JP4887198B2 - Silver halide photographic light-sensitive material and image forming method - Google Patents

Description

  The present invention relates to a silver halide photographic light-sensitive material and a light-sensitive transfer material having an antistatic layer and a protective layer, and in particular, a halogenation excellent in scratch resistance at the time of use by a user, and less loss of matting agent and adhesion of dust. The present invention relates to a silver photographic light-sensitive material and to an image forming method capable of recording digital information on the silver halide photographic light-sensitive material with little deterioration.

  A silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) is generally a light-sensitive silver halide photographic emulsion layer (silver halide photographic light-sensitive layer) and an antihalation layer on a substrate such as an electrically insulating plastic film. And a protective layer, an intermediate layer, an undercoat layer, an antistatic layer and the like.

In recent years, the manufacturing technology of photosensitive materials has improved remarkably. Powder fall and sensitive materials tend to be charged with static electricity and dust (dust and dust). Furthermore, the development processing and printing speed of users are increasing, and the above problems have arisen as new problems as the speed increases. On the other hand, methods for defining a hardener in the antistatic layer and for defining the structure of metal oxide particles that are antistatic agents are disclosed (see, for example, Patent Documents 1 and 2). .
However, particularly in a film for a movie, the printing speed is remarkably increased, and there is not necessarily a tendency that the user is rubbed, the dust of the photosensitive material is scraped off, and the photosensitive material is charged with static electricity and dust (dust and dust) is easily attached. In addition, during such high-speed printing, it is a feature of recent years that dust that is different from metal oxide removal has emerged, and a new improvement technique has been required.

Conventional movie production is a method in which image information shot using a negative film for shooting is used as a master image, a copy is produced by printing on an intermediate film, and this is further printed on a positive film for movie use for projection. It was taken.
In many cases, intermediate films for replicating are used twice. The original negative film is printed on a negative intermediate film to create a master positive. The master positive is then printed again on the intermediate film to create a duplicate negative. Finally, the duplicate negative is printed on motion picture positive film to produce a screen print. By making a copy, the original image is deteriorated such as sharpness.
In recent years, due to an increase in the number of prints that can be printed at once due to simultaneous screening in the world and an increase in the demand for finishing prints in a short period of time, the speed of printing has increased, and scratch resistance and photosensitive materials required for intermediate films after development The need to prevent the matting agent from falling off as dust and to prevent the adhesion of dust (dust and dust) is becoming increasingly important.
On the other hand, in the production of this movie, digitization, in which an original image is digitally synthesized and edited, and converted again into an analog image on a film by a film recorder, has rapidly spread. This is because by combining and editing by a computer, it is possible to create a video that is impossible in reality and to expand the degree of freedom of video expression. As the original image, various kinds of information such as image information photographed on a photographing negative film as digital image information by a film scanner, image information photographed by an HD video camera, and computer graphics can be used.
When the original image is produced as digital information in a convenient manner as described above, and this is screened by conventional analog projection, the original image produced as digital information is printed on an intermediate film, which is compared with the conventional method. Similarly, the process of printing on movie positive film is performed.
However, when this method is used, a new problem has occurred as the resolution of digital information is increased. When an original image is printed on a silver halide photographic light-sensitive material, there is a problem that image quality is deteriorated and sufficient film quality cannot be maintained. There has been a need to improve image quality performance degradation caused by photographic characteristics of analog silver halide photosensitive materials, such as blurring, sharpness degradation, and color reproducibility. Japanese Patent Application Laid-Open No. 10-20461 discloses a silver halide color photographic light-sensitive material characterized in that the N value of a magenta image by laser scanning exposure is 100 μm to 200 μm. The N value is an amount corresponding to the blur of the image, and it is shown that the blur of characters is reduced in recording on color photographic paper. However, the pixel size is 12 μm or less at a resolution of 2000 dpi or more, which has been used in recent years in the field of movie production, and the N value as described above is clearly inappropriate for resolving fine image information. Furthermore, the film converted into analog image information by the film recorder becomes the original image, but in order to maintain the resolution of the original image, the process of printing directly on movie positive film is increasing, and the printing speed is increased. In response to this trend, the use of polyester supports is increasing. Therefore, a silver halide color photographic photosensitive material that records digital information on a polyester support without deterioration and is provided with scratch resistance, prevention of matting agent removal and prevention of dust (dust and dust) adhesion even during high-speed printing. The material was highly desired.
JP-A-8-36239 JP 2002-144493 A Japanese Patent Laid-Open No. 10-20461

  The present invention is superior in that it is excellent in scratch resistance, matting agent dropout and dust adhesion when used by a user, and is capable of realizing image formation capable of recording digital information on a silver halide photographic light-sensitive material with little deterioration. An object of the present invention is to provide a photosensitive material.

The object of the present invention has been achieved by the following means as a result of intensive studies.
<1>
On one side of the polyester support, it has a silver halide emulsion layer having at least one blue-sensitive layer, green-sensitive layer, and red-sensitive layer, and a non-photosensitive hydrophilic colloid layer. On the other side of the support, a conductive antistatic layer and a protective layer having a film thickness of 0.2 μm to 1 μm are provided in this order, and the protective layer is made of diacetylcellulose and polyacrylonitrile. A silver halide photographic light-sensitive material containing a matting agent.
<2>
The conductive antistatic layer includes at least one conductive metal oxide of ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, V ₂ O ₅ and a composite metal oxide thereof. And at least one metal oxide selected from the group consisting of metal oxides containing different atoms in addition to these metal oxides. The silver halide photographic light-sensitive material according to <1> .
<3>
When digital image information is recorded with a resolution of 2000 dpi or more, or when digital image information is recorded with digital image information of 3 million pixels or more, the blur k of the obtained image satisfies the following formula (A): The silver halide photographic light-sensitive material according to <1> or <2>.
k <4.5 × (D−0.2) ² (A)
In formula (A),
D: Color density of silver halide photographic material
Bleeding k: Bleeding at the color density D (μm)
<4>
The silver halide photographic light-sensitive material according to any one of <1> to <3>, wherein a color purity ratio is 80% or more in color reproduction at the time of image recording.
<5>
The silver halide photographic light-sensitive material according to any one of <1> to <4>, wherein the silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material for an intermediate film.
<6>
<1> An image forming method for recording digital image information recorded on the silver halide photographic light-sensitive material according to any one of <5> onto the silver halide photographic light-sensitive material in an analog manner.
Although the present invention relates to the above <1> to <6>, other matters (for example, matters described in the following (1) to (13)) are also described for reference.

(1) A silver halide emulsion layer having at least one blue-sensitive layer, green-sensitive layer, and red-sensitive layer on one side of the polyester support, and a non-photosensitive hydrophilic colloid An antistatic layer having conductivity and a protective layer are provided in this order on the other side of the support, and the protective layer contains a matting agent that is diacetylcellulose and polyacrylonitrile. A silver halide photographic light-sensitive material characterized by
(2) The conductive antistatic layer according to claim 1 is coated with at least one conductive metal oxide of ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, and V ₂ O _5. The at least one metal oxide selected from the group consisting of a metal oxide, a composite metal oxide thereof, and a metal oxide further containing a heteroatom in the metal oxide. Silver halide photographic light-sensitive material.
(3) The silver halide photographic light-sensitive material according to (1) or (2), wherein the protective layer according to (1) has a thickness of 0.2 μm to 1 μm.
(4) A method for forming a digital image on a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material has at least one blue-sensitive layer and green-sensitive layer on one side of a polyester support. And a silver halide emulsion layer having a red photosensitive layer, a non-photosensitive hydrophilic colloid layer, and a conductive antistatic layer and protective layer on the other side of the support. A silver halide photographic light-sensitive material provided in this order and containing a matting agent which is diacetyl cellulose and polyacrylonitrile in the protective layer, and digital image information on the silver halide photographic light-sensitive material has a resolution of 2000 dpi or more. An image forming method, wherein the image information can be recorded with little deterioration at the time of forming the recorded image.
(5) The silver halide photographic light-sensitive material according to any one of (1) to (3), wherein the image information can be recorded with little deterioration at the time of image formation in which digital image information is recorded at a resolution of 2000 dpi or more.
(6) The conductive antistatic layer according to claim 4, wherein at least one conductive metal oxide of ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, V ₂ O ₅ is used. 5 or at least one metal oxide selected from the group consisting of: a metal oxide, a composite metal oxide thereof, and a metal oxide further containing a heteroatom in the metal oxide. Image forming method.
(7) The silver halide photographic light-sensitive material according to (4) or (6), wherein the protective layer according to (4) has a thickness of 0.2 μm to 1 μm.
(8) A method for forming a digital image on a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material has at least one blue-sensitive layer and green-sensitive layer on one side of a polyester support. And a silver halide emulsion layer having a red photosensitive layer, a non-photosensitive hydrophilic colloid layer, and a conductive antistatic layer and protective layer on the other side of the support. A silver halide photographic light-sensitive material that is provided in this order and contains a matting agent that is diacetyl cellulose and polyacrylonitrile in the protective layer. Digital image information of 3 million pixels or more is recorded on the silver halide photographic light-sensitive material. An image forming method, wherein recording is performed with little deterioration.
(9) The silver halide photographic light-sensitive material according to any one of (1) to (3), wherein digital image information of 3 million pixels or more can be recorded with little deterioration.
(10) The conductive antistatic layer according to claim 8, wherein the conductive metal oxide is at least one of ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, and V ₂ O _5. The at least one metal oxide selected from the group consisting of a metal oxide, a composite metal oxide thereof, and a metal oxide further containing a heteroatom in the metal oxide. Image forming method.
(11) The silver halide photographic light-sensitive material according to claim 8 or 10, wherein the protective layer according to claim 8 has a thickness of 0.2 μm to 1 μm.
(12) The image forming method according to claim 5 or 9, wherein the blur k during image recording satisfies the following formula (A).
k <4.5 × (D−0.2) ² (A)
In formula (A),
D: Color density blur of silver halide photographic material k: Bleeding at color density D (μm)
(13) The image forming method according to any one of (5) to (9), wherein the color purity ratio is 80% or more in color reproduction during image recording.

  The present invention is superior in that it is excellent in scratch resistance, matting agent dropout and dust adhesion when used by a user, and is capable of realizing image formation capable of recording digital information on a silver halide photographic light-sensitive material with little deterioration. Photosensitive material A photosensitive material can be provided.

Hereinafter, the present invention will be described in more detail. The silver halide photographic light-sensitive material of the present invention has a silver halide emulsion layer having at least one blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on one side of a polyester support, And it has a non-photosensitive hydrophilic colloid layer, and on the other side of the support, a conductive antistatic layer and a protective layer are provided in this order, and diacetylcellulose and polyacrylonitrile are provided on the protective layer. It is characterized by containing the matting agent which is.
With the above-described configuration, the printing dust during use can be reduced, and the silver halide photographic light-sensitive material can realize image formation that is excellent in scratch resistance and matting agent removal and can record digital information with little deterioration. It can be used as a material.

  In the present invention, examples of the polyester support include polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and the like. Polyethylene terephthalate is particularly preferable, and in particular biaxial. Stretched and heat-set polyethylene terephthalate is particularly preferred from the viewpoints of stability, toughness and the like.

  The thickness of the support is not particularly limited, but is generally in the range of 15 to 500 μm, and particularly preferably in the range of 40 to 200 μm because it is advantageous in terms of ease of handling and versatility. The support may be transparent, and may contain an anthraquinone dye, dyed silicon, silicon dioxide, alumina sol, chromium salt, zirconium salt, titanium oxide and the like.

Next, the conductive antistatic layer of the present invention will be described.
The antistatic layer having electrical conductivity used in the present invention is not particularly limited as an antistatic agent, and may be either a polymer electrolyte or a metal oxide. The product is particularly preferred. For example, at least one conductive material selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ . Examples thereof include metal oxides or composite oxides thereof, and metal oxide fine particles further containing different atoms in these metal oxides. ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, V ₂ O ₅ , at least one conductive metal oxide or composite oxide thereof, and further different from these metal oxides More preferably, it is a metal oxide containing atoms. Examples of containing a small amount of different atoms include Zn or Al, In, TiO ₂ Nb or Ta, In ₂ O ₃ Sn, and SnO ₂ Sb, Nb or halogen elements. An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. When the added amount of the different element is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide. When the added amount exceeds 30 mol%, the degree of blackening of the particles increases, and the charge is increased. Since the prevention layer is darkened, it is not suitable as a sensitive material. Therefore, in the present invention, the material of the conductive metal oxide particles is preferably one containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure. These conductive oxide or composite oxide fine particles have a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. The primary particle size is preferably 0.002 to 0.7 μm, particularly preferably 0.005 to 0.3 μm. The resulting antistatic layer has a resistance of 10 ¹² Ω or less, more preferably 10 ¹⁰ Ω or less, and even more preferably 10 ⁹ Ω or less.

Next, the protective layer of the present invention will be described.
The protective layer used in the present invention is a silver halide light-sensitive material that can prevent desired scratch resistance and matting from falling off by using diacetylcellulose as a binder and polyacrylonitrile as a matting agent. Can be obtained. The coating amount of the matting agent is preferably 1 to 50 mg / m ² , and if it is less than 1 mg / m ² , the above problem cannot be achieved due to scratch resistance. Further, the matting agent may not be spherical, but the particle size in the direction parallel to the support surface is preferably 0.1 to 6 μm. Further, it is not preferable because the matting agent is lost and the transparency is lost.
The thickness of the protective layer is preferably 0.2 μm to 1 μm. If the thickness is 0.2 μm or less, the scratch resistance is lost, and if it is 1 μm or more, the transparency is lost and the above-described problem cannot be achieved. The film thickness referred to in the present invention is not based on the convex portion of the matting agent exposed on the film surface but on the surface parallel to the support.

Next, the overall antistatic layer and protective layer having conductivity according to the present invention will be described.
The binder used in the conductive antistatic layer of the present invention is Research Disclosure No. 17643, page 26, and ibid. The hydrophilic binder described on pages 18716 and 651 may be used, and it is represented by known thermoplastic resins, thermosetting resins, radiation curable resins and reactive resins used in various films. Hydrophobic binders may be used, but hydrophilic binders are preferred. Examples of the hydrophilic binder include water-soluble polymers such as gelatin, gelatin derivatives, casein, agar, starch, and polyvinyl alcohol, cellulose esters, and water-soluble polyesters. Most preferred is gelatin, and a gelatin derivative or the like may be used in combination. As gelatin, lime-processed gelatin and acid-processed gelatin are preferably used.

Furthermore, the antistatic layer having conductivity according to the present invention may contain various curing agents. Examples of the curing agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5. -Triazine, other compounds having reactive halogen, divinyl sulfone, 5-acetyl-1,3-diaacryloylhexahydro-1,3,5-triazine, compounds having reactive olefin, N-hydroxymethyl Mention may be made of halogen carboxaldehydes such as phthalimide, N-methylol compounds, isocyanates, aziridine compounds, acid derivatives, epoxy compounds and mucochloric acid.
For example, an isocyanate can be used for the protective layer. Examples of the aromatic isocyanate that can be used include toluene diisocyanate (TDI) and the like, and adducts of these isocyanates with active hydrogen compounds. Examples of the aliphatic isocyanate include hexamethylene diisocyanate (HMDI) and the like, and adducts of these isocyanates with active hydrogen compounds. Among these adducts of isocyanate and active hydrogen compound, those having a molecular weight in the range of 100 to 3000 are preferable. Of the aliphatic isocyanates, non-alicyclic isocyanates and adducts of these compounds and active hydrogen compounds are preferred. The amount of isocyanate to be used is preferably 5 to 75 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the binder.

  Next, the solvent or swelling agent for both the antistatic layer and the protective layer having conductivity in the present invention will be described. The solvent or swelling agent in the present invention is not particularly limited as long as it dissolves or swells the binder to be used. Examples of usable solvents for many binders include benzoic acid, salicylic acid, salicylic acid ester, monochloroacetic acid, Dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-nitropropanol, benzyl alcohol, benzaldehyde, acetonylacetone, acetophenone, benzamide, benzonitrile, benzylamine, methyl nicotinate, phenol, orthochlorophenol, parachlorophenol , Cresol, resorcin and other phenolic compounds are preferred. Among these, phenol compounds are more preferable, and phenol, orthochlorophenol, parachlorophenol, and resorcin are particularly preferable. As the usage-amount of these phenol type compounds, it is preferable to use in 0.01 to 1000% of range with respect to the binder of the layer to add, and the range of 0.1 to 100% is more preferable. If it is used more than 1000%, the sensitivity and storability as a photosensitive material are adversely affected and are unacceptable. On the other hand, if the content is less than 0.01%, sufficient adhesiveness required by the present invention cannot be obtained. The solvent or swelling agent of the present invention may be used for either or both of the antistatic layer and the protective layer.

  In the present invention, other components such as a surfactant and a slipping agent may be used in combination with both the antistatic layer and the protective layer having conductivity within a range that does not impair the effects of the present invention.

Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
Examples of the slip agent include phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; silicone compounds, and the like.

  The conductive antistatic layer and protective layer coating solution can be applied to the surface of the polyester support (the side on which the photosensitive layer is not provided) by a known coating method and dried to form a layer.

  Examples of the known coating methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, and extrusion coating.

The polyester support used in the present invention will be described in detail.
For the purpose of firmly adhering each layer to both surfaces of the polyester support, chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma in advance. It is preferable to perform surface activation treatment such as treatment, laser treatment, mixed acid treatment, or ozone acid treatment.

  For example, when a silver halide photographic light-sensitive material is produced by applying a coating solution for forming a silver halide photographic light-sensitive layer (hereinafter sometimes referred to as “a coating solution for a silver halide light-sensitive layer”), the support is used. (1) A method of obtaining an adhesive force by applying a coating solution for a silver halide photosensitive layer directly on the surface after the surface activation treatment, (2) Once the surface activation treatment is performed, an undercoat layer is provided, and a silver halide photosensitive layer coating solution is applied on the layer. Among these, the method (2) is more effective and widely used.

Next, the primer method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

The silver halide emulsion used in the present invention will be described.
A preferred silver halide used in the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing about 2 mol% to about 10 mol% of silver iodide.

  Silver halide grains in photographic emulsions have regular (three-dimensional isotropic) crystals such as cubes, octahedrons, and tetradecahedrons, and irregular crystal shapes such as spheres and plates. May have a crystal defect such as a twin plane, or a composite form thereof. In the present invention, it is preferable to use cubic particles.

The grain size of the silver halide grains used in the present invention can be evaluated using an electron microscope. Specifically, in the case of those having a regular crystal, the projected area equivalent diameter obtained by observation with an electron microscope (the diameter of this circle when the projected area of the particle is equivalent to the area of the circle) is obtained. The particle volume is calculated from the projected area equivalent diameter using the fact that it is a regular (three-dimensional isotropic) crystal, and the diameter of the sphere when the particle volume is equivalent to the volume of the sphere. Can be obtained by calculating. In the case of irregular (such as not three-dimensional isotropic) particles such as a plate shape, the volume is calculated from the projected area equivalent diameter and particle thickness obtained by electron microscope observation, and the sphere equivalent diameter is obtained. I can do it. The equivalent sphere diameter can also be obtained by the turbidity measurement method described in Particle Characterrization, 2nd edition, pages 14 to 19 (1985).
The average spherical equivalent diameter of the silver halide grains preferably used in the present invention is 0.02 μm or more and 0.5 μm or less, preferably 0.03 μm or more and 0.35 μm or less, more preferably 0.03 μm or more and 0.2 μm or less. is there.

  Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, I. Emulsion preparation and types, and ibid. 18716 (November 1979), p. 648, ibid. 307105 (November 1989), 863-865, and Grafkide, "Photophysics and Chemistry", published by Paul Montel (P. Glafkides, Chimie et Phisique Photographiques, Paul Montel, 1967), Duffin "Photographic Emulsion Chemistry". ”Published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966),“ Production and Coating of Photoemulsions ”by Zerikman et al., Published by Focal Press (VL Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 164) and the like.

  Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred.

  Tabular grains having an aspect ratio of about 3 or more can also be preferably used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); U.S. Pat. No. 4,434,226, 4, 414,310, 4,433,048, 4,439,520 and British Patent 2,112,157, and can be prepared easily.

  The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used.

  The above emulsion may have dislocations. In particular, tabular grains preferably have dislocations in the fringes. As a method for introducing dislocations, a method of forming a high silver iodide layer by adding an aqueous solution of alkali iodide or the like, a method of adding AgI fine particles, a method described in JP-A-5-323487, or the like is used. Can do.

  The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. . Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The contents relating to the overall emulsion of the present invention will be described below.
The reduction sensitization preferably used in the present invention is a method of adding a reduction sensitizer to silver halide, a method of growing or ripening silver halide grains in a low pAg atmosphere of pAg 1 to 7 called silver ripening. Any of the methods of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can also be selected. Also, two or more of these methods can be used in combination.
In particular, the method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.
As a reduction sensitizer, stannous salt, ascorbic acid and its derivatives, hydroquinone and its derivatives, catechol and its derivatives, hydroxylamine and its derivatives, amine and polyamines, hydrazine and its derivatives, paraphenylenediamine and its derivatives, form Examples include amidine sulfinic acid (thiourea dioxide), silane compounds, and borane compounds. These reduction sensitizers can be selected and used in the reduction sensitization of the present invention, and two or more compounds can be used in combination. Regarding the method of reduction sensitization, U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, 3,930, Regarding the method disclosed in No. 867 and the method of using a reducing agent, the methods disclosed in JP-B-57-33572, JP-A-58-1410 and JP-A-57-179835 can be used. Catechol and its derivatives, hydroxylamine and its derivatives, and formamidine sulfinic acid (thiourea dioxide) are preferred compounds as reduction sensitizers. The following general formulas (I) and (II) are also preferred reduction sensitizers.

In the general formulas (I) and (II), W ₅₁ and W ₅₂ represent a sulfo group or a hydrogen atom. However, at least one of W ₅₁ and W ₅₂ represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as an ammonium salt. Specific examples of preferable compounds include 3,5-disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, 2,3-dihydroxy-6,7-di And sulfonaphthalene potassium salt.
Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but a range of 10 ⁻⁷ to 10 ⁻¹ mol per mol of silver halide is appropriate. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth.
Examples of the silver halide solvent that can be used in the present invention include U.S. Pat. Nos. 3,271,157, 3,531,289, 3,574,628, and JP-A-54-1019. (B) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, JP-A-55-2982, etc. (C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A No. 53-144319, and (d) imidazoles as described in JP-A No. 54-1000071 (E) ammonia, (f) thiocyanate and the like.
Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. The amount of the solvent used varies depending on the type. For example, in the case of thiocyanate, a preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide.

In preparation of the emulsion of the present invention, for example, at the time of grain formation, desalting step, chemical sensitization, it is preferable that a metal ion salt is present before coating, depending on the purpose. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. As described above, it is possible to select a method of doping the whole particle and a method of doping only the core part of the particle, only the shell part, or only the epitaxial part. For example, Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For _{example, CdBr 2, CdCl 2, Cd} (NO 3) 2, Pb (NO 3) 2, Pb (CH 3 COO) 2, K 4 [Fe (CN) 6], (NH 4) 4 [Fe (CN) ₆ ], K ₂ IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) ₆ . The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one kind of metal compound, but may be used in combination of two or more kinds.
The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous hydrogen halide solution (for example, HCl, HBr) or an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. Moreover, you may add an acid, an alkali, etc. as needed. The metal compound can be added to the reaction vessel before particle formation or can be added during particle formation. Further, it can be added to a water-soluble silver salt (for example, AgNO ₃ ) or an alkali halide aqueous solution (for example, NaCl, KBr, KI) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.
A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 may be useful. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.
The silver halide grains of the present invention may contain at least one of sulfur sensitization, selenium sensitization, tellurium sensitization, gold sensitization, palladium sensitization, noble metal sensitization, and reduction sensitization in any step of the silver halide emulsion production process. Can be applied in the process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion of the present invention, the location of chemical sensitization nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemical sensitization nucleus is formed in the vicinity of the surface.
One chemical sensitization that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan. 1977, (TH James, The Theory of the Photographic Process, 4th ed, Macmillan, 1977), pages 67-76, and can also be performed using active gelatin. Disclosure, 120, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3, 772,031, No. 3,857,711, No. 3,901, No. 14, No. 4,266,018, and No. 3,904,415, and British Patent No. 1,315,755, pAg 5-10, pH 5-8 and temperature 30- At 80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers can be used. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable.

  In gold sensitization, P.I. Gold salts described by Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.

Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, US Pat. No. 2,642,361 (such as gold sulfide and gold selenide), 3503749 (such as gold thiolate having a water-soluble group), No. 5049484 (bis (methylhydantoinato) gold complex, etc.), No. 5049485 (mesoionic thiolate gold complex, such as 1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold complex) ), Macrocyclic gold complexes of 5252455 and 5391727, 5620841, 5700651, 5759760, 5759761, 5912111, 5912112, 5939245, JP-A-1-147537 No., 8-69074, No. 8-69075, No. -269554, Japanese Patent Publication No. 45-29274, German Patents DD-264524A, 264525A, 265474A, 298321A, JP-A-2001-75214, JP-A-2001-75215, JP-A-2001-75216, JP-A-2001. Gold compounds described in JP-A-75217 and JP-A-2001-75218 can also be used.
The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.
Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferable. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.

  In sulfur sensitization, unstable sulfur compounds are used. The unstable sulfur compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.

  Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, dicarboxymethyl- Dimethylthiourea, carboxymethyl-trimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethylrhodanine, 5-benzylidene-N-ethylrhodanine), phosphine sulfides (eg, trimethylphosphine) Sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg dimorpholine disulfide, cystine, hexathiocanthion), mercapto compounds (eg cysteine), polythionate , Elemental Such known sulfur compounds and active gelatin, such as yellow may also be used. Particularly preferred are thiosulfates, thioureas, phosphine sulfides and rhodanines.

  In selenium sensitization, unstable selenium compounds are used, and Japanese Patent Publication Nos. 43-13489, 44-15748, JP-A-4-25832, 4-109340, 4-271341, and 5-40324. 5-11385, JP-A-6-51415, JP-A-6-175258, JP-A-6-180478, JP-A-6-208186, JP-A-6-208184, JP-A-6-317867, Selenium compounds described in, for example, Kaihei 7-92599, JP-A-7-98483, and JP-A-7-140579 can be used.

  Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (for example, selenoamide, N, N -Diethylphenylselenamide), phosphine selenides (eg triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters (for example, methoxyphenylselenocarboxy-2,2-dimethoxycyclohexa) Ester), or the like may be used diacylselenides. Furthermore, non-labile selenium compounds described in JP-B Nos. 46-4553 and 52-34492, such as selenious acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, selenides, and the like may be used. I can do it. In particular, phosphine selenides, selenoureas, selenoesters and selenocyanic acids are preferred.

  In tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595, JP-A-4-271341, JP-A-4-3333043, JP-A-5-303157, JP-A-4-185004, and JP-A-4-330495. No. 4-333330, No. 5-4203, No. 5-4204, No. 5-106977, No. 5-286916, etc. can be used.

  Specifically, phosphine tellurides (for example, butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxydiphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis ( Ethoxycarbonyl) telluride), telluroureas (for example, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea) telluramides, telluroesters, etc. may be used.

  Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned daffine. It is described in the book “photographic emulsion chemistry”, pp. 138-143.

The amount of gold sensitizer and chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but is 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide, Preferably, about 10 ⁻⁷ to 10 ⁻³ mol can be used.

  The conditions for chemical sensitization in the present invention are not particularly limited, but pAg is 6 to 11, preferably 7 to 10, pH is 4 to 10, preferably 5 to 8, and temperature is 40 ° C to 40 ° C. 95 ° C, preferably 45 ° C to 85 ° C.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ · H ₂ O ₂ · 3H ₂ O, 2NaCO ₃ · 3H ₂ O ₂ , Na ₄ P ₂ O ₇ · 2H ₂ O _{2 , 2Na 2 SO 4 · H 2} O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (e.g., _{K 2 [Ti (O 2)} C 2 O 4] · 3H 2 O, 4K 2 SO 4 · Ti (O 2) OH · SO 4 · 2H 2 O, Na 3 [VO (O 2) (C 2 H 4 ) ₂ ] · 6H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ), oxyacid salt, iodine or bromine, halogen element, Halates (eg, potassium periodate), high valence Metal salts such as potassium hexacyanoferric acid and thiosulfonates.
Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).
Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents, and quinone organic oxidizing agents. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. The method can be selected from a method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both. These methods can be selected and used in either the particle formation step or the chemical sensitization step.
The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; for example, thioketo compounds such as oxadrine thione; azaindenes, for example , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.
The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.
The merocyanine dye or the complex merocyanine dye has a ketomethylene structure as a nucleus, for example, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine A 5- or 6-membered heterocyclic nucleus of a nucleus or a thiobarbituric acid nucleus can be applied.
These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.
Along with the 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. The timing when the sensitizing dye is added to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it is carried out after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. Spectral sensitization can be performed simultaneously with chemical sensitization, or prior to chemical sensitization as described in JP-A No. 58-113928, and silver halide grains can be precipitated. Spectral sensitization can be started by adding before completion of the production. Further, as taught in U.S. Pat. No. 4,225,666, these compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the remainder is chemically enhanced. It can be added after the sensitization, and may be any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide.

  Next, the silver halide photographic light-sensitive material of the present invention may use type 1 and type 2 compounds.

(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

First, the compound of type 1 will be described.
JP-A-9-211769 (specific example: 28-) shows a compound that can be emitted from a one-electron oxidant produced by one-electron oxidation of a type 1 compound, with a subsequent bond cleavage reaction. Compounds PMT-1 to S-37 described in Table E and Table F on page 32), JP-A-9-211774, JP-A-11-95355 (specific examples: compounds INV1-36), JP-T 2001-500996 (Specific Examples: Compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747,236, European Patent 786662A1 (Specific Examples: Compounds INV1-35), “One-photon two-electron sensitizer” or “deprotonated electron-donating sensitizer” described in patents such as European Patent No. 893732A1, US Pat. No. 6,054,260, US Pat. Compounds referred to. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

  Further, as a compound of type 1 that can be emitted by one-electron oxidant formed by one-electron oxidation and further undergoing bond cleavage reaction, one or more electrons can be emitted from the general formula (1) ( General formula (1) described in JP-A-2003-114487), general formula (2) (synonymous with general formula (2) described in JP-A-2003-114487), general formula (3) (JP-A-2003-114487) General formula (1) described in 2003-114488), general formula (4) (synonymous with general formula (2) described in Japanese Patent Application Laid-Open No. 2003-114488), general formula (5) (Japanese Patent Application Laid-Open No. 2003-114488). 114488 (synonymous with general formula (3)), general formula (6) (synonymous with general formula (1) described in Japanese Patent Application Laid-Open No. 2003-75950), and general formula (7) (Japanese Patent Application Laid-Open No. 2003-75950). In the general formula (2)), the general formula (8) The reaction represented by the general formula (1) described in 004-239934) or the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in JP-A-2004-245929) may occur. Among the compounds, a compound represented by the general formula (9) (synonymous with the general formula (3) described in JP-A No. 2004-245929) can be given. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formulas (1) and (2), RED ₁ and RED ₂ represent a reducing group. R ₁ represents a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form of a 5-membered or 6-membered aromatic ring (including an aromatic heterocycle) or a hexahydro form together with carbon atom (C) and RED _1. To express. R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Lv ₁ and Lv ₂ represent a leaving group. ED represents an electron donating group.

In the general formulas (3), (4), and (5), Z ₁ represents an atomic group that can form a 6-membered ring with a nitrogen atom and two carbon atoms of a benzene ring. R ₅ , R ₆ , R ₇ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ represent a hydrogen atom or a substituent. R ₂₀ represents a hydrogen atom or a substituent. When R ₂₀ represents a group other than an aryl group, R ₁₆ and R ₁₇ are bonded to each other to form an aromatic ring or an aromatic heterocycle. R ₈ and R ₁₂ represent a substituent that can be substituted on the benzene ring, m1 represents an integer of 0 to 3, and m2 represents an integer of 0 to 4. Lv ₃ , Lv ₄ and Lv ₅ represent a leaving group.

In the general formulas (6) and (7), RED ₃ and RED ₄ represent a reducing group. R _{21 to} R ₃₀ represent a hydrogen atom or a substituent. Z ₂ represents —CR ₁₁₁ R ₁₁₂ —, —NR ₁₁₃ —, or —O—. R ₁₁₁ and R ₁₁₂ each independently represents a hydrogen atom or a substituent. R ₁₁₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (8), RED ₅ is a reducing group and represents an arylamino group or a heterocyclic amino group. R ₃₁ represents a hydrogen atom or a substituent. X represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Lv ₆ is a leaving group and represents a carboxy group or a salt thereof, or a hydrogen atom.

The compound represented by the general formula (9) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by further oxidation after two-electron oxidation accompanied by decarboxylation. In General Formula (9), R ₃₂ and R ₃₃ each represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5-membered or 6-membered heterocycle with C═C. Z ₅ represents a group which forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group together with C—C. In the chemical reaction formula (1), R ₃₂ , R ₃₃ and Z ₃ have the same meanings as those in the general formula (9). Z ₄ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. Z ₆ represents a group which forms a 5-membered or 6-membered heterocyclic group together with C—C. M represents a radical, a radical cation, or a cation.

Chemical reaction formula (1)

Next, the type 2 compound will be described.
As a compound in which a one-electron oxidant produced by one-electron oxidation with a type 2 compound can further emit one or more electrons with a subsequent bond formation reaction, a compound represented by the general formula (10) A compound capable of causing the reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in JP-A-2004-245929). And a compound represented by the general formula (11) (synonymous with the general formula (2) described in JP-A No. 2004-245929). An organic compound that generates an (n + m) -valent cation with an intramolecular cyclization reaction from an n-valent cation radical described in JP-A-2003-121954 and the like (where n and m are each independently an integer of 1 or more) Are also included in type 2 compounds. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formula (10), RED ₆ represents a reducing group that is one-electron oxidized. Y is a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site capable of forming a new bond by reacting with a one-electron oxidant formed by one-electron oxidation of RED _6. Reactive group containing a non-aromatic heterocyclic moiety of a benzo-fused ring. Q represents a linking group that connects RED ₆ and Y.

The compound represented by the general formula (11) is a compound that causes a bond formation reaction represented by the chemical reaction formula (1) by being oxidized. In chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5-membered or 6-membered heterocycle with C═C. Z ₄ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. Z ₅ and Z ₆ represent a group which forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group together with C—C. M represents a radical, a radical cation, or a cation. In general formula (11), R ₃₂ , R ₃₃ , Z ₃ , and Z ₄ have the same meanings as in chemical reaction formula (1).

  Of the compounds of types 1 and 2, “a compound having an adsorptive group to silver halide in the molecule” or “a compound having a partial structure of a spectral sensitizing dye in the molecule” is preferable. Typical examples of the adsorptive group to silver halide are those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. The partial structure of the spectral sensitizing dye is a structure described on page 17, right line 34 to page 18, left line 6 of the same specification.

  More preferably, the compound of type 1 or 2 is “a compound having at least one adsorptive group to silver halide in the molecule”. More preferred is “a compound having two or more adsorptive groups to silver halide in the same molecule”. When two or more adsorptive groups are present in a single molecule, these adsorptive groups may be the same or different.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferred examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing heterocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  A quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing The quaternary salt structure of phosphorus includes a phosphonio group (trialkylphosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.). Can be mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably, a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salts include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As the counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.

  A preferred structure of the compound represented by type 1 or 2 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (X).

In general formula (X), P and R each independently represent a quaternary salt structure of nitrogen or phosphorus that is not a partial structure of a sensitizing dye. Q ₁ and Q ₂ each independently represent a linking group, specifically a single bond, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR _N —, —C (═O ) —, —SO ₂ —, —SO—, —P (═O) — each independently or a combination of these groups. Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. S is a residue obtained by removing one atom from a compound represented by type (1) or (2). i and j are integers of 1 or more, and i + j is selected from the range of 2-6. Preferably, i is 1 to 3, and j is 1 to 2, more preferably i is 1 or 2, and j is 1, and particularly preferably i is 1 and j is 1. The compound represented by the general formula (X) preferably has a total carbon number of 10 to 100. More preferably, it is 10-70, More preferably, it is 11-60, Most preferably, it is 12-50.

  Specific examples of the compounds represented by type 1 and type 2 are listed below, but the present invention is not limited thereto.

  The type 1 and type 2 compounds of the present invention may be used at any time during the preparation of the emulsion and during the photosensitive material production process. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of particle formation to before the desalting step, at the time of chemical sensitization (from immediately before the start of chemical sensitization to immediately after the end), and before application, more preferably at the time of chemical sensitization and before application.

  The compounds of type 1 and type 2 of the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added.

In the present invention, the compound of type 1 and / or type 2 is contained in an emulsion layer having the above-mentioned average sphere equivalent diameter of 0.35 μm or less and containing reduction-sensitized silver halide grains. It may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 mol per mol of silver halide, regardless of before and after the sensitizing dye. X10 ^-3 mol in a silver halide emulsion layer.

Next, the image recording method referred to in the present invention will be described.
(Bleeding evaluation method)
In the present invention, the blur k during image recording preferably satisfies the following formula (A).
k <4.5 × (D−0.2) ² (A)
In formula (A),
D: Color density density blur of silver halide photographic material k: Color blur (μm) at color density D
Here, the expression (A) needs to hold for all exposure light sources used during image recording. For example, when the exposure light source uses a three-color light source of red, green, and blue, each of these single-color exposures is performed, and the color density D at that time and the blur k at that density satisfy Expression (I).
In addition, it is preferable that the formula (A) holds for all the regions from Dmin + 0.2 to Dmax, but the evaluation is simply performed with two points of the color density Dmin + 1 and Dmin + 2, and the formula (A) is satisfied at any density. May be used as a condition. Here, Dmin represents the minimum value of the color density in the photosensitive material and corresponds to the density after processing of the unexposed film. Dmax represents the maximum value of the color density in the photosensitive material. The maximum value of the color density is made to correspond to the maximum value of the density of the digital image information. In the case of the widely used Cineon format, the maximum density is about Dmin + 2.
As shown in FIG. 1, the blur k is a blur width of the color image in the surface direction of the photosensitive material at a density of Dmin + 0.2 when the exposure amount is adjusted so that the photosensitive material develops a color density D as shown in FIG. Is measured as bleeding k (μm).

In the present invention, in order to record with little deterioration, the blur k during image recording preferably satisfies the above formula (A), more preferably satisfies the following formula (A-2), and the following formula (A- It is more preferable to satisfy 3). The smaller k is, the better.
k <4.0 × (D−0.2) ² (A-2)
k <3.5 × (D−0.2) ² (A-3)
(Evaluation method of color purity rate)
In the present invention, the color purity rate means sensitometric exposure for each of red, green, and blue, and the image density obtained for the main color density in the single color exposure is a, and the color density is mixed. This is expressed by the following formula (B) where b is the color density of another color different from the main color density and a high density color.
Color purity ratio (%) = (a−b) / a × 100 (B)
The requirement that the color purity ratio represented by the formula (B) is equal to or higher than a specific value needs to hold for all the regions where the main color density is from Dmin + 0.1 to Dmax, and single color exposure of red, green, and blue is performed. It is necessary to hold in either case. Dmin represents the minimum value of color density in the photosensitive material and corresponds to the density after processing of the unexposed film. Dmax represents the maximum value of the color density in the photosensitive material. In the case of the widely used Cineon format, the maximum density is about Dmin + 2.
In order to record with little deterioration, the silver halide photographic material of the present invention preferably has a color purity ratio of 80% or more, more preferably 85% or more, and still more preferably 90% or more during image recording.
The silver halide photographic material of the present invention preferably has a standard deviation of each blur k of cyan, magenta and yellow of 1.7 or less during image recording. More preferably, it is 1.35 or less, More preferably, it is 1.0 or less.
Although there is no particular limitation on an apparatus for recording digital information on a silver halide photographic light-sensitive material, a so-called film recorder, which can be used in the method of the present invention, a commercially available apparatus can be used. For example, ARRI ARRISER, ARRILASER HD using BGR semiconductor laser as the light source method, CELCO FURY, FIRETORM using CRT method, IMAGICA realtime, HSR high-speed recorder, DLP method using LCOS method Cinevater Cinevater One, Cinevater Five, etc. made by CINEVATION are used.

  In the present invention, “recording with little deterioration” means to suppress the disappearance of the image structure included in the digital image information at the time of recording, and to suppress the change at the time of recording the color information to a small amount. In order to suppress the disappearance of the image structure, it is effective to reduce the blur at the time of image recording, and it is effective to suppress the color purity rate at the time of image recording to suppress the change of the color information.

  In order to achieve the present invention, as a result of intensive studies, it has become clear that it is extremely effective to use a silver halide photographic light-sensitive material designed so as to reduce image deterioration during recording. The main cause of image blur is the scattering of the recording light inside the photosensitive material, and the blur of the image can be remarkably improved by reducing the scattered light. Since light scattering is greatly affected by the silver halide fine particles in the photosensitive material, it is effective to reduce the amount of silver halide fine particles used as much as possible, but it is also effective to reduce the size of the silver halide fine particles It is. Since all of these means cause a decrease in sensitivity of the photosensitive material, it is preferable to increase the sensitivity of the silver halide fine particles. From this point of view, it has been clarified that the sensitivity can be improved by adding a highly sensitized metal complex dopant to the silver halide emulsion. Further, it is known that a dye can be used to absorb scattered light, and this can be preferably used. There are water-soluble dyes and oil-soluble dyes. Water-soluble dyes are widely used in conventional light-sensitive materials, but oil-soluble dyes can also be preferably used. In order to increase color purity, it is effective to prevent color mixing. The color mixing inhibitor used in the intermediate layer between each color-sensitive layer generates processing color mixing when the amount used is insufficient, but if it is too much, the sensitivity of the photosensitive material is lowered, so it is set optimally. It is effective. It is also important to reduce spectral color mixing caused by exposure of a color-sensitive layer different from the exposure color. For example, the spectral color mixture can be reduced by increasing the difference between the green sensitivity and the blue sensitivity with respect to the red sensitivity of the red color-sensitive layer.

  In the light-sensitive material to which the method of the present invention can be applied, it is sufficient that at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer is provided on the support. As a typical example, a blue-sensitive, green-sensitive, and red-sensitive photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity are provided on a support. A silver halide photographic material having at least one non-photosensitive layer. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is composed of a high-sensitivity emulsion layer, a low-sensitivity emulsion layer, a low-sensitivity emulsion layer, as described in German Patent 1,121,470 or British Patent 923,045. Two layers of the sensitive emulsion layer are preferably arranged so that the photosensitivity decreases sequentially toward the support. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer is formed on the side away from the support. A high-sensitivity emulsion layer may be provided on the side close to the body.

  As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) or BH / BL / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH It can be installed in the order of.

  Further, as described in JP-B-55-34932, the blue photosensitive layer / GH / RH / GL / RL can be arranged in this order from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, they may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. it can.

  In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged, and an arrangement composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitive emulsion layer / high in the same color-sensitive layer from the side away from the support. They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer.

In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.
Further, the arrangement may be changed as described above even when there are four or more layers.

  In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used.

  Silver halide grains with fogged grain surfaces as described in US Pat. No. 4,082,553, grain interiors as described in US Pat. No. 4,626,498 and JP-A-59-214852 The fogged silver halide grains and colloidal silver are preferably applied to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of the unexposed and exposed areas of the photosensitive material. The preparation method is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. Any silver chloride, silver bromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but it is monodisperse (at least 95% of the silver halide grain mass or number of grains has a grain size within ± 40% of the average grain size). Are preferred).

  In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. Spectral sensitization or chemical sensitization may be performed on the surface of the silver halide grain, but it is not necessary to perform it. Prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver.
Coated silver amount of the light-sensitive material of the present invention, such as for to improved sharpness, preferably 8.0 g / ^{m 2} or less, more preferably 5.0 g / ^{m 2} or less, 3.0 g / ^{m 2} or less Most preferred.

Photographic additives that can be used in the present invention are also described in the RD, and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1. Chemical sensitizer, page 23, page 648, right column, page 8662. Sensitivity increasing agent, right column, page 648 Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer to page 649, right column 4. Brightener 24 pages 647 pages right column 868 pages 5. 5. Light absorber, 25-26 pages, 649, right column, page 873 Filters, -page, left page, 650 Dyes, ultraviolet absorbers Binder page 26 page 651 left column page 873-874 Plasticizer, page 27, page 650, right column, page 876 Lubricant 8. Coating aid, page 26-27, page 650, right column, page 875-876, surface active agent 9. Static page 27 page 650 right column pages 876-877 inhibitor
Ten. Matting agents 878-879.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.
Yellow coupler: coupler represented by formulas (I) and (II) described in EP 502,424A; formulas (1) and (2) described in EP 513,496A (Especially Y-28 on page 18); coupler represented by the formula (I) of claim 1 described in EP 568,037A; column 1 of US Pat. No. 5,066,576 A coupler represented by the general formula (I) described in lines 45 to 55; a coupler represented by the general formula (I) described in paragraph 0008 of JP-A-4-74425; European Patent Application Publication No. 498,381A1 Couplers described in claim 1 on page 40 (especially D-35 on page 18); couplers represented by formula (Y) described on page 4 of EP-A-447,969A1 (especially Y-1 (Page 17), Y-54 (page 41)); couplers represented by formulas (II) to (IV) described in columns 7 to 36-58 of US Pat. No. 4,476,219 (particularly II-17, 19 ( Lamb 17), II-24 (column 19)).

  Magenta couplers; L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13) described in JP-A-3-9737; European Patent No. 456,257 (A-4) -63 (page 134), (A-4) -73, -75 (page 139); M-4, -6 (page 26) described in EP 486,965 M-7 (page 27); M-45 (page 19) described in European Patent Application No. 571,959A; (M-1) (page 6) described in JP-A-5-204106; M-22 described in paragraph 0237 of JP-A-4-362631.

Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14 to 16) described in JP-A-4-204843; C-7 described in JP-A-4-43345 , 10 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385, general formula (1) A coupler represented by Ia) or (Ib).
Polymer coupler: P-1, P-5 (page 11) described in JP-A-2-44345.

  As couplers in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,873B and German Patent No. 3,234,533 are preferable.

  A coupler for correcting unwanted absorption of a coloring dye is a yellow colored compound represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP-A-456,257A1. Cyan couplers (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251) described in the European Patent Application Publication, Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US Pat.No. 4,833,069, (2) (column 8) described in US Pat. A colorless masking coupler represented by the formula (A) of claim 1 described in the pamphlet of WO92 / 11575 (especially exemplified compounds on pages 36 to 45) is preferred.

  Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of EP-A-378,236A1 (especially T-101 (page 30)) ), T-104 (31 pages), T-113 (36 pages), T-131 (45 pages), T-144 (51 pages), T-158 (58 pages)), European Patent Application Publication No. 436, 938A2 The compound represented by the formula (I) described on page 7 of the specification (especially D-49 (page 51)), the compound represented by the formula (1) of EP 568,037A (particularly ( 23) (page 11)), and compounds represented by formulas (I), (II), (III) described on pages 5 to 6 of European Patent Application Publication No. 440,195A2 (especially I- ( 1)); bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP-A 310,125A2 (especially (60) and (61) on page 1) And a compound represented by formula (I) in claim 1 of JP-A-6-59411 (particularly (7) (page 7)); ligand releasing compound: LIG- described in claim 1 of US Pat. No. 4,555,478 Table with X Compound (especially the compound in columns 21 to 41 of column 12); Leuco dye releasing compound: US Pat. No. 4,749,641, columns 3 to 8 of compound 1-6; Fluorescent dye releasing compound: US Pat. No. 4,774,181 Compound represented by COUP-DYE of claim 1 of the specification (especially compounds 1 to 11 of columns 7 to 10); development accelerator or fogging agent releasing compound: Formula (1) of column 3 of US Pat. No. 4,656,123 , (2), (3) (especially (I-22) in column 25) and ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2; A compound that releases a group that becomes a dye for the first time: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (particularly, Y-1 to Y-19 in columns 25 to 36).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 described in JP-A-62-215272 (Pages 140-144); Latex for impregnation with oil-soluble organic compounds: Latex described in US Pat. No. 4,199,363; Oxidizing agent scavenger: In columns 2, lines 54-62 of US Pat. No. 4,978,606 Compounds of formula (I) as described (especially I- (1), (2), (6), (12) (columns 4-5), 5-10 of column 2 of US Pat. No. 4,923,787 The formulas described in the rows (especially compound 1 (column 3); stain inhibitors: formulas (I) to (III) described in European Patent Application Publication No. 298321A, page 4, lines 30 to 33, especially I-47 , 72, III-1,27 (pages 24-48); antifading agent: A-6,7,20,21,23,24,25,26,30 described in European Patent Application Publication No. 298321A , 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69 to 118), U.S. Pat.No. 5,122,444, columns 25 to 38, II-1 to III-23, especially III-10 , Europe I-1 to III-4 described on pages 8 to 12 of the permitted application 471347A, in particular II-2, A-1 to 48 described in columns 32 to 40 of U.S. Pat.No. 5,139,931. In particular, A-39, 42; a material that reduces the amount of color-enhancing agent or color mixing inhibitor used: I-1 to II-15 described on pages 5 to 24 of EP-A-411324A, particularly I- 46; formalin scavenger: SCV-1 to 28 described on pages 24 to 29 of European Patent Application Publication No. 477932A, particularly SCV-8; hardener: described on page 17 of JP 1-214845 A Compounds (H-1 to 54) represented by formulas (VII) to (XII) described in columns 13 to 23 of H-1,4,6,8,14, U.S. Pat. No. -214852, compound (H-1 to 76) represented by formula (6) described at the lower right of page 8, particularly H-14, compound described in claim 1 of US Pat. No. 3,325,287; development inhibition Agent precursor: P-24,37,39 (pages 6-7) described in JP-A-62-168139; U.S. Pat.No. 5,019,492 Compounds of claim 1 in particular, 28, 29 of column 7; preservatives, fungicides: I-1 to III-43, in particular II-, of columns 3 to 15 of US Pat. No. 4,923,790 1,9,10,18, III-25; Stabilizer, antifoggant: I-1 to (14) described in columns 6 to 16 of U.S. Pat.No. 4,923,793, in particular I-1,60, ( 2), (13), compounds 1 to 65 described in columns 25 to 32 of U.S. Pat.No. 4,952,483, especially 36: chemical sensitizer: triphenylphosphine selenide, described in JP-A-5-40324 Compound 50; Dye: a-1 to b-20, particularly a-1,12,18,27,35,36, b-5,27 to 29 described on pages 15 to 18 of JP-A-3-156450 Pages V-1 to 23, especially V-1, FI-1 to F-II-43, particularly FI-11, F-II-8 described on pages 33 to 55 of EP-A-445627A. III-1 to 36 described on pages 17 to 28 of EP-A-457153A, especially III-1,3, Dye-1 described on pages 8 to 26 of WO88 / 04794. ~ 124 microcrystalline dispersion , Compounds 1 to 22 described on pages 6 to 11 of EP 319999A, particularly compound 1, compounds D represented by formulas (1) to (3) of EP 519306A -1 to 87 (pages 3 to 28), compounds 1 to 22 (columns 3 to 10) represented by formula (I) described in U.S. Application No. 4,268,622, formulas described in U.S. Application No. 4,923,788 Compounds (1) to (31) represented by (I) (Columns 2 to 9); UV absorbers: Compounds (18b) to (18r) represented by the formula (1) described in JP-A-46-3335 ), 101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) and formula (III) represented by the formula (I) described in EP-A-520938A Compounds HBT-1 to 10 (page 14), and compounds (1) to (31) represented by formula (1) described in European Patent Application No. 521823A (columns 2 to 9).

In the light-sensitive material of the present invention, the thickness from the light-sensitive silver halide layer closest to the support to the surface of the photographic light-sensitive material is preferably 24 μm or less, more preferably 22 μm or less, and most preferably 20 μm or less. The membrane swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer is defined as the saturated film thickness. It is defined as The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A.Green et al. (Photogr. Sci. Eng.), 19 卷, 2, 124-129. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.

  The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at 60 cm / min with respect to a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.

  Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and examples of polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.

  The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. . It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve matting properties, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm. )), Polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).

Examples of the present invention are shown below. However, the present invention is not limited to this example.
Example 1
<Preparation of silver halide photographic material>
[Preparation of support]
After biaxial stretching (3.3 times each in length and width), heat-fixing at 240 ° C. for 10 minutes, a polyethylene terephthalate film (PET film) having a thickness of 125 μm with both surfaces subjected to corona discharge treatment was prepared.

[Formation of support undercoat layer, antistatic layer and protective layer]
1) Adhesion (undercoating) layer After an ultraviolet irradiation (UV) treatment was performed on both sides of a PET film having a thickness of 125 μm, an adhesive layer having the following composition was provided on the emulsion surface side. The coating amount was 10 cc / m ² . Irradiation with ultraviolet rays was carried out by the method shown in the example of JP-B-45-3828.
Gelatin 4 parts by weight Distilled water 4 parts by weight Salicylic acid 1 part by weight Methanol 363 parts by weight Epoxidized polyamide 3 parts by weight p-chlorophenol 75 parts by weight

2) Back first layer The back first layer was coated with a liquid having the following formulation in the same manner as the undercoat layer.
Gelatin 5 parts by weight Distilled water 82 parts by weight Acetic acid 1 part by weight Methanol 1133 parts by weight Epoxidized polyamide 3 parts by weight p-chlorophenol 243 parts by weight

3) Back second layer 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N sodium hydroxide aqueous solution was added dropwise to this solution until the pH of the previous solution reached 3, thereby obtaining a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was allowed to stand at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated three times to remove excess ions. 200 parts by weight of colloidal precipitate from which excess ions have been removed are re-dispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 500 ° C. to give a bluish average particle diameter of 0.005 μm of stannic antimony monoxide composite Fine particles were obtained. The resistivity of the fine particle powder was 25 Ω · cm. A mixture of 40 parts by weight of the above fine powder and 60 parts by weight of water was prepared to pH 7.0, and after coarse dispersion with a stirrer, the residence time was 30 minutes with a horizontal sand mill (Dynomill, manufactured by Willy A. Backfen AG). A dispersion was prepared in which the primary particles were partly aggregated to become 0.05 μm as secondary aggregates.

A solution having the following formulation was applied so that the dry film thickness was 0.2 μm, and dried at 110 ° C. for 30 seconds.
・ The above conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₃ , 0.15 μm)
1806 parts by weight-gelatin 35 parts by weight-water 314 parts by weight-methanol 3945 parts by weight-NaOH 10 parts by weight-isopropyl alcohol 1092 parts by weight-higher alcohol nonionic surfactant 1 part by weight-epoxy hardener 9 parts by weight

4) Back third layer A liquid having the following formulation was applied so that the dry film thickness was 0.42 μm. Drying was performed at 70 ° C.
-118 parts by weight of diacetyl cellulose-6428 parts by weight of acetone-1 part by weight of polyacrylonitrile-8 parts by weight of methyl ethyl ketone-364 parts by weight of an isocyanate-based crosslinking agent-7 parts by weight Isocyanate-based crosslinking agent As shown in Table 1, a coated PET support was prepared.

[Preparation of silver halide emulsion]
(Preparation of emulsion Em-A)
An AgBrI monodisperse cubic emulsion was prepared according to the following. The following solutions were prepared.

<< Solution A >> Aqueous solution containing lime-processed ossein gelatin: 30 g, KBr: 0.4 g, and water: 1.3 L << Solution B >> 0.2 L aqueous solution containing AgNO ₃ : 20 g
<< Solution C >> 0.2 L of aqueous solution containing KBr: 15 g and KI: 0.6 g
<< Solution D >> 0.65 L of aqueous solution containing 162.5 g of AgNO ₃
<< Solution E >> 0.7 L of an aqueous solution containing KBr: 124.8 g, KI: 5.4 g, and NaCl: 0.6 g.

Solution A was placed in a reaction vessel and kept at 60 ° C. and stirred. 150 mL of Solution B was added over 5 minutes. During this time, Solution C was added while controlling the amount of addition so that pBr in the reaction vessel was maintained at 3.5. After completion of the addition, the temperature of the solution in the reaction vessel was raised to 70 ° C. Subsequently, 540 mL of solution D was added over 15 minutes. During this time, solution E was added while controlling the amount added so that pBr in the reaction vessel was maintained at 3.5. During this addition, 0.005 g of thiourea dioxide: 0.005 g of sodium benzenesulfonate: 0.0003 g of K ₂ IrCl ₆ : 0.0003 g was added to the reaction vessel.

  After completion of the addition, a desalting step was performed by a flocculation method. After the desalting step, the following chemical sensitization treatment and spectral sensitization treatment were performed. The emulsion after desalting is kept at 60 ° C., and the sensitizing dye, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, 4-hydroxy-6-methyl-1,3,3a 7-tetrazaindene (TAI), Compound 1, Compound 2, and Compound 3 were added for optimal spectral sensitization and chemical sensitization. As the sensitizing dye, the dyes shown in Table 1 were added in the amounts shown in Table 1. The obtained particles were cubic particles having an average sphere equivalent diameter of 0.18 μm and a coefficient of variation of 11%.

(Preparation of emulsion Em-B)
In the preparation of the emulsion Em-A, the temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to E, the addition rate of the solutions B to E, the pBr of the solution in the reaction vessel, thiourea dioxide, benzenesulfonic acid Emulsion Em-B was prepared in the same manner as Emulsion Em-A, except that sodium, K ₂ IrCl ₆ addition amount, sensitizing dye after completion of desalting, and chemical sensitization were appropriately changed.

(Preparation of emulsion Em-D)
In the preparation of the emulsion Em-A, the temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to E, the addition rate of the solutions B to E, the pBr of the solution in the reaction vessel, thiourea dioxide, benzenesulfonic acid Emulsion Em-D was prepared in the same manner as Emulsion Em-A, except that sodium, K ₂ IrCl ₆ addition amount, sensitizing dye after completion of desalting, and chemical sensitization were appropriately changed.

(Preparation of emulsion Em-G)
In the preparation of the emulsion Em-A, the temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to E, the addition rate of the solutions B to E, the pBr of the solution in the reaction vessel, thiourea dioxide, benzenesulfonic acid Emulsion Em-G was prepared in the same manner as Emulsion Em-A, except that sodium, K ₂ IrCl ₆ addition amount, sensitizing dye after completion of desalting, and chemical sensitization were appropriately changed.

(Preparation of emulsion Em-C)
An AgBrI monodisperse cubic emulsion was prepared according to the following. The following solutions were prepared.

<< Solution A >> Aqueous solution containing lime-treated ossein gelatin: 30 g, KBr: 0.4 g, and water: 1.5 L << Solution B >> 0.65 L of aqueous solution containing AgNO ₃ : 162.5 g
<< Solution C >> 0.7 L of an aqueous solution containing KBr: 125.4 g, KI: 4.5 g, and NaCl: 0.3 g.

Solution A was placed in a reaction vessel and kept at 55 ° C. and stirred. 540 mL of Solution B was added over 10 minutes. During this time, Solution C was added while controlling the amount of addition so that pBr in the reaction vessel was maintained at 3.5. During this addition, 0.007 g of thiourea dioxide: 0.007 g of sodium benzenesulfonate and 0.0005 g of K ₂ IrCl ₆ were added to the reaction vessel.

  After completion of the addition, a desalting step was performed by a flocculation method. After the desalting step, the following chemical sensitization treatment and spectral sensitization treatment were performed. The emulsion after desalting is kept at 62 ° C., and the sensitizing dye, chloroauric acid, sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI), Compound 1 Compound 2 and Compound 3 were added for optimal spectral sensitization and chemical sensitization. As the sensitizing dye, the dyes shown in Table 1 were added in the amounts shown in Table 1. The obtained particles were cubic particles having an average equivalent circle diameter of 0.10 μm and a coefficient of variation of 13%.

(Preparation of emulsions Em-E, F, H, I)
In the preparation of the emulsion Em-C, the temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to E, the addition rate of the solutions B to E, the pBr of the solution in the reaction vessel, thiourea dioxide, benzenesulfonic acid Emulsions Em-E, F, H, and I were the same as Emulsion Em-C, except that sodium, K ₂ IrCl ₆ addition amount, sensitizing dye after completion of desalting, and chemical sensitization were appropriately changed. Was prepared.

Table 1 shows the silver halide grains of Em-A to I.
Table 2 gives an introduction to the reduction sensitization of Em-A, D and G silver halide emulsions.
It was shown to.

[Preparation of multilayer color light-sensitive material sample]
Samples 101 to 112, which are multilayer color photosensitive materials composed of layers having the compositions shown below, were prepared on the other side of PET film supports 101 to 112 on which an antistatic layer and a protective layer having conductivity were coated.

(Sensitivity composition)
The amount of the silver coating amount for silver halide and colloidal silver, expressed in units of g / m ^2, also couplers, for additives and gelatin indicating the quantity, expressed in g / m ^2.

First layer (Anti-halation layer)
Black colloidal silver Silver coating amount 0.090
Silver iodobromide emulsion grains (average grain size 0.07 μm, silver iodide content 2 mol%) Silver coating amount 0.020
Gelatin 0.910

Second layer (intermediate layer)
Gelatin 2.160
ExF-4 0.694

Third layer: low-sensitivity red-sensitive emulsion layer Em-I silver coating amount 0.265
Gelatin 1.900
ExC-1 0.141
ExC-2 0.194
ExC-3 0.019
ExC-4 0.034
ExC-5 0.029
Cpd-2 0.105
Solv-1 0.440

Fourth layer: Intermediate red-sensitive emulsion layer Em-H Silver coating amount 0.236
Gelatin 1.067
ExC-1 0.091
ExC-2 0.125
ExC-3 0.012
ExC-4 0.028
ExC-5 0.008
Cpd-2 0.069
Solv-1 0.293.

5th layer; high sensitivity red-sensitive emulsion layer Em-G silver coating amount 0.228
Gelatin 0.757
ExC-1 0.057
ExC-2 0.079
ExC-3 0.019
ExC-5 0.005
Cpd-2 0.044
Solv-1 0.165.

Layer 6: Intermediate layer Gelatin 1.489
Cpd-1 0.069
ExF-5 0.074
ExF-7 0.098
ExF-8 0.028
Solv-1 0.223

Seventh layer: low-sensitivity green-sensitive emulsion layer Em-F silver coating amount 0.306
Gelatin 1.614
ExM-1 0.164
ExM-3 0.095
ExM-4 0.148
Solv-1 0.473
Solv-2 0.050

Eighth layer: Medium sensitivity green-sensitive emulsion layer Em-E Silver coating amount 0.187
Gelatin 0.525
ExM-1 0.048
ExM-2 0.037
ExM-3 0.021
ExM-4 0.043
Solv-1 0.171
Solv-2 0.020

Ninth layer: High-sensitivity green-sensitive emulsion layer Em-D Silver coating amount 0.254
Gelatin 0.447
ExM-1 0.040
ExM-2 0.031
ExM-3 0.018
ExM-4 0.036
Solv-1 0.150
Solv-2 0.010

10th layer: Yellow filter layer Yellow colloidal silver Silver coating amount 0.064
Gelatin 0.950
Cpd-1 0.105
ExF-8 0.049
Solid disperse dye ExF-9 0.125
Solv-1 0.121

Eleventh layer; low-sensitivity blue-sensitive emulsion layer Em-C silver coating amount 0.137
Gelatin 1.514
ExY-1 0.056
ExY-2 0.561
ExC-2 0.008
Solv-1 0.234

12th layer: Medium sensitivity blue-sensitive emulsion layer Em-B Silver coating amount 0.149
Gelatin 0.859
ExY-1 0.039
ExY-2 0.391
ExC-3 0.009
Solv-1 0.163.

13th layer: High-sensitivity blue-sensitive emulsion layer Em-A Silver coating amount 0.283
Gelatin 0.371
Type 1, Type 2 Compound 7 0.002
ExY-1 0.010
ExY-2 0.101
ExC-3 0.003
Solv-1 0.042.

14th layer; 1st protective layer Silver iodobromide emulsion grains Silver coating amount 0.211
(Average grain size 0.07 μm, silver iodide content 2 mol%)
Gelatin 0.683
Solid disperse dye ExF-9 0.054
ExF-1 0.073
H-1 0.160.

15th layer; 2nd protective layer Gelatin 0.727
B-1 (diameter 2.0 μm) 0.007
B-2 (diameter 2.0 μm) 0.005
B-3 0.047
H-1 0.170.

(Preparation of dispersion of organic solid disperse dye)
Tenth layer ExF-9 was dispersed by the following method.
ExF-9 wet cake (containing 17.6 wt% water) 2.800 kg
Sodium octylphenyldiethoxymethanesulfonate (31 mass% aqueous solution) 0.376 kg
F-15 (7% aqueous solution) 0.011 kg
4.020 kg of water
Total 7.210kg
(Adjusted to pH = 7.2 with NaOH).

After the slurry having the above composition is roughly dispersed by stirring with a dissolver, it is dispersed using an agitator mill LMK-4 at a peripheral speed of 10 m / s, a discharge rate of 0.6 kg / min, and a filling rate of zirconia beads having a diameter of 0.3 mm of 80%. Dispersion was performed until the absorbance ratio of the liquid reached 0.29 to obtain a solid fine particle dispersion. The average particle size of the dye fine particles was 0.29 μm.

  In addition to the above, Samples 101 to 112 thus prepared included 1,2-benzisothiazolin-3-one (average 200 ppm with respect to gelatin), n-butyl-p-hydroxybenzoate (about 1000 rpm), and 2- Phenoxyethanol (about 10000 rpm) was added.

Furthermore, Cpd-3 to Cpd-7, B-4, B-5, W-1 to W-13, F-1 to F-21, ExF-2, ExF-3, ExF-6, UV-1 to UV -5 was added.
The structural formulas of the substances used in the photosensitive material are shown below.

  About the samples 101-obtained above, the ARRILASER manufactured by ARRI using a BGR semiconductor laser as a light source system was used for calibration according to the ARRILASER procedure manual to obtain an exposed sample. These exposed samples were color developed according to the following procedure.

Treatment process Temperature (° C) Time (1) Prebath 27 ± 1 10 seconds (2) Removal of backing
Spray washing 27-38 5 seconds (3) Color development 41.1 ± 0.1 3 minutes (4) Stop 27-38 30 seconds (5) Water washing 27-38 30 seconds (6) Bleaching 27 ± 13 3 minutes (7 ) Washing 27 to 38 1 minute (8) Fixing 38 ± 12 2 minutes (9) Washing 27 to 38 2 minutes (10) Stable 27 to 38 10 seconds The prescription of the treatment liquid used in each treatment step is as follows .

Prescription of each treatment solution (1) Pre-bath Prescription value Water of 27-38 ° C 800ml
Borax (10 hydrate) 20.0g
Sodium sulfate (anhydrous) 100g
Sodium hydroxide 1.0g
Add water 1.00 liter pH (27 ° C.) 9.25.

(2) Color development Prescription value 21-38 ° C water 850ml
Kodak Anti-Calcium No. 4 2.0ml
Sodium sulfite (anhydrous) 2.0g
Eastman Anti-Fog AF-2000 5.0ml
Sodium bromide (anhydrous) 1.20 g
Sodium carbonate (anhydrous) 25.6g
Sodium bicarbonate 2.7g
Color developing agent;
4-Amino-3-methyl-N-ethyl-
N- (β-Methanesulfonamidoethyl) -aniline
4.0g
Add water 1.00 liter pH (27 ° C.) 10.20.

(3) Stop 900-ml water at 21-38 ° C
7.0N sulfuric acid 50ml
Add water 1.00 liter pH (27 ° C) 0.9.

(4) Bleaching solution 700-ml water at 24-38 ° C
Proxel GXL 0.07ml
Kodak Killing Agent No. 1 24.2g
28% ammonium hydroxide 30.0ml
Ammonium bromide 32.5g
Glacial acetic acid 10.0ml
Ferric nitrate (9 salt) 28.8g
Add water 1.0 liter pH (27 ° C.) 5.0 ± 0.2.

(5) Fixing Prescription value 20-38 ° C water 700ml
Kodak Anti-Calcium No. 4 2.0ml
185 ml of 58% ammonium thiosulfate solution
Sodium sulfite (anhydrous) 10.0 g
Sodium bisulfite (anhydrous) 8.4g
Add water 1.0 liter pH (27 ° C.) 6.5.

(6) Stable Prescription Value 21-27 ° C Water 1.00 L Kodak Stabilizer Additive 0.14 ml
Formalin (37.5% solution) 1.5ml
For these treated samples, scratch resistance, matting agent detachment, haze, charging characteristics, image bleeding, and color purity rate were evaluated as follows.

(1) Scratch resistance 0.025R diamond needle pressed using a scratch strength tester (HEIDON-18, manufactured by Shinto Chemical Co., Ltd.) after storing the above sample in an atmosphere of 25 ° C. and 65% RH for 3 days. Was measured under the condition of continuously increasing the load of 0 to 100 g. The load at which the scratches on the sample 101 started to enter was assumed to be 100 and expressed as a relative value. A smaller value than 100 indicates better scratch resistance.

(2) Dust adhesion and matting agent removal confirmation test In the above sample, the film was processed into an 18 cm wide long film and stored in an atmosphere of 25 ° C. and 65% RH for 3 days. Using a handling test machine, transport a long film at a line speed of 100 m / min, and rotate the driving roll (flat roll) with a wrap angle of 180 degrees reversely to 90 m / min for 5 minutes. After the conveyance, the amount of the powdery substance adhering to the surface of the driving roll, the scratch on the film back surface and the dropping of the matting agent were visually evaluated according to the following criteria.
[Standard]
○: Dust adhesion was not recognized at all.
Δ: Slight adhesion of dust was observed. The back surface was observed to confirm the matting agent falling off.
X: Adherence of dust was recognized. The back surface was observed to confirm the matting agent falling off.

(3) Haze In the above sample, before providing the silver halide photographic photosensitive layer (that is, the first and second undercoat layers are formed on one side of the PET film, and the antistatic layer and the surface layer are formed on the other side. ) Was measured based on the method described in the haze value of JIS-K-6714-1977 and used as an index indicating transparency. The measurement was performed using a haze meter (NDH-1001P, Nippon Denshoku Industries Co., Ltd.). The larger the value, the lower the transparency.

(4) Charging characteristics Each photosensitive material obtained above was measured based on the method described in the resistivity of JIS-K-6911-1979. The measurement was performed by conditioning each photosensitive material for 6 hours in an atmosphere of 23 ° C. and 65% RH, and then using a constant voltage power supply (TR-300C, manufactured by Takeda Riken Kogyo Co., Ltd.) and an ammeter (TR- 8651, Takeda Riken Kogyo Co., Ltd.) and a sample chamber (TR-42, Takeda Riken Kogyo Co., Ltd.).

(5) Image blur and color purity ratio Evaluation was performed by the method described in the text.

  Table 4 shows the evaluation results of the above (1) to (4).

  The blur k value of each of the blue photosensitive layer, the green photosensitive layer, and the red photosensitive layer is 4.4, 4.3, and 4.4, and the color purity ratio is 85%, 86%, and 87%. When digital image information was recorded at high resolution, a projection image with less deterioration and better sharpness and excellent color saturation was obtained.

  From the table, it can be seen that by adopting the constitution of the present invention, it is possible to obtain a silver halide color light-sensitive material excellent in scratch resistance, matting agent detachment, and charging characteristics without the haze. Furthermore, sensory evaluation of the image quality of the sample was performed by the following method. A landscape image with digital information of the number of pixels (2048 x 1556) is exposed to a 0.8 x 0.6 inch size with a B, G, R laser and subjected to color development processing. The resulting negative image and this negative image The film was further exposed to a Fuji color positive film F-CP, and then developed by the method described in the section “FUJIFILM PROCESSING MANUAL Motion Picture Films”, to obtain a positive image. In these projections, the sharpness of the negative image was evaluated, and the sharpness and color saturation of the positive image were evaluated.

Claims (6)

On one side of the polyester support, it has a silver halide emulsion layer having at least one blue-sensitive layer, green-sensitive layer, and red-sensitive layer, and a non-photosensitive hydrophilic colloid layer. On the other side of the support, a conductive antistatic layer and a protective layer having a film thickness of 0.2 μm to 1 μm are provided in this order, and the protective layer is made of diacetylcellulose and polyacrylonitrile. A silver halide photographic light-sensitive material containing a matting agent. The conductive antistatic layer includes at least one conductive metal oxide of ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, V ₂ O ₅ and a composite metal oxide thereof. and a silver halide photographic material as claimed in claim 1, characterized in that it contains at least one metal oxide selected from the group consisting of metal oxides, comprising the further heteroatom of these metal oxides .   When digital image information is recorded with a resolution of 2000 dpi or more, or when digital image information is recorded with digital image information of 3 million pixels or more, the blur k of the obtained image satisfies the following formula (A): The silver halide photographic light-sensitive material according to claim 1 or 2.
k <4.5 × (D−0.2) ²           (A)
In formula (A),
D: Color density of silver halide photographic material
Bleeding k: Bleeding at the color density D (μm)   The silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein a color purity ratio is 80% or more in color reproduction at the time of image recording. The silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein the silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material for an intermediate film. 6. An image forming method for recording the digital image information recorded on the silver halide photographic light-sensitive material according to claim 1 further on the silver halide photographic light-sensitive material in an analog manner.