 ° C. for 30 seconds.

  There are a variety of methods for obtaining a silver halide photographic light-sensitive material having a gamma of 4.0 or more. For example, by using a silver halide emulsion containing a heavy metal (for example, a metal belonging to Group VIII) capable of realizing a high contrast, halogenation is performed. The gamma of the silver photographic material can be adjusted. In particular, a silver halide emulsion containing a rhodium compound, an iridium compound, a ruthenium compound or the like is preferably used. Moreover, it is also preferable to contain at least one compound such as a hydrazine derivative, an amine compound, or a phosphonium compound as a nucleating agent on the side including the emulsion layer.

The silver halide photographic light-sensitive material of the present invention preferably contains a hydrazine compound as a nucleating agent. In particular, it is preferable to contain at least one hydrazine derivative represented by the following general formula (D).
Formula (D)

In the formula, R ²⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ¹⁰ represents a hydrogen atom or a blocking group, and G ¹⁰ represents —CO—, —COCO—, —C (═S) —. _{, -SO 2 -, - SO -} , - PO (R 30) - group (. R ³⁰ is selected from the same range as the groups defined in R ^10, may be different from R ^10), or an iminomethylene Represents a group. A ¹⁰ and A ²⁰ both represent a hydrogen atom, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (D), the aliphatic group represented by R ²⁰ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms. In the general formula (D), the aromatic group represented by R ²⁰ is a monocyclic or condensed aryl group, and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic group represented by R ²⁰ is a monocyclic or condensed ring, saturated or unsaturated, aromatic or non-aromatic heterocyclic group such as a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring. Quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, piperidine ring, triazine ring and the like. R ²⁰ is preferably an aryl group, particularly preferably a phenyl group.

The group represented by R ²⁰ may be substituted. Typical examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), alkyl group (aralkyl group, cycloalkyl group, active methine). Group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, quaternized heterocyclic group containing nitrogen atom (for example, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Group, carboxy group or salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethyleneoxy group or propyleneoxy group) A group containing a repeating unit), Oxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, N-substituted nitrogen-containing Heterocyclic group, acylamino group, sulfonamido group, ureido group, thioureido group, isothioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4 Primary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, N-acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle) O group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, N-acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid amide or phosphorus And a group containing an acid ester structure.
These substituents may be further substituted with these substituents.

The substituent which R ²⁰ may have is preferably an alkyl group having 1 to 30 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group, a sulfonamide group, or a ureido. Group, sulfamoylamino group, imide group, thioureido group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group ( (Including salts thereof), (alkyl, aryl, or heterocyclic) thio groups, sulfo groups (including salts thereof), sulfamoyl groups, halogen atoms, cyano groups, nitro groups, and the like.

In the general formula (D), R ¹⁰ represents a hydrogen atom or a blocking group. Specific examples of the blocking group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, Represents an amino group or a hydrazino group.

The alkyl group represented by R ¹⁰ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, trifluoromethyl group, difluoromethyl group, 2-carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl. Group, difluorocarboxymethyl group, 3-hydroxypropyl group, methanesulfonamidomethyl group, benzenesulfonamidomethyl group, hydroxymethyl group, methoxymethyl group, methylthiomethyl group, phenylsulfonylmethyl group, o-hydroxybenzyl group, etc. It is done. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and examples thereof include a vinyl group, 2,2-dicyanovinyl group, 2-ethoxycarbonylvinyl group, 2-trifluoro-2-methoxycarbonylvinyl group and the like. . The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed ring aryl group is preferable, and a group containing a benzene ring is particularly preferable. Examples thereof include a phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 2-carbamoylphenyl group, 4-cyanophenyl group, 2-hydroxymethylphenyl group and the like.

  The heterocyclic group is preferably a 5- to 6-membered saturated or unsaturated monocyclic or condensed heterocyclic group containing at least one nitrogen, oxygen and sulfur atom, and a quaternized nitrogen atom. A morpholino group, piperidino group (N-substituted), piperazino group, imidazolyl group, indazolyl group (4-nitroindazolyl group, etc.), pyrazolyl group, triazolyl group, benzoimidazolyl group, Examples include a tetrazolyl group, a pyridyl group, a pyridinio group (such as N-methyl-3-pyridinio group), a quinolinio group, and a quinolyl group. A morpholino group, piperidino group, pyridyl group, pyridinio group and the like are particularly preferable.

  As an alkoxy group, a C1-C8 alkoxy group is preferable, for example, a methoxy group, 2-hydroxyethoxy group, a benzyloxy group etc. are mentioned. The aryloxy group is preferably a phenoxy group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized). A nitrogen-containing heterocyclic group containing a nitrogen atom) is preferred. Examples of amino groups include 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolyl. A ruamino group, an N-benzyl-3-pyridinioamino group, and the like. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (such as 4-benzenesulfonamidophenylhydrazino group) is particularly preferable.

The group represented by R ¹⁰ may be substituted, and preferred substituents include those exemplified as the substituent for R ²⁰ .

R ¹⁰ in the general formula (D) disrupts the portion of the G ¹⁰ -R ¹⁰ from the remainder molecule, such as to rise to cyclization reaction to form a cyclic structure containing a -G ¹⁰ -R ¹⁰ parts of atoms Examples thereof include those described in, for example, JP-A No. 63-29751.

  The hydrazine derivative represented by the general formula (D) may incorporate an adsorptive group that adsorbs to silver halide. Such adsorbing groups include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercaptoheterocyclic groups, triazole groups and the like in U.S. Pat. Nos. 4,385,108 and 4,459,347. JP-A-59-195233, 59-200231, 59-201045, 59-201046, 59-201047, 59-201048, 59-201049. Japanese Patent Laid-Open Nos. 61-170733, 61-270744, 62-948, 63-234244, 63-234245, 63-234246 Is mentioned. Further, these adsorbing groups to silver halide may be made into a precursor. Examples of such a precursor include groups described in JP-A-2-285344.

R ¹⁰ or R ^{20 in} the general formula (D) may be incorporated with a ballast group or polymer commonly used in an immobile photographic additive such as a coupler. In the present invention, the ballast group is a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), alkylthio having 6 or more carbon atoms. Group or a group having these as a partial structure, more preferably a straight chain or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group) having 7 to 24 carbon atoms, An alkylamino group (or alkyleneamino group), an alkylthio group, or a group having these as a partial structure is represented. Examples of the polymer include those described in JP-A-1-100530.

R ¹⁰ or R ²⁰ in the general formula (D) may contain a plurality of hydrazino groups as a substituent, and at this time, the compound represented by the general formula (D) represents a multimer related to the hydrazino group, Specifically, for example, JP-A-64-86134, JP-A-4-16938, JP-A-5-97091, International Publication WO95 / 32452, International Publication WO95 / 32453, JP-A-9- 179229, JP-A-9-235264, JP-A-9-235265, JP-A-9-235266, JP-A-9-235267, and the like.

R ¹⁰ or R ^{20 in} the general formula (D) includes a cationic group (specifically, a group containing a quaternary ammonio group, a group containing a quaternized phosphorus atom, or quaternization). Nitrogen-containing heterocyclic groups containing nitrogen atoms, etc.), groups containing repeating units of ethyleneoxy or propyleneoxy groups, (alkyl, aryl, or heterocyclic) thio groups, or dissociable groups (in alkaline developers) It means a group or a partial structure having a proton with low acidity that can be dissociated, or a salt thereof. Specifically, for example, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonic acid group (— PO ₃ H), phosphate group (—OPO ₃ H), hydroxy group (—OH group), mercapto group (—SH), —SO ₂ NH ₂ group, N-substituted sulfonamide group (—SO ₂ NH—) Group, -CONH O ₂ - group, -CONHSO ₂ NH- group, -NHCONHSO ₂ - group, -SO ₂ NHSO ₂ - group), - CONHCO- group, active methylene group, -NH- group inherent in the nitrogen-containing heterocyclic group, or, These salts etc.) may be included. Examples of these groups include JP-A-7-234471, JP-A-5-333466, JP-A-6-19032, JP-A-6-19031, and JP-A-5-45761. U.S. Pat. No. 4,994,365, U.S. Pat. No. 4,988,604, JP-A-7-259240, JP-A-7-5610, JP-A-7-244348, German Examples include compounds described in Japanese Patent No. 4006032, the specification of JP-A-11-7093, and the like.

In general formula (D), A ¹⁰ and A ²⁰ are each a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group, or a sum of Hammett's substituent constants of −0.5 or more. A substituted phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more, or a straight chain or branched chain Or a cyclic substituted or unsubstituted aliphatic acyl group (in this case, examples of the substituent include a halogen atom, an ether group, a sulfonamido group, a carbonamido group, a hydroxy group, a carboxy group, and a sulfo group)) It is. A ¹⁰ and A ²⁰ are most preferably a hydrogen atom.

Next, hydrazine derivatives particularly preferably used in the present invention will be described.
R ²⁰ is particularly preferably a substituted phenyl group, and examples of the substituent include a sulfonamide group, an acylamino group, a ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group, and an N-acylsulfamoylamino group. A sulfonamide group and a ureido group are more preferable, and a sulfonamide group is most preferable.
The hydrazine derivative represented by the general formula (D) is a group containing a ballast group, an adsorbing group to silver halide, a quaternary ammonio group, directly or indirectly as a substituent in R ²⁰ or R ¹⁰ ; A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, a group containing an ethyleneoxy group repeating unit, a (alkyl, aryl, or heterocyclic) thio group, a dissociable group capable of dissociating in an alkaline developing solution Or at least one of hydrazino groups (groups represented by —NHNH—G ¹⁰ —R ¹⁰ ) capable of forming multimers is particularly preferred. Furthermore, as the substituent of R ^20, directly or indirectly, preferably have any one group described above, most preferably represents a phenyl group R ²⁰ is substituted benzenesulfonamide group, This is a case where any one of the aforementioned groups is directly or indirectly used as a substituent on the benzene ring of the benzenesulfonamide group.

Among the groups represented by R ¹⁰ , when G ¹⁰ is a —CO— group, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group is more preferable. A hydrogen atom, an alkyl group, and a substituted aryl group (a substituent is particularly preferably an electron-withdrawing group or an o-hydroxymethyl group), and most preferably a hydrogen atom or an alkyl group. When G ¹⁰ is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferable, and a substituted amino group, particularly an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is preferable. . When G ¹⁰ is a —SO ₂ — group, R ¹⁰ is preferably an alkyl group, an aryl group or a substituted amino group.

In the general formula (D), G ¹⁰ is preferably a —CO— group or a —COCO— group, particularly preferably a —CO— group.

  Next, specific examples of the compound represented by the general formula (D) are shown below. However, the compounds that can be used in the present invention are not limited to the following specific examples.

  As the hydrazine derivative used in the present invention, the following hydrazine derivatives are preferably used in addition to the above. The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following publications.

  A compound represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, a compound described on pages 3 and 4 of the same publication; a general formula described in JP-B-6-93082 ( A compound represented by I), specifically, compounds 1 to 38 described on pages 8 to 18 of the same publication; general formulas (4) and (5) described in JP-A-6-230497; And compounds represented by formula (6), specifically, compound 4-1 to compound 4-10 described on pages 25 and 26 of the same publication, compound 5-1 to pages 28 to 36, and 5-42, and compounds 6-1 to 6-7 described on pages 39 and 40; compounds represented by general formula (1) and general formula (2) described in JP-A-6-289520. Specifically, compounds 1-1) to 1-17) and 2-1) described in pages 5 to 7 of the same publication; Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-13936, specifically, compounds described on pages 6 to 19 of the same publication; (Chemical formulas described in JP-A-6-313951) 1), specifically the compounds described on pages 3 to 5 of the publication; compounds represented by the general formula (I) described in JP-A-7-5610, specifically Is a compound represented by the general formula (II) described in JP-A-7-77783, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same publication; specifically, page 10 of the same publication. Compounds II-1 to II-102 described on page 27; compounds represented by general formula (H) and general formula (Ha) described in JP-A-7-104426; Compounds H-1 to H-44 described on pages 15 to 15; hydrides described in JP-A-9-22082 A compound having an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the gin group, particularly the general formula (A), the general formula (B), the general formula ( C), compounds represented by general formula (D), general formula (E), and general formula (F), specifically, compounds N-1 to N-30 described in the same publication; JP-A-9-22082 In particular, compounds represented by the general formula (1) described in the Japanese Patent Publication No., specifically, compounds D-1 to D-55 described in the same publication can be given. In addition, International Publication No. WO95 / 32452, International Publication No. WO95 / 32453, JP-A-9-179229, JP-A-9-235264, JP-A-9-235265, JP-A-9-235266 JP-A-9-235267, JP-A-9-319019, JP-A-9-319020, JP-A-10-130275, JP-A-11-7093, JP-A-6-332096, JP-A-7-209789, JP-A-8-6193, JP-A-8-248549, JP-A-8-248550, JP-A-8-262609, JP-A-8-314044, JP-A-8 -328184, JP-A-9-80667, JP-A-9-127632, JP-A-9-146208 Gazette, JP-A-9-160156, JP-A-10-161260, JP-A-10-221800, JP-A-10-213871, JP-A-10-254082, JP-A-10-254088, JP-A-7-120864, JP-A-7-244348, JP-A-7-333773, JP-A-8-36232, JP-A-8-36233, JP-A-8-36234, JP The hydrazine derivatives described in JP-A-8-36235, JP-A-8-272202, JP-A-9-22083, JP-A-9-22084, JP-A-9-54381, and JP-A-10-175946 are also used. Can be mentioned.

In the present invention, the hydrazine-based nucleating agent is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in
In addition, using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be made and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

In the present invention, the hydrazine nucleating agent may be added to any layer as long as it is on the silver halide emulsion layer side with respect to the support. For example, it can be added to a silver halide emulsion layer or another hydrophilic colloid layer, but it is preferably added to a silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto. Two or more hydrazine nucleating agents can be used in combination.
The addition amount of the nucleating agent in the present invention is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, relative to 1 mol of silver halide, 2 ×. 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferable.

A nucleation accelerator can be incorporated in the silver halide photographic light-sensitive material of the present invention.
Examples of the nucleation accelerator used in the present invention include amine derivatives, onium salts, disulfide derivatives, and hydroxymethyl derivatives. Specifically, compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described on pages 49 to 58; Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in JP-A-7-84331, specifically, compounds described on pages 6 to 8 of the publication; JP-A-7-104426 Compounds represented by the general formula [Na] and general formula [Nb] described in the Japanese Patent Publication No. To Nb-12 compounds: general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (described in JP-A-8-272023) 6) and a compound represented by the general formula (7), specifically, compounds 1-1 to 1-19 described in the publication, -1 to 2-22, 3-1 to 3-36, 4-1 to 4-5, 5-1 to 5-41, 6-1 to 6-58, and Compounds 7-1 to 7-38; nucleation accelerators described in JP-A-9-297377, p55, column 108, line 8 to p69, column 136, line 44.

  As the nucleation accelerator used in the present invention, quaternary salt compounds represented by the following general formulas (a) to (f) are preferable, and compounds represented by the general formula (b) are most preferable. .

In the general formula (a), Q ¹ represents a nitrogen atom or a phosphorus atom, and R ¹⁰⁰ , R ¹¹⁰ , and R ¹²⁰ each represents an aliphatic group, an aromatic group, or a heterocyclic group, which are bonded to each other to form a cyclic structure. It may be formed. M represents an m ¹⁰ valent organic group bonded to Q ¹ at a carbon atom contained in M, and m ¹⁰ represents an integer of 1 to 4.
In General Formula (b), General Formula (c), or General Formula (d), A ¹ , A ² , A ³ , A ⁴ , and A ⁵ are each an unsaturated heterocyclic ring containing a quaternized nitrogen atom. And L ¹⁰ and L ²⁰ each represent a divalent linking group, and R ¹¹¹ , R ²²² , and R ³³³ each represent a substituent.
The quaternary salt compound represented by the general formula (a), the general formula (b), the general formula (c), or the general formula (d) has a repeating unit of ethyleneoxy group or propyleneoxy group in the molecule. Although it has 20 or more, you may have over two or more places.

In the general formula (e), Q ² represents a nitrogen atom or a phosphorus atom. R ²⁰⁰ , R ²¹⁰ and R ²²⁰ represent the same groups as R ¹⁰⁰ , R ¹¹⁰ and R ^{120 in the} general formula (a).
In the general formula (f), A ⁶ represents a group having the same meaning as A ¹ or A ² in the general formula (b). However, the nitrogen-containing unsaturated heterocycle formed by A ⁶ may have a substituent, but does not have a primary hydroxyl group on the substituent. In the general formula (e) and the general formula (f), L ³⁰ represents an alkylene group, Y represents —C (═O) — or —SO ₂ —, and L ⁴⁰ contains 2 containing at least one hydrophilic group. Represents a valent linking group. In the general formulas (a) to (f), X ⁿ⁻ represents an n-valent counter anion, and n represents an integer of 1 to 3. However, X ⁿ⁻ is not necessary when an anionic group is separately provided in the molecule and an intramolecular salt is formed with (Q ¹ ) ⁺ , (Q ² ) ⁺ or N ⁺ .

In the general formula (a), the aliphatic groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl. Group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, octadecyl group and the like linear or branched alkyl group; substituted or unsubstituted benzyl group and the like aralkyl group; cyclopropyl group, cyclopentyl group, cyclohexyl Cycloalkyl groups such as groups; alkenyl groups such as allyl groups, vinyl groups, and 5-hexenyl groups; cycloalkenyl groups such as cyclopentenyl groups and cyclohexenyl groups; and alkynyl groups such as phenylethynyl groups. Aromatic groups include aryl groups such as phenyl, naphthyl, and phenanthryl groups, and heterocyclic groups include pyridyl, quinolyl, furyl, imidazolyl, thiazolyl, thiadiazolyl, benzotriazolyl, Examples thereof include a benzothiazolyl group, a morpholyl group, a pyrimidyl group, and a pyrrolidyl group.

Examples of the substituents substituted on these groups include, in addition to the groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, (Alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamido group, carbamoyl group, ureido group, thioureido group, sulfonylureido group, sulfonamido group, sulfamoyl group, hydroxyl group, Sulfonyl group, carboxyl group (including carboxylate), sulfo group (including sulfonate), cyano group, oxycarbonyl group, acyl group, heterocyclic group (including heterocyclic group containing quaternized nitrogen atom), etc. Is mentioned. These substituents may be further substituted with these substituents.
The groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ in the general formula (a) may be bonded to each other to form a cyclic structure.

Examples of the group represented by M in the general formula (a) include groups having the same meanings as R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ when m ¹⁰ represents 1. When m ¹⁰ represents an integer of 2 or more, M represents a m ¹⁰ valent linking group bonded to Q ¹ at a carbon atom contained in M, specifically, an alkylene group, an arylene group, a heterocyclic group, Is formed by combining these groups with —CO— group, —O— group, —N (RN) — group, —S— group, —SO— group, —SO ₂ —, —P═O— group. that m represents a ^10-valent linking group (RN represents a hydrogen atom or R ^100, R ^110, R ¹²⁰ group having the same meaning as, when a plurality of RN in the molecule, these are different even in the same Or may be bonded to each other). M may have an arbitrary substituent, and examples of the substituent include the same substituents that the group represented by R ¹⁰⁰ , R ¹¹⁰ , and R ¹²⁰ may have.

In the general formula (a), R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ are preferably groups having 20 or less carbon atoms, and when Q ¹ represents a phosphorus atom, an aryl group having 15 or less carbon atoms is particularly preferable, and Q ¹ is When a nitrogen atom is represented, an alkyl group having 15 or less carbon atoms, an aralkyl group, and an aryl group are particularly preferable. m ¹⁰ is preferably 1 or 2, and when m ¹⁰ represents 1, M is preferably a group having 20 or less carbon atoms, particularly preferably an alkyl group, aralkyl group or aryl group having a total carbon number of 15 or less. When m ¹⁰ represents 2, the divalent organic group represented by M is preferably an alkylene group, an arylene group, or these groups and a —CO— group, —O— group, —N (RN) —. It is a divalent group formed by combining a group, —S— group, and —SO ₂ — group. When m ¹⁰ represents 2, M is preferably a divalent group having a total of 20 or less carbon atoms bonded to Q ¹ at a carbon atom contained in M. When M or R ¹⁰⁰ , R ¹¹⁰ , and R ¹²⁰ contain a plurality of repeating units of ethyleneoxy group or propyleneoxy group, the preferred range of the total carbon number described above is not limited thereto. Further When m ¹⁰ represents an integer of 2 or more, R ^100, R ¹¹⁰ in the molecule, R ¹²⁰ is each plurality of, the plurality of R ^100, R ^110, R ¹²⁰ is optionally substituted by one or more identical respectively May be.

The quaternary salt compound represented by the general formula (a) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule, which may be substituted at one place or plural places. It may be substituted across. When m ¹⁰ represents an integer of 2 or more, the linking group represented by M preferably has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group.

In the general formula (b), the general formula (c), or the general formula (d), A ¹ , A ² , A ³ , A ⁴ , and A ^{5 each} contain a quaternized nitrogen atom and are substituted or unsubstituted non-substituted. It represents an organic residue for completing a saturated heterocycle, may contain carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and hydrogen atoms, and may be condensed with a benzene ring. Examples of unsaturated heterocycles formed by A ¹ , A ² , A ³ , A ⁴ and A ⁵ include pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, thiazole ring, thiadiazole ring, benzotriazole ring, benzothiazole A ring, a pyrimidine ring, a pyrazole ring, etc. can be mentioned. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring. The unsaturated heterocycle formed by A ¹ , A ² , A ³ , A ⁴ and A ⁵ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case include the same substituents that the group represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ in the general formula (a) may have. As the substituent, a halogen atom (particularly a chlorine atom), an aryl group having 20 or less carbon atoms (particularly a phenyl group is preferred), an alkyl group, an alkynyl group, a carbamoyl group, an (alkyl or aryl) amino group, (alkyl or aryl) ) Oxycarbonyl group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, hydroxy group, mercapto group, carbonamido group, sulfonamido group, sulfo group (including sulfonate), carboxyl group (including carboxylate) , A cyano group, and the like. Particularly preferred are a phenyl group, an alkylamino group, a carbonamido group, a chlorine atom, an alkylthio group and the like, and most preferred is a phenyl group.

The divalent linking group represented by L ¹⁰ and L ²⁰ is alkylene, arylene, alkenylene, alkynylene, divalent heterocyclic group, —SO ₂ —, —SO—, —O—, —S—, —N. Those composed of (RN ′) —, —C (═O) —, and —PO— alone or in combination are preferred. However, RN ′ represents an alkyl group, an aralkyl group, an aryl group, or a hydrogen atom. The divalent linking group represented by L ¹⁰ and L ²⁰ may have an arbitrary substituent. As an example of a substituent, the same thing as the substituent which the group represented by R ^{< 100 >} , R ^{< 110>} , R ^{<120 >} of general formula (a) may have is mentioned. Particularly preferred examples of L ¹⁰ and L ²⁰ include alkylene, arylene, —C (═O) —, —O—, —S—, —SO ₂ —, —N (RN ′) — alone or in combination. Can be mentioned.

R ¹¹¹ , R ²²² , and R ³³³ are preferably an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and may be the same or different. R ¹¹¹ , R ²²² , and R ³³³ may have a substituent, and the substituent may have a group represented by R ¹⁰⁰ , R ¹¹⁰ , or R ¹²⁰ in the general formula (a). The same thing as a substituent is mentioned. Particularly preferably, R ¹¹¹ , R ²²² and R ³³³ are each an alkyl group having 1 to 10 carbon atoms or an aralkyl group. Examples of preferable substituents include carbamoyl group, oxycarbonyl group, acyl group, aryl group, sulfo group (including sulfonate), carboxyl group (including carboxylate), hydroxy group, (alkyl or aryl) amino group, An alkoxy group can be mentioned.
However, when R ¹¹¹ , R ²²² and R ³³³ contain a plurality of repeating units of ethyleneoxy group or propyleneoxy group, the preferred range of the carbon number described above for R ¹¹¹ , R ²²² and R ³³³ is not limited thereto. .

The quaternary salt compound represented by the general formula (b) or the general formula (c) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule, but this is substituted at one place. Or may be substituted at a plurality of positions, and may be substituted at any of A ¹ , A ² , A ³ , A ⁴ , R ¹¹¹ , R ²²² , L ¹⁰ , L ²⁰ , The linking group represented by L ¹⁰ or L ²⁰ preferably has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group.

The quaternary salt compound represented by the general formula (d) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule, which may be substituted at one place or at plural places. ^May be substituted with either A ⁵ or R ³³³ , but preferably, the group represented by R ³³³ contains a total of 20 repeating units of an ethyleneoxy group or a propyleneoxy group It is preferable to have the above.

The quaternary salt compounds represented by the general formula (a), the general formula (b), the general formula (c), and the general formula (d) may repeatedly contain an ethyleneoxy group and a propyleneoxy group at the same time. Good. In the case where a plurality of repeating units of ethyleneoxy group or propyleneoxy group are contained, the number of repeating units may take exactly one value or may be given as an average value. The compound is a mixture having a certain molecular weight distribution.
In the present invention, it is more preferable to have a total of 20 or more repeating units of ethyleneoxy group, and it is more preferable to have a total of 20 to 67 total units.

In the general formula (e), Q ² , R ²⁰⁰ , R ²¹⁰ and R ²²⁰ each represent a group having the same meaning as Q ¹ , R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ in the general formula (a), and their preferred ranges are also the same. It is.
In the general formula (f), A ⁶ represents a group having the same meaning as A ¹ or A ² in the general formula (b), and its preferred range is also the same. However, the nitrogen-containing unsaturated heterocycle formed by A ⁶ in the general formula (f) together with the quaternized nitrogen atom may have a substituent, but has a substituent containing a primary hydroxyl group. There is nothing.

In the general formula (e) and the general formula (f), L ³⁰ represents an alkylene group. The alkylene group is preferably a linear, branched, or cyclic, substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. Further, not only a saturated group represented by an ethylene group but also an unsaturated group represented by -CH ₂ C ₆ H ₄ CH ₂ -or -CH ₂ CH = CHCH ₂ -may be contained. Further, when L ³⁰ has a substituent, examples of the substituent include the substituents that the group represented by R ¹⁰⁰ , R ¹¹⁰ , and R ¹²⁰ in the general formula (a) may have.
L ³⁰ is preferably a linear or branched saturated group having 1 to 10 carbon atoms. More preferred is a substituted or unsubstituted methylene group, ethylene group or trimethylene group, particularly preferred is a substituted or unsubstituted methylene group or ethylene group, and most preferred is a substituted or unsubstituted methylene group.

In the general formula (e) and the general formula (f), L ⁴⁰ represents a divalent linking group having at least one hydrophilic group. -SO ₂ The here hydrophilic group -, - SO -, - O -, - P (= O) =, - C (= O) -, - CONH -, - SO 2 NH -, - NHSO 2 NH —, —NHCONH—, an amino group, a guanidino group, an ammonio group, a group of a heterocyclic group containing a quaternized nitrogen atom, or a combination of these groups. L ⁴⁰ is constituted by appropriately combining these hydrophilic group and an alkylene group, alkenylene group, arylene group, or heterocyclic group.
A group such as an alkylene group, an arylene group, an alkenylene group, or a heterocyclic group constituting L ⁴⁰ may have a substituent. Examples of the substituent include the same as the examples of the substituent which the group represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ in the general formula (a) may have.
Also the hydrophilic group in L ⁴⁰ is present in the form of dividing the L ^40, may it be present as part of a substituent on L ^40, that are present in the form of dividing the L ⁴⁰ Is more preferable. For example -C (= O) -, - SO 2 -, - SO -, - O -, - P (= O) =, - CONH -, - SO 2 NH -, - NHSO 2 NH -, - NHCONH-, Consists of a cationic group (specifically, a quaternary salt structure of nitrogen or phosphorus, or a nitrogen-containing heterocycle containing a quaternized nitrogen atom), an amino group, a guanidino group, or a combination of these groups This is a case where a divalent group is present in a form that divides L ⁴⁰ .

One preferred example of the hydrophilic group possessed by L ⁴⁰ is a group having a plurality of repeating units of an ethyleneoxy group or a propyleneoxy group, in which an ether bond and an alkylene group are combined. The polymerization degree or average polymerization degree is preferably 2 to 67.
Examples of the hydrophilic group that L ⁴⁰ has include —SO ₂ —, —SO—, —O—, —P (═O) ═, —C (═O) —, —CONH—, —SO ₂ NH—, As a result of combining a group such as —NHSO ₂ NH—, —NHCONH—, an amino group, a guanidino group, an ammonio group, a quaternized heterocyclic group containing a nitrogen atom, or a substituent of L ⁴⁰ , It is also preferred when it contains a dissociable group. Here, the dissociable group means a group or a partial structure having a low acidity proton that can be dissociated by an alkaline developer, or a salt thereof, and specifically includes, for example, a carboxy group (—COOH), sulfo group. Group (—SO ₃ H), phosphonic acid group (—PO ₃ H), phosphoric acid group (—OPO ₃ H), hydroxy group (—OH group), mercapto group (—SH), —SO ₂ NH ₂ group, N-substituted sulfonamide group (—SO ₂ NH— group, —CONHSO ₂ — group, —SO ₂ NHSO ₂ — group), —CONHCO— group, active methylene group, —NH— inherent in nitrogen-containing heterocyclic group Group or a salt thereof.

L ⁴⁰ is preferably an alkylene group or an arylene group, -C (= O) -, - SO 2 -, - O -, - CONH -, - SO 2 NH -, - NHSO 2 NH -, - NHCONH-, and A suitable combination of amino groups is used. More preferably an alkylene group having 2 to 5 carbon atoms -C (= O) -, - SO 2 -, - O -, - CONH -, - SO 2 NH -, - NHSO 2 NH -, - NHCONH- appropriate A combination is used.
Y represents —C (═O) — or —SO ₂ —. Preferably -C (= O)-is used.

Examples of the counter anion represented by X ⁿ⁻ in the general formula (a) to the general formula (f) include halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion, Examples thereof include carboxylate ions such as benzoate ions, sulfonate ions such as p-toluenesulfonate, methanesulfonate, butanesulfonate, and benzenesulfonate, sulfate ions, perchlorate ions, carbonate ions, and nitrate ions.
The counter anion represented by X ⁿ⁻ is preferably a halogen ion, a carboxylate ion, a sulfonate ion, or a sulfate ion, and n is preferably 1 or 2. X ⁿ⁻ is particularly preferably a chloro ion or a bromo ion, and most preferably a chloro ion.
However, X ⁿ⁻ is not necessary when it has an anionic group separately in the molecule and forms an inner salt with (Q ¹ ) ⁺ , (Q ² ) ⁺ or N ⁺ .

The quaternary salt compound used in the present invention is more preferably a quaternary salt compound represented by general formula (b), general formula (c), or general formula (f), among which general formula (b) and general formula ( The quaternary salt compound represented by f) is particularly preferred. Further, in the general formula (b), the case where the linking group represented by L ¹⁰ has 20 or more repeating units of ethyleneoxy group is preferred, and the case where it has 20 to 67 is particularly preferred. In general formula (f), it is particularly preferred that the unsaturated heterocyclic compound formed by A ⁶ represents 4-phenylpyridine, isoquinoline, or quinoline.

  Next, specific examples of the quaternary salt compounds represented by the general formulas (a) to (f) are shown. In the following, Ph represents a phenyl group. However, the present invention is not limited by the following compound examples.

  The quaternary salt compounds represented by the general formulas (a) to (f) can be easily synthesized by known methods.

  Nucleation promoters that can be used in the present invention include suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cell. It can be used by dissolving in a solve.

  In addition, using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be made and used. Alternatively, the nucleation accelerator powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The nucleation accelerator that can be used in the present invention is preferably added to a non-light-sensitive layer composed of a hydrophilic colloid layer not containing a silver halide emulsion on the side of the silver halide emulsion layer with respect to the support. It is preferably added to a non-photosensitive layer comprising a hydrophilic colloid layer between the silver emulsion layer and the support.
The addition amount of the nucleation accelerator is preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol, relative to 1 mol of silver halide, and 2 × 10 ^−5. Most preferred is ˜1 × 10 ⁻² mol. Two or more kinds of nucleation accelerators can be used in combination.

  Various additives used in the silver halide photographic light-sensitive material of the present invention are not particularly limited. For example, JP-A-3-39948, page 10, lower right line 11 to page 12, lower left line 5, line. (Specifically, compounds of compounds (III) -1 to 25 described in the publication); a substance represented by the general formula (I) described in JP-A 1-118832 Specifically, a compound having no absorption maximum in the visible range (specifically, compounds I-1 to I-26 described in the same publication); JP-A-2-103536, page 17, lower right, line 19 Antifoggant described in page 4, upper right line, page 18; polymer latex described in JP-A-2-103536, page 18, lower left line 12 to page, lower left line 20; JP-A-9-179228 It is represented by the general formula (I) described in Polymer latex having an active methylene group (specifically, compounds I-1 to I-16 described in the publication); Polymer latex having a core / shell structure described in JP-A-9-179228 (specifically, Compounds P-1 to P-55 described in the above publication; acidic polymer latex described in JP-A-7-104413, page 14, left line 1 to right line 30, line 30 (specifically, reference 15) Compounds II-1) to II-9)) described on page: Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15 A hardening agent described in JP-A-2-103536, page 18, upper right line 5 to upper-right line 17, line 18; JP-A-2-103536, page 18, lower right line 6-page 19 upper left Compound having an acid group described in the first line; No. 18542, page 2, lower left line 13 to the upper right line, page 3, upper right line 7, conductive material (specifically, page 2, lower right line 2, page 10 lower right line) And the conductive polymer compound of compounds P-1 to P-7 described in the above publication); JP-A-2-103536, page 17, lower right, line 1 to upper right, line 18 Water-soluble dyes described in the eyes; solid disperse dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243 (specific examples) The compounds F1 to F34 described in the publication, (II-2) to (II-24) described in JP-A-7-152112, and (III-5) to (III-) described in JP-A-7-152112. 18), (IV-2) to (IV-7) described in JP-A-7-152112, and JP-A-2-294638. And solid disperse dyes described in JP-A-5-11382); redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816, preferably as described in JP-A-5-274816 Redox compounds represented by formula (R-1), general formula (R-2), and general formula (R-3) (specifically, compounds R-1 to R-68 described in the publication) And binders described in JP-A-2-18542, page 3, lower right, lines 1 to 20;

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer on the support, and can also be provided with at least one protective layer and at least one antihalation layer as required. .
The silver halide photographic light-sensitive material of the present invention has at least one back layer on the side opposite to the silver halide emulsion layer on the support, and can also be provided with at least one protective layer as required.

As the binder of the hydrophilic colloid layer used in the present invention, gelatin is advantageously used, 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, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Use various synthetic hydrophilic polymer materials such as mono- or copolymers of polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Can do.
As gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used.

The protective layer used in the present invention may contain a fluorine-containing surfactant described in JP-A-60-80849 or the like for the purpose of preventing charging. For the purpose of preventing black spots, a chelating agent such as EDTA, 5-chloro-8-hydroxyquinoline, 1,5-dihydroxy-2-benzaldoxime may be contained. Further, a part or all of an antifoggant, an anti-irradiation dye, a surfactant, a hardener, a poorly soluble synthetic polymer and the like may be contained in the protective layer. The protective layer used in the present invention may have a multilayer structure of two or more layers.
The thickness of the protective layer used in the present invention is preferably 0.05 to 5 μm, more preferably 0.2 to 2 μm.
It is advantageous to use gelatin as a binder for the protective layer used in the silver halide photographic light-sensitive material of the present invention. The coating amount of gelatin as a binder is preferably 0.2 to 3.0 g / m ² , more preferably 0.5 to 2.0 g / m ² .

It is advantageous to use gelatin as a binder for the silver halide emulsion layer used in the silver halide photographic light-sensitive material of the present invention. The coating amount of gelatin as a binder is preferably 0.5 to 4.0 g / m ² , more preferably 1.0 to 3.0 g / m ² .

As the binder for the back layer used in the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin. Coating amount of gelatin as the binder is at 6.0 g / m ² or less, preferably 2.0 to 6.0 g / m ^2. More preferably, it is 3.0-5.0 g / m < ² >.

The swelling ratio of the hydrophilic colloid layer including the emulsion layer and protective layer of the silver halide photographic light-sensitive material of the present invention is preferably in the range of 80 to 150%, more preferably in the range of 90 to 140%. The swelling ratio of the hydrophilic colloid layer was determined by measuring the thickness (d ₀ ) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material, and distilling the silver halide photographic material at 25 ° C. After immersing in water for 1 minute, the swollen thickness (Δd) is measured, and the swelling ratio (%) = (Δd ÷ d ₀ ) × 100 is calculated.

  The film surface pH on the side on which the silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention is coated is preferably 7.5 or less, more preferably 4.5 to 6.0, More preferably, it is 4.8 to 6.0. If it is less than 4.5, the hardening of the emulsion layer tends to slow.

Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected according to the intended use of the silver halide photographic material.
A support made of a styrene polymer having a syndiotactic structure described in JP-A-7-234478 and US Pat. No. 5,558,979 is also preferably used. The thickness of the support is particularly preferably 160 to 200 μm.

  The processing agents and processing methods such as developer and fixing solution in the present invention will be described below, but it goes without saying that the present invention is not limited to the following descriptions and specific examples.

  For the development processing of the silver halide photographic light-sensitive material of the present invention, any known method can be used. A known developing solution can be used.

There are no particular limitations on the developing agent used in the developer used in the present invention (hereinafter, both development initiator and developer replenisher are collectively referred to as developer), but dihydroxybenzenes, ascorbic acid derivatives, hydroquinone, etc. Monosulfonates are preferably included, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent that exhibits superadditivity with this, and a combination of dihydroxybenzenes or ascorbic acid derivatives and 1-phenyl-3-pyrazolidones, or dihydroxybenzenes or Examples include combinations of ascorbic acid derivatives and p-aminophenols.
Among the developing agents used in the present invention, examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, and methyl hydroquinone. Hydroquinone is particularly preferable. As the ascorbic acid derivative developing agent, there are ascorbic acid and isoascorbic acid and their salts. Sodium erythorbate is particularly preferable from the viewpoint of material cost.

As developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone and the like.
As p-aminophenol developers used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, There are o-methoxy-p- (N, N-dimethylamino) phenol, o-methoxy-p- (N-methylamino) phenol, among others, N-methyl-p-aminophenol, Aminophenols described in JP-A No. 297377 and JP-A-9-297378 are preferred.

  It is preferable that the dihydroxybenzene developing agent is usually used in an amount of 0.05 mol / L to 0.8 mol / L. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / L to 0.6 mol / L, preferably 0.10 mol / L to 0.00. It is preferable to use 5 mol / L and the latter in an amount of 0.06 mol / L or less, preferably 0.03 mol / L to 0.003 mol / L.

  The ascorbic acid derivative developing agent is usually preferably used in an amount of 0.01 mol / L to 0.5 mol / L, more preferably 0.05 mol / L to 0.3 mol / L. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is added in an amount of 0.01 mol / L to 0.5 mol / L, 1-phenyl-3-pyrazolidones. Alternatively, p-aminophenols are preferably used in an amount of 0.005 mol / L to 0.2 mol / L.

The developer used for processing the silver halide photographic light-sensitive material of the present invention can contain commonly used additives (for example, developing agents, alkali agents, pH buffering agents, preservatives, chelating agents, etc.). . Specific examples of these are shown below, but what can be used in the present invention is not limited thereto.
Examples of the buffer used in the developing solution during development processing include carbonates, boric acid described in JP-A-62-286259, saccharides (for example, saccharose) described in JP-A-60-93433, and oximes. (For example, acetoxime), phenols (for example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like are used, and carbonate is preferably used. The amount of the buffer, particularly carbonate used is preferably 0.05 mol / L or more, particularly 0.08 to 1.0 mol / L.

  In the present invention, it is preferable that both the development starter and the development replenisher have a pH increase of 0.8 or less when 0.1 mol of sodium hydroxide is added to 1 L of the solution. As a method for confirming that the development starting solution or development replenisher used has this property, the pH of the development starting solution or development replenisher to be tested is adjusted to 10.5, and then sodium hydroxide is added to 0.1 L of this solution. 1 mol is added, and the pH value of the liquid at this time is measured. If the increase in pH value is 0.8 or less, it is determined that the liquid has the properties defined above. In the present invention, it is particularly preferable to use a development starter and a development replenisher that have a pH value increase of 0.7 or less when the above test is performed.

Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulphite is preferably used in an amount of 0.2 mol / L or more, particularly 0.3 mol / L or more. However, if added too much, it causes silver stains in the developer, so the upper limit should be 1.2 mol / L. desirable. Most preferably, it is 0.35-0.7 mol / L.
As a preservative for a dihydroxybenzene developing agent, a small amount of the ascorbic acid derivative may be used in combination with sulfite. Of these, sodium erythorbate is preferably used from the viewpoint of material cost. The addition amount is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10, with respect to the dihydroxybenzene-based developing agent. When using an ascorbic acid derivative as a preservative, it is preferable that the developer does not contain a boron compound.

Additives used other than the above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide, and alkanolamines such as diethanolamine and triethanolamine. , Development accelerators such as imidazole or derivatives thereof, heterocyclic mercapto compounds (for example, sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.), JP-A-62-2 The compounds described in JP-A-221651 can also be added as a physical development unevenness inhibitor.
Further, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be contained as an antifoggant or a black pepper inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2- Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4, thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like. The amount of these additives is usually from 0.01 to 10 mmol, and more preferably from 0.1 to 2 mmol, per liter of the developing solution.

Furthermore, various organic and inorganic chelating agents can be used alone or in combination in the developer used in the present invention.
Examples of the inorganic chelating agent that can be used include sodium tetrapolyphosphate and sodium hexametaphosphate.
On the other hand, as organic chelating agents, organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be mainly used.
Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, malein Examples include acid, itaconic acid, malic acid, citric acid, and tartaric acid.

  Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, Triethylenetetramine hexaacetic acid, 1,3-diamino-2-propanol tetraacetic acid, glycol ether diamine tetraacetic acid, other JP-A Nos. 52-25632, 55-67747, 57-102624, and special Mention may be made of the compounds described in JP-A-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid and research disclosure described in, for example, US Pat. Nos. 3,214,454, 3,794,591 and German Patent Publication No. 2227369. 181 volume, Item 18170 (May 1979 issue) etc. are mentioned.
Examples of aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition, Research Disclosure 18170, JP-A-57-208554, 54. -61125 gazette, 55-29883 gazette, 56-97347 gazette etc. can also be mentioned.

  Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, and 55-126241. And JP-A-55-65955, 55-65956, and Research Disclosure 18170 described above.

These organic and / or inorganic chelating agents are not limited to those described above. Moreover, you may use in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol per liter of the developer.

Further, as silver stain preventing agents in the developer, for example, JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, JP-A-4-362294, JP-A-8- In addition to the compounds described in JP 6215 A, triazines having one or more mercapto groups (for example, compounds described in JP-B-6-23830, JP-A-3-282457, JP-A-7-175178), mercapto Pyrimidines having one or more groups (eg 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2, 4, 6- Trimercaptopyrimidine, compounds described in JP-A-9-274289, etc.), pyridine having one or more mercapto groups ( For example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, compounds described in JP-A-7-24887), and a mercapto group 1 Two or more pyrazines (for example, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc.), pyridazines having one or more mercapto groups (for example, 3 -Mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177, US Pat. No. 5,457 , 011 polyoxyalkyl phosphonic acid ester etc. used It can be. These silver stain preventing agents can be used singly or in combination, and the addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol per liter of the developer.
Moreover, the compound of Unexamined-Japanese-Patent No. 61-267759 can be used as a solubilizing agent.
Furthermore, a color toning agent, a surfactant, an antifoaming agent, a hardening agent, and the like may be included as necessary.

  The preferred pH of the developer is 9.0 to 12.0, particularly preferably 9.0 to 11.0, and further preferably 9.5 to 11.0. As the alkali agent used for pH adjustment, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

  As cations in the developer, potassium ions do not suppress development more than sodium ions, and there are fewer jagged edges around the blackened portion called fringe. Furthermore, when it is stored as a concentrated solution, generally potassium salts are preferred because of their high solubility. However, in the fixing solution, potassium ions inhibit fixing to the same extent as silver ions. Therefore, when the potassium ion concentration of the developer is high, the developer is brought into the fixing solution by the silver halide photographic material. A potassium ion concentration becomes high and is not preferable. From the above, the molar ratio of potassium ions to sodium ions in the developer is preferably between 20:80 and 80:20. The ratio of potassium ion to sodium ion can be arbitrarily adjusted within the above range by a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishment amount of the developer is 470 ml or less, preferably 30 to 325 ml, per 1 m ^{2 of the} silver halide photographic light-sensitive material. The development replenisher may have the same composition and / or concentration as the development starter, or may have a composition and / or concentration different from that of the starter.

  As the fixing agent of the fixing processing agent in the present invention, ammonium thiosulfate, sodium thiosulfate, and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be appropriately changed, but is generally about 0.7 to about 3.0 mol / L.

The fixing solution in the present invention may contain a water-soluble aluminum salt and a water-soluble chromium salt that act as a hardening agent, and a water-soluble aluminum salt is preferable. Examples include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are preferably contained at 0.01 to 0.15 mol / L as the aluminum ion concentration in the working solution.
In the case where the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts with a hardener or the like as a separate part, or may be a one-part type composition including all components.

  As a fixing treatment agent, a preservative (for example, 0.015 mol / L or more, preferably 0.02 mol / L to 0.3 mol / L, for example, sulfite, bisulfite, metabisulfite, etc.), pH buffering agent, if desired. (For example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc. are 0.1 mol / L to 1 mol / L, preferably 0.2 mol / L to 0.7 mol / L), aluminum Compounds with stabilizing ability and water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tyrone , Ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and These derivatives and their salts, saccharides and the like can be contained in 0.001 mol / L to 0.5 mol / L, preferably 0.005 mol / L to 0.3 mol / L). From the point of view, it is better not to contain boron compounds.

  In addition, compounds described in JP-A No. 62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and amphoteric surfactants described in JP-A No. 57-6840. A known antifoaming agent is used. You can also Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B Nos. 45-35754, 58-122535, and 58-122536. Thiourea derivatives described above, alcohols having triple bonds in the molecule, thioether compounds described in US Pat. No. 4,126,459, JP-A-64-4739, JP-A-1-4739, Mercapto compounds described in JP-A-1-159645 and JP-A-3-101728, mesoionic compounds described in JP-A-4-170539, and thiocyanate can be included.

  The pH of the fixing solution in the present invention is preferably 4.0 or more, and more preferably 4.5 to 6.0. The pH of the fixing solution rises due to the mixing of the developer by the processing. In this case, the pH of the fixing solution is preferably 6.0 or less, more preferably 5.7 or less, In the non-hard film fixing solution, it is preferably 7.0 or less, and more preferably 6.7 or less.

The replenishing amount of the fixing solution is preferably 500 ml or less, more preferably 390 ml or less, and particularly preferably 80 to 325 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be regenerated and reused by a known fixing solution regeneration method such as electrolytic silver recovery. An example of the playback apparatus is FS-2000 manufactured by Fuji Photo Film Co., Ltd.
Moreover, it is also preferable to remove pigment | dyes etc. using adsorption filters, such as activated carbon.

  When the developing and fixing treatment agent in the present invention is a liquid agent, it is preferably stored in a packaging material having low oxygen permeability as described in, for example, JP-A-61-73147. Furthermore, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Even if the development processing agent and the fixing processing agent in the present invention are solid, the same result as the liquid agent can be obtained. The solid processing agent will be described below.
In the present invention, a solid agent having a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film in order to separate components that react with each other upon contact, or components that react with each other may be separated in a plurality of layers. These may be used in combination.

  Known coating agents and granulation aids can be used, but polyvinyl pyrrolidone, polyethylene glycol, polystyrene sulfonic acid, and vinyl compounds are preferably used. In addition, JP-A-5-45805, column 2, line 48 to column 3, line 13 can be referred to.

  In the case of a plurality of layers, a component that does not react even when contacted may be sandwiched between components that react with each other, and processed into tablets, briquettes, etc. It may be configured and packaged. These methods are disclosed in, for example, JP-A Nos. 61-259921, 4-16841, 4-78848, and 5-93991.

The bulk density of the solid processing agent is preferably 0.5 to 6.0 g / cm ^3, particularly tablets preferably 1.0 to 5.0 g / cm ^3, the granules is 0.5 to 1.5 g / cm ³ preferable.

  Any known method can be used for producing the solid processing agent in the present invention. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, 4-32837, 4-78848, 5-93991, 4 -85533, 4-85534, 4-85535, 5-134362, 5-197070, 5-204098, 5-224361, 6- Reference can be made to JP-A-138604, JP-A-6-138605, and 8-286329.

  More specifically, rolling granulation method, extrusion granulation method, compression granulation method, pulverization granulation method, stirring granulation method, spray drying method, dissolution coagulation method, briquetting method, roller compacting method, etc. Can be used.

  The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smooth, porous, etc.), partially changing the thickness, or making it into a hollow donut shape. Furthermore, it is also possible to take a plurality of shapes in order to give different solubility to a plurality of granulated products or to match the solubility of materials having different solubility. Moreover, the multilayer granulated material from which a composition differs in the surface and an inside may be sufficient.

  The packaging material of the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known material such as a bag shape, a cylindrical shape, or a box shape. JP-A-6-242585 to JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, JP-A-6-301189, JP-A-7-5664, JP-A-7-5666. In order to reduce the storage space for the waste packaging material, it is also preferable to use a foldable shape as disclosed in JP-A-7-5669. These packaging materials may have a screw cap, a pull top, an aluminum seal attached to the processing agent outlet, or heat-sealing the packaging material, but other known materials may be used, and there is no particular limitation. do not do. Furthermore, it is preferable to recycle or reuse waste packaging materials for environmental conservation.

  The method for dissolving and replenishing the solid processing agent is not particularly limited, and a known method can be used. These methods include, for example, a method in which a fixed amount is dissolved and replenished with a dissolution apparatus having a stirring function, a dissolution having a dissolution part and a part for stocking a finished liquid as described in JP-A-9-80718. A processing agent is supplied to the circulation system of an automatic processor as described in a method of dissolving in an apparatus and replenishing from a stock section, JP-A-5-119454, JP-A-6-19102, and JP-A-7-261357. There are a method of charging and dissolving / replenishing, a method of charging and dissolving a processing agent according to the processing of the silver halide photographic light-sensitive material with an automatic processor having a dissolution tank, and any other known method. Can also be used. In addition, the processing agent may be input manually, or may be automatically opened and automatically input by a dissolution apparatus or an automatic developing machine having an opening mechanism as described in JP-A-9-138495, The latter is preferable from the viewpoint of the working environment. Specifically, there are a method of breaking through the take-out port, a method of peeling, a method of cutting, a method of cutting out, and methods described in JP-A-6-19102 and JP-A-6-95331.

The silver halide photographic light-sensitive material that has been developed and fixed is then washed with water or stabilized (hereinafter referred to as water washing, including stabilization, unless otherwise specified). Called water). The water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. These replenishing amounts are generally about 8 L to about 17 L per 1 m ^{2 of the} silver halide photographic light-sensitive material, but can be carried out with a replenishing amount below that. In particular, a replenishment amount of 3 L or less (including 0, that is, rinsing with water) not only enables water-saving processing, but also eliminates the need for piping for installing an automatic processor. When washing with a low replenishing amount, it is more preferable to provide a squeeze roller and crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. In addition, various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) are used to reduce pollution load, which is a problem when washing with small amounts of water, and to prevent scaling. Addition and filter filtration may be combined.

As a method for reducing the replenishment amount of washing with water, a multi-stage counter-current system (for example, 2 stages, 3 stages, etc.) has been known for a long time, and the washing replenishment amount is preferably 50 to 200 ml per 1 m ^{2 of} silver halide photographic light-sensitive material. This effect can be obtained in the same manner even in an independent multi-stage system (a method in which a new liquid is individually replenished in a multi-stage washing tank without using a countercurrent flow).

Furthermore, you may give a scale prevention means to the washing process. As the scale preventing means, known means can be used, although not particularly limited, a method of adding an antifungal agent (so-called scale preventing agent), a method of energizing, a method of irradiating ultraviolet rays, infrared rays or far infrared rays, There are a method of applying a magnetic field, a method of ultrasonic treatment, a method of applying heat, and a method of emptying the tank when not in use. These scales may be used in accordance with the processing of the silver halide photographic light-sensitive material, may be performed at regular intervals regardless of the usage status, or only during periods when processing is not performed, such as at night. Also good. Alternatively, it may be preliminarily applied to washing water and replenished. Furthermore, it is also preferable to perform different scale prevention means for each fixed period in order to suppress the generation of resistant bacteria.
As the water saving scale device, Fujifilm Corporation AC-1000 and Fuji Film Corporation AB-5 may be used, or the method disclosed in JP-A-11-231485 may be used.
There is no particular limitation on the anti-corrosive agent, and known ones can be used. In addition to the above-mentioned oxidizing agents, there are chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-mercaptopyridine-N-oxide, etc.), etc. But you can.
As a method of energizing, the methods described in JP-A-3-224855, JP-A-3-224687, JP-A-4-16280, JP-A-4-18980 and the like can be used.

  In addition, a known water-soluble surfactant or antifoaming agent may be added for preventing water bubble unevenness and dirt transfer. Further, a dye adsorbent described in JP-A-63-163456 may be installed in a washing system in order to prevent contamination with dyes eluted from the silver halide photographic light-sensitive material.

  A part or all of the overflow solution from the washing step can be mixed and used in a processing solution having fixing ability as described in JP-A-60-235133. In addition, biochemical oxygen demand by microbial treatment (eg, sulfur-oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic), oxidation treatment with electricity or oxidant, etc. Drainage after reducing the amount (BOD), chemical oxygen demand (COD), iodine consumption, etc., and forming a slightly soluble silver complex such as a filter using a polymer with affinity for silver or trimercaptotriazine It is also preferable from the viewpoint of conservation of the natural environment to add a compound to be added, to precipitate silver and to filter it, and to reduce the silver concentration in the waste water.

  Further, there is a case where a stabilization treatment is performed following the water washing treatment, and examples thereof are described in JP-A-2-2013357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446. A bath containing the above compound may be used as the final bath of the silver halide photographic material. In this stabilizing bath, metal compounds such as ammonium compounds, Bi and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, antifungal agents, alkanolamines and surfactants as necessary Agents can also be added.

  Additives and stabilizers such as an anti-bacterial agent added to the water-washing and stabilizing bath can be made into solid agents as in the above-described development and fixing treatment agents.

  The developer, fixing solution, washing water, and stabilizing solution waste solution used in the present invention are preferably disposed of by incineration. Further, these waste liquids can be disposed of after being concentrated or liquefied by a concentrating device as described in, for example, Japanese Patent Publication No. 7-83867 and US Pat. No. 5,439,560. .

  When reducing the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent liquid evaporation and air oxidation. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,779 and 3,545,971. In this specification, it is simply referred to as a roller-conveying type automatic developing machine. To do. This automatic machine is composed of four steps of development, fixing, washing and drying. When processing the silver halide photographic light-sensitive material of the present invention, other steps (for example, a stop step) are not excluded, but these four steps are not excluded. Most preferably, the process is followed. Further, a rinsing bath, a water washing tank or a washing tank may be provided between the development fixing and / or the fixing water washing.

  When developing the silver halide photographic light-sensitive material of the present invention, it is preferable to carry out the drying to dry process from 25 to 160 seconds, and the development and fixing time is 40 seconds or less. It is more preferable that it is 6 to 35 seconds, and the temperature of each solution is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the silver halide photographic light-sensitive material that has been developed, fixed and washed may be dried by squeezing the washing water, that is, through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and is not particularly limited. However, the drying method is disclosed in Japanese Patent Application Laid-Open Nos. 4-15534, 5-2256, and 5-289294. Heat roller drying, drying by far infrared rays, etc., and a plurality of methods may be used in combination.

Below, based on drawing, one Embodiment regarding the packaging material of this invention is described.
As shown in FIG. 1, a laminated body 1 of sheet-shaped silver halide photographic light-sensitive materials with rounded corners is protected by a protective plate 2 made of a polypropylene sheet having a U-shaped cross section and is housed in an interior bag 3. The four sides of the storage bag 3 form a heat seal portion 4 having a width.
As shown in FIG. 2, the interior bag 3 is stored in a rectangular parallelepiped container (box) composed of a body 6 and a lid 7, and the box body 6 and the lid 7 are fixed by an adhesive tape 9. The cushioning member 8 sandwiched between the box body 6 and the lid 7 presses at least a part of the heat seal portion against the inside of the bottom surface of the body 6 or the top plate of the lid 7 so as to suppress the movement of the interior bag. It is configured.
The shape of the buffer member has various shapes as shown in FIG. 3, and is preferably a shape that substantially uniformly fixes the four sides of the heat seal portion around the interior bag. As shown in FIG. 4, the degree of fixation depends on a width a that holds the heat seal portion and a height b at which the buffer member is compressed.

  In the package of the present invention, it is preferable that a laminate of sheet-like silver halide photographic light-sensitive material is enclosed in a light-shielding interior bag and the interior bag is stored in an outer box in a fitting form. The laminate of the silver halide photographic light-sensitive material may be directly enclosed in a light-shielding interior bag, or the laminate may be packaged with a protective plate and then stored in the interior bag. The protective plate is a packaging member of a laminate of silver halide photographic light-sensitive materials, and it is desired that the protective plate does not adversely affect the silver halide photographic light-sensitive material because it is in direct contact with the silver halide photographic light-sensitive material. Usually, the protective plate material has a content of a harmful substance to the silver halide photographic light-sensitive material of 1,000 PPM or less, and it is necessary that the protective plate material has substantially no influence on the silver halide photographic light-sensitive material. In order to prevent spot generation, it is preferable to use a material that generates less dust.

  Specifically, the protective plate uses a material in which the content of each of the photographic harmful substances is 1,000 PPM or less, or by providing a protective film of an ultraviolet curable resin on the surface of the protective plate, It is preferable to detoxify the effects of these harmful substances. As the protective plate, it is preferable to use various papers and plastic sheets made of pulp having a fiber length of 3 mm or more. Specific examples of paper include paper strength enhancer-added paper, resin-laminated paper, latex or resin-impregnated paper, resin or starch or PVA surface-coated paper, surface sizing paper, synthetic paper, dust-free paper, neutral paper Is mentioned. Specific examples of the plastic sheet include a polyethylene sheet and a polypropylene sheet. As the protective plate used in the present invention, a plastic sheet is preferably used, and a polypropylene sheet is particularly preferably used.

The thickness of the protective plate is preferably 300 to 700 μm, and the stiffness is preferably 0.0005 to 0.001 N · m. Stiffness refers to the bending moment of the protective plate, and details of the measuring method are defined in JIS P8125. The surface roughness of the protective plate is preferably 10 to 500 μm. The surface roughness means an average interval of the unevenness of the protective plate, and details of the measuring method are defined in JIS standard B0601. Further, the wetting tension of the protective plate is preferably 4000 to 5000 dyne / m. Details of the measuring method of the wetting tension are defined in JIS standard K6768.
In the sheet-like silver halide photographic light-sensitive material of the present invention, it is preferable to round the four corners of the rectangle in order to reduce bag breakage.
The protective plate preferably has a shape that covers the entire bottom surface of the laminate of sheet-like silver halide photographic light-sensitive materials, and preferably has a U-shaped cross section that covers the entire top surface of the laminate.

  The laminate of sheet-shaped silver halide photographic light-sensitive material is packaged directly or by a protective plate and stored in a light-shielding interior bag. The interior bag used in the present invention is preferably a completely light-shielding interior material having moisture resistance. Various types of known bags such as a single flat bag, a double flat bag, a single gusset bag, and a double gusset bag can be adopted as the interior bag.

Specifically, in a single bag, extruded PE (equivalent to a thickness of 13 μm) is extruded into 40 μm thick BOPP (Black Oriented Polypropylene), and this is used as an adhesive to form a 80 μm thick BPE (Black Polyethylene) is used. For the double bag, the above-mentioned interior material is used as an outer bag, and the interior material obtained by extruding and laminating PE (thickness equivalent to 13 μm) melted on the BOPP surface of the interior material is used as an inner bag.
The rigidity of the interior material is preferably 0.0001 N · m or more, and the tear strength of the interior material is preferably 0.015 N · m or more. Here, the measuring method of the tear strength of the interior material complies with the provisions of JIS standard P8116.

  According to the properties of the interior material to be used, conventionally known plastic film sealing methods such as heat sealing, fusing sealing, impulse sealing, ultrasonic sealing, and high frequency sealing can be appropriately selected and used as the bag making method. It is also possible to make a bag using an appropriate adhesive, pressure-sensitive adhesive, or the like. In the present invention, the four sides of the light-shielding interior bag are heat-sealed. If the rigidity of the heat seal portion 4 in FIG. 4 is not sufficient, even if the interior bag is pressed with a buffer material, the bag will move in the box, and damage to the silver halide photographic material cannot be prevented. Moreover, when rigidity is too high, workability will worsen. Accordingly, the rigidity of the heat seal portion 4 is required to be 0.0005 N · m or more and preferably 0.01 N · m or less.

The box for storing the interior bag is for protecting and storing the light-shielding interior bag containing the laminated sheet-like silver halide photographic light-sensitive material. A specific example of the box is configured by a fitting inner box (body) and a lid, which is a thin rectangular parallelepiped as a whole.
The material of the box is not particularly limited, and it may be a paper box or a plastic box as long as it has a strength that can be used according to the size and weight of the laminate of sheet-like silver halide photographic light-sensitive materials. From the viewpoint of preventing dust generation, a plastic box is preferable. When the box is a paper box, the inside of the box is attached with paper using long fiber pulp with high surface strength, or a plastic film or dust-free paper is used. It is preferable to use a dust-generating flexible sheet by being attached inside. Further, it is preferable to contain carbon black or a conductive substance in the box in terms of preventing dust adsorption and static.

In the package of the present invention, it is preferable to reduce the pressure in the interior bag immediately before or immediately after heat sealing the interior bag. When the pressure is reduced to about 10 to 500 mm · H ₂ O, the movement of the laminate of the silver halide photographic light-sensitive material in the interior bag can be suppressed.

In the package of the present invention, an interior bag is accommodated inside the box. In this case, the movement of the interior bag in the box can be suppressed using a flexible cushioning member. By preventing the movement of the interior bag in the box, breakdown such as broken bags, scratches on the silver halide photographic light-sensitive material sheet, friction fogging, and generation of dust can be prevented.
The cushioning member can be arranged on the upper part (upper enclosure) or lower part (lower enclosure) of the heat seal part (hereinafter also referred to as “edge”) of the interior bag housed in the inner box (body). By closing, the edge of the interior bag is pressed, and the movement of the interior bag in the box can be prevented during transportation. When the cushioning member is arranged at the upper part of the edge of the interior bag, the edge of the interior member is pressed by the cushioning member and the lid, and when the cushioning member is arranged at the lower part of the edge of the interior bag, the edge of the interior member is the cushioning member. It will be held by the inner box (body).

  The buffer member may be either an upper enclosure or a lower enclosure, but the lower enclosure is preferable in consideration of workability. Further, the buffer member may be arranged in any way as long as the movement of the interior bag in the box in both the vertical and horizontal directions can be suppressed. Although it is most effective to dispose the cushioning member on the entire circumference of the four sides of the interior bag, the effect can be obtained even if only the corner of the interior bag or a part of the four sides. That is, the object of the present invention is achieved as long as all or part of the heat seal portion of the inner bag is held in the box while being pressed by the buffer member, and undesirable movement of the inner bag in the box can be prevented.

2-10 mm is preferable and the width | variety (pressing amount a) which hold | suppresses a heat seal part with a buffer member has especially preferable 4-6 mm.
The height (box holding amount b) of the heat seal portion pressed by the buffer member and the box lid when the buffer member is sealed below is 1 in the state before the lid is closed when the box depth is 20 mm. -5 mm is preferable, and 2-4 mm is particularly preferable.
In order for the buffer member to exert its role, the buffer member needs to be compressed by the bottom plate and the top plate of the box with the heat seal portion sandwiched in the box. For this reason, when using a fitting body and lid, it is preferable to fix both by appropriate means, for example, a method of fixing the body and lid with an adhesive tape for each box. Several boxes may be stacked, and the outside may be fixed vertically and horizontally with a strong tape.

As the buffer member, a conventionally known material can be appropriately selected as long as it is a flexible material, but a material having low dust generation is preferable. For example, various polyethylene resins, various polypropylene resins, polyolefin resins such as polybutene resins, ethylene copolymer resins such as polystyrene resins, copolymer resins mainly composed of propylene, polyolefin cross-linked resins, polyamide resins, etc. Alternatively, two or more kinds of mixed resins, polyurethane, natural rubber (sponge-like one produced from a rubber stock latex), and a foam obtained by adding a foaming agent to a synthetic rubber such as SBR can be used.
Preferred foaming agents to which the present invention can be effectively applied are substantially polyolefin resins (including modified / crosslinked resins), for example, various high density, medium density, low density polyethylene resins, and linear low density polyethylene. (L-LDPE) resin, polypropylene resin, propylene / ethylene copolymer resin, ethylene / vinyl acetate copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-acrylic acid copolymer resin, and polystyrene copolymer It is a thermoplastic resin foaming agent mainly composed of a resin. In particular, foamed polyethylene is preferable in terms of cost and characteristics. The expansion ratio is 10 to 70 times, preferably 20 to 40 times.

  As the foaming agent, either an inorganic foaming agent or an organic foaming agent may be used. Examples of the inorganic foaming agent include sodium hydrogen carbonate, ammonium carbonate, and ammonium hydrogen carbonate, and examples of the organic foaming agent include azo. Examples thereof include bisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate. There are gas mixing method, foaming agent decomposition method, solvent volatilization method, chemical reaction method, sintering method and elution method, etc., as methods for forming foam by blending with plastic material or rubber material. May be used.

  In addition, an antistatic agent can be added in order to prevent adhesion of dust and dirt due to charging of the foam. As an antistatic agent, an alkyl phosphate as an anionic one, an alkylamino derivative as a cationic one, a quaternary ammonium salt, an imidazoline type metal salt as an amphoteric one, a polyoxyethylene alkylamine as a nonionic one, There are polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, and the like. Specifically, dioxyethylene stearate amine, alkylamine-based lubricant (for example, trade name Electro Stripper), stearic acid monoglyceride, and the like are preferably used. In the present invention, it is also possible to use an air cushion or the like instead of the foam as the buffer member.

  The relative humidity in the interior bag in the present invention is preferably 30 to 55%, more preferably 35 to 45%.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Production Example 1> Preparation of Emulsion A In this production example, the production method of Emulsion A used for producing a silver halide photographic light-sensitive material is described.

1 liquid 650ml
20g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g

Two liquids 300ml
150 g silver nitrate

3 liquid 300ml
Sodium chloride 21g
Potassium bromide 58g
(NH ₄ ) ₃ [RhCl ₅ (H ₂ O)]
(0.001%, 20% NaCl aqueous solution) 15 ml

(NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] (0.001%) used in the third solution is obtained by dissolving the powder in a 20% aqueous solution of KCl and a 20% aqueous solution of NaCl, respectively, at 40 ° C. for 120 minutes. Prepared by heating.

  To 1 liquid maintained at 38 ° C. and pH 4.5, an amount corresponding to 67% of 2 liquid and 3 liquid was simultaneously added over 20 minutes with stirring to form 0.18 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 33% of the 2nd and 3rd liquids were added over 2 minutes to grow to 0.20 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.

4 liquid 100ml
Silver nitrate 50g

5 liquid 100ml
Sodium chloride 8.6g
Potassium bromide 19.2g
K ₄ [Fe (CN) ₆ ] .3H ₂ O (yellow blood salt) 20 mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitating agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated (in the range of pH 3.2 ± 0.2). Met). Next, about 2 L of the supernatant was removed (first water washing). Further, 2 L of distilled water was added, and sulfuric acid was added until silver halide precipitated. 2 L of the supernatant was again removed (second water washing). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. Gelatin 45g was added to the emulsion after washing and desalting, adjusted to pH 5.6, pAg 7.5, sodium benzenethiosulfonate 10mg, sodium benzenethiosulfinate 3mg, sodium thiosulfate pentahydrate 6.0mg 4.0 mg of gold acid was added and chemically sensitized so as to obtain an optimum sensitivity at 55 ° C., and 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene as a stabilizer and an antiseptic ( 100 mg of ICI (Proxel) was added.
Finally, a silver iodochlorobromide cubic grain emulsion containing 55 mol% of silver bromide and 0.08 mol% of silver iodide and having an average grain size of 0.21 μm and a coefficient of variation of 9% was obtained. The final emulsion was pH = 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 to 1.25 × 10 ³ kg / m ³ , and viscosity = 50 mPa · s. Further, the molar amount of silver inside the metal complex was 92.5% of the total silver amount.

<Production Example 2> Preparation of Emulsions B to H Preparation of Emulsions B to H was carried out in the same manner as Emulsion A, except that the halogen composition and grain size were changed as shown in Table 1. The halogen composition is adjusted by changing the addition amounts of sodium chloride and potassium bromide used in the third and fifth solutions, respectively, and the particle size is adjusted by adding the sodium chloride and preparation temperature of one solution. It was done by changing.
Emulsions B to H were used for preparing samples of a silver halide photographic light-sensitive material described later.

<Example 1> Preparation and test of samples 1 to 8 of silver halide photographic light-sensitive material << Preparation of coating solution >>
In the silver halide photographic light-sensitive material prepared in this example, a UL layer / emulsion layer / lower protective layer / upper protective layer is formed on one surface of a biaxially stretched polyethylene terephthalate film support having an undercoat layer on both sides. In addition, a conductive layer / back layer is formed on the opposite surface.
The composition of the coating solution used for forming each layer is shown below.

UL layer coating solution Gelatin 0.8g / m ²
Polyethyl acrylate latex 260mg / m ²
Compound (Cpd-7) 40 mg / m ²
Compound (Cpd-14) 10 mg / m ²
5-methylbenzotriazole 20 mg / m ²
Preservative (ICI, Proxel) 1.5mg / m ²

Emulsion layer coating solution Gelatin 1.2 g / m ²
Ag 2.9 g / m ²
Spectral sensitizing dye (III-3) 5.7 × 10 ⁻⁴ mol / Agmol
KBr 3.4 × 10 ⁻⁴ mol / Agmol
Compound (Cpd-1) 2.0 × 10 ⁻⁴ mol / Agmol
Compound (Cpd-2) 2.0 × 10 ⁻⁴ mol / Agmol
Compound (Cpd-3) 8.0 × 10 ⁻⁴ mol / Agmol
4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene
1.2 × 10 ⁻⁴ mol / Agmol
Hydroquinone 1.2 × 10 ^-2 mol / Agmol
Citric acid 3.0 × 10 ⁻⁴ mol / Agmol
5-methylbenzotriazole 20 mg / m ²
Hydrazine compound (Cpd-4)
7.0 × 10 ⁻⁴ mol / Agmol
Nucleation promoter (Cpd-5) 1.0 × 10 ⁻⁴ mol / Agmol
2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt
90 mg / m ²
Aqueous latex (Cpd-6) 100 mg / m ²
Polyethyl acrylate latex 150mg / m ²
Colloidal silica (particle size 10μm)
15% by weight based on gelatin
Compound (Cpd-7) 4% by mass relative to gelatin
Methyl acrylate and 2-acrylamide
Latex copolymer of 2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (mass ratio 88: 5: 7) 150 mg / m ²
Core-shell type latex (core: styrene / butadiene copolymer (mass ratio 37/63),
Shell: Styrene / 2-acetoxyethyl acrylate (mass ratio 84/16), core / shell ratio = 50/50)
150 mg / m ²
The coating solution pH was adjusted to 5.6 using citric acid.

Protective layer lower layer coating solution Gelatin 0.7g / m ²
Compound (Cpd-12) 15 mg / m ²
1,5-dihydroxy-2-benzaldoxime 10 mg / m ²
Polyethyl acrylate latex 300mg / m ²
Colloidal silica having a particle size of 10 to 20 μm (Nissan Chemical, Snowtex C) 300 mg / m ²
Compound (Cpd-13) 3 mg / m ²
Compound (Cpd-20) 5 mg / m ²
Preservative (ICI, Proxel) 1.5mg / m ²

Protective layer upper layer coating solution Gelatin 0.3 g / m ²
Matting agent of amorphous barium strontium sulfate with an average of 1.5 μm
25 mg / m ²
Compound (Cpd-8) (gelatin dispersion) 20 mg / m ²
Colloidal silica with a particle size of 10-20 μm (Nissan Chemical, Snowtex C) 30 mg / m ²
Compound (Cpd-9) 50 mg / m ²
Sodium dodecylbenzenesulfonate 20mg / m ²
Compound (Cpd-10) 20 mg / m ²
Compound (Cpd-11) 20 mg / m ²
Preservative (ICI, Proxel) 1 mg / m ²
In addition, the following thickener-Z was added to the coating liquid of each layer, and viscosity was adjusted.

Back layer coating solution Gelatin 3.8 g / m ²
Compound (Cpd-15) 40 mg / m ²
Compound (Cpd-16) 20 mg / m ²
Compound (Cpd-17) 90 mg / m ²
Compound (Cpd-18) 40 mg / m ²
Compound (Cpd-19) 26 mg / m ²
1,3-divinylsulfonyl-2-propanol 60 mg / m ²
Polymethylmethacrylate fine particles (average particle size 6.5 μm)
3mg / m ²
Liquid paraffin 78mg / m ²
Compound (Cpd-7) 120 mg / m ²
Compound (Cpd-20) 5 mg / m ²
Colloidal silica (particle size 10μm)
15% by weight based on gelatin
Calcium nitrate 20mg / m ²
Preservative (ICI, Proxel) 12mg / m ²

Conductive layer coating solution Gelatin 0.1 g / m ²
Sodium dodecylbenzenesulfonate 20mg / m ²
SnO ₂ / Sb (9/1 mass ratio,
(Average particle size 0.25 μm) 200 mg / m ²
Preservative (ICI, Proxel) 0.3 mg / m ²

<Method of coating on support>
A biaxially stretched polyethylene terephthalate support (thickness: 175 μm) on both sides of the support wound in the form of a roll with a subbing layer on the both sides, the emulsion layer side from the side closer to the support, the UL layer, the emulsion layer, 4 layers in order of protective layer lower layer and protective layer upper layer were coated simultaneously with a hardener solution added by a slide bead coater method while maintaining at 35 ° C., passed through a cold air set zone (5 ° C.), and then the emulsion surface Apply the coating layer on the inner surface of the support wound on the opposite side of the roll from the side closer to the support in the order of the conductive layer and back layer in the order of the curtain coater method while applying the hardener solution, and set the cold air Passed through zone (5 ° C). When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after apply | coating the back surface side, it conveyed in the state without contact at all to a roller and others until winding up. The coating speed at this time was 200 m / min.

《Drying conditions》
After setting, dry with 30 ° C dry air until the water / gelatin mass ratio reaches 800%, dry with 800 ° C to 200% dry air with 35 ° C and 30% relative humidity, and apply wind as it is. After 30 seconds from the time when the surface temperature reached 34 ° C. (deemed to be the end of drying), drying was performed for 1 minute with air at 48 ° C. and 2% relative humidity. At this time, the drying time was 50 seconds from the start of drying to 800% water / gelatin ratio, 35 seconds from 800% to 200%, and 5 seconds from 200% to the end of drying.

  The silver halide photographic light-sensitive material is wound up at 25 ° C. and a relative humidity of 65%, and then 100 sheets are cut into a size of 50.8 × 61 cm under the same environment, and as shown in FIG. The body was wrapped with a protective plate made of a polypropylene sheet, housed in an interior bag, and heat sealed on all four sides. The rigidity of the heat seal part was 0.0015 N · m. As shown in FIG. 2, the cushioning member covering the entire length of the heat seal portion of the four pieces of the inner bag is housed in a fitting box while being pressed and sealed, and sample 1 using silver halide emulsion A is used. The package was made. When the relative humidity in the bag of this package was measured on the seventh day after heat sealing, it was 50%.

<< Preparation of Samples 2-8 >>
The total gelatin amount per unit area and the back layer are provided on the side having the silver halide emulsion layer of the photosensitive material so that the flatness of the film becomes -8 mm, -5 mm, -3 mm, 0 mm, 3 mm, 5 mm, and 8 mm in order. Except for adjusting the total amount of gelatin per unit area on the side, packaging bodies of Samples 2 to 8 were prepared in exactly the same manner as the above Sample 1 preparation method.

<Evaluation>
(Evaluation of film flatness)
The silver halide photographic light-sensitive material of each sample was cut into 30 cm × 25 cm and placed on a horizontal surface with the emulsion surface facing upward in an environment of 25 ° C. and a relative humidity of 55% (after conditioning for 24 hours). The height of rising from the lower surface was measured, and the average value (mm) was taken as the flatness of the film. When the curl of the film was in the reverse direction, the measurement was made in the same manner with the emulsion surface facing downward, and it was expressed with a minus sign.

(Evaluation of black spots by vibration test)
A vibration test defined in JIS standard Z0200 was performed on each package of Samples 1-8. Then, using the silver halide photographic light-sensitive material in the package, a developer (Fuji Photo Film Co., ND-1) and a fixing solution (Fuji Photo Film Co., NF-1) are used. Using an automatic developing machine (manufactured by Fuji Photo Film Co., Ltd., FG-860KX), the film was processed under development conditions of 35 ° C. for 30 seconds, and the number of black spots per film was evaluated. Only black spots that could be confirmed with the naked eye using a 20-times magnifier were counted. The results are summarized in Table 2.

(Film transportability evaluation)
100 sheets of each of the sheet-like silver halide photographic light-sensitive materials of Samples 1 to 8 were used in a 25 ° C. and 55% relative humidity environment (after 24 hours of preparation humidity) using a film plotter (manufactured by Orbotech, LP-7008). An automatic conveyance test was performed. Table 2 shows the number of sheets conveyed normally.

  From the results shown in Table 2, a package produced by packaging a silver halide photographic light-sensitive material satisfying the conditions of the present invention according to the present invention can effectively control the occurrence of black spots in the silver halide photographic light-sensitive material. It is clear that the transportability is also good.

Example 2 Preparation and Test of Samples 9 to 23 of Silver Halide Photosensitive Material Using Emulsions B to H instead of Emulsion A, packaging bodies of Samples 9 to 15 were prepared in the same manner as in Example 1. . The flatness of the sheet-like photosensitive materials of Samples 9 to 15 was -1.5 mm.
(Examples 16 to 23)
A package of Samples 16 to 23 was prepared in the same manner as Samples 1 and 9 to 15 except that a silver halide emulsion layer was coated on the inside of a polyester film support wound in a roll. The flatness of the sheet-like photosensitive materials of Samples 16 to 23 was 3.0 mm.

  Table 3 summarizes the results of the vibration test and the transportability test performed in the same manner as Samples 1-8.

  From the results shown in Table 3, the package prepared by packaging the silver halide photographic light-sensitive material satisfying the conditions of the present invention according to the present invention can effectively control the occurrence of black spots in the silver halide photographic light-sensitive material. It is clear that the transportability is also good.

1 is a perspective view showing an embodiment of a state in which a laminate of a silver halide photographic light-sensitive material of the present invention is housed in an interior bag. FIG. It is a disassembled perspective view which shows typically one embodiment of the package of this invention. It is a perspective view which shows typically some arrangement | positioning of the buffer member in the package of this invention. It is sectional drawing of the package which shows typically the pressing amount and box pressing amount of the buffer member in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laminated body of sheet-like silver halide photographic light sensitive material 2 Protection plate 3 Interior bag 4 Heat seal part 6 Inner box (body)
7 Lid 8 Buffer material 9 Adhesive tape to fix the box body and lid a Pressing amount b Box pressing amount

Claims (7)

A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains on one side of a polyester film support and having a back layer on the other side. The flatness of the material is in the range of -10.0 to +2.0 mm, the silver halide grains contained in the emulsion layer have a halogen composition containing 40 mol% or more of silver bromide on average, and the halogenated The total gelatin amount per unit area on the side having the silver emulsion layer is 1.0 to 5.0 g / m ² , and the total gelatin amount per unit area on the side having the back layer has the silver halide emulsion layer. A silver halide photographic light-sensitive material characterized by being larger than the total amount of gelatin per unit area on the side. The silver halide photographic light-sensitive material according to claim 1, wherein the flatness is in the range of -5.0 to 0 mm. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the polyester film support has a thickness of 160 µm to 200 µm. The silver halide according to any one of claims 1 to 3, wherein the silver halide grains contained in the silver halide emulsion layer have a halogen composition containing 45 mol% to 75 mol% of silver bromide on average. Silver photographic material. The silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein a silver halide emulsion layer is coated on the outer surface of the polyester film support wound in a roll. The silver halide photographic light-sensitive material according to any one of claims 1 to 5, which is in a sheet form. The silver halide photographic light-sensitive material according to claim 6 is housed in a storage mating box in which all of the front, back and cross-section of the paperboard constituting the inner box and the lid are covered with plastic. A package of silver halide photographic light-sensitive material.

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