JP2821505B2 - Silver halide photographic light-sensitive material with improved pressure resistance and processing method - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material having ultra-rapid processing suitability and improved pressure resistance, and a processing method. About.

[Background of the Invention]

In recent years, the demand for rapid processing of silver halide photographic light-sensitive materials has become extremely severe in the printing industry in order to cope with an increase in the amount of information and speed as a part of the information industry. On the other hand, in order to improve workability and stability, rapid access development which has improved the preservation which is a drawback from so-called lith development conventionally used in the development of printing photosensitive materials has come to be used. In this case, by including a high contrast agent such as a tetrazolium compound or a hydrazine compound in the silver halide emulsion, high contrast equivalent to lith development was achieved, and development for 20 to 30 seconds became possible. However, the above demands are more demanding for development of 20 seconds or less,
Moreover, of course, a decrease in image quality is not allowed. On the other hand, in printing, there is an operation called reduction, and therefore, it is not possible to simply reduce the amount of silver for the purpose of speeding up processing. Therefore, for rapid processing and silver saving, it is important to develop the silver halide in a short time without waste and to activate it effectively. In consideration of rapid processing and saving of silver, it is necessary to reduce the amount of gelatin. However, when the amount of gelatin is reduced, pressure resistance generally deteriorates. Therefore, there is an extremely strong demand for a silver halide photographic light-sensitive material and a processing method capable of ultra-rapid development, saving silver, and having improved pressure resistance.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in pressure resistance, effectively develops silver of the light-sensitive material, and provides a high-contrast image, even in ultra-rapid processing. Is to provide a way.

[Configuration of the invention]

The object of the present invention is to provide a water-soluble rhodium salt, a water-soluble iridium salt, a water-soluble osmium salt and a water-soluble ruthenium salt at any time until 95% of the total amount of silver nitrate added in the silver halide grain formation step. This is achieved by a silver halide photographic light-sensitive material characterized by having a silver halide photographic emulsion obtained by rush addition of at least one selected from the group consisting of:

Further, the light-sensitive material of the present invention is characterized in that the weight ratio of Ag / gelatin on the emulsion layer side is 1.0 or more, and the negative-working silver halide photographic light-sensitive material of the present invention is processed within a processing time of 19 seconds or less. , And the total processing time of Dry to Dry is 20 seconds to 60 seconds
It is characterized by being seconds.

 Hereinafter, the details of the present invention will be described.

In the present invention, Dry to Dry is the entire time from when the tip of a photosensitive material is inserted into an automatic developing machine to development, fixing, washing, drying and drying until the tip comes out of the automatic developing machine. That is, the quotient (sec) is obtained by dividing the total length (m) of the processing line including the crossing part of each tank by the line transfer speed (m / sec), and the value is characterized by being 60 seconds or less.

In the embodiment of the present invention, the amount of gelatin refers to the amount of gelatin on the side including the photosensitive silver halide emulsion tank with respect to the support.
The total amount of gelatin in the layers or more is not limited to the amount of gelatin in the silver halide emulsion layer. When the amount of silver is applied to a plurality of layers on the same side with respect to the support, the amount of silver is defined relative to the total amount of silver in each layer.

The water-soluble rhodium salt, iridium salt, osmium salt and ruthenium salt (hereinafter collectively referred to as water-soluble metal salt) used in the present invention include all conventionally known water-soluble metal salts. Typical examples thereof include rhodium chloride, hexachlorodium hydrochloride, iridium chloride, hexachloroiridate, osmium chloride, hexachloroosmate, ruthenium chloride, and hexachlororuthenate.

By doping these salts inside the grains during grain formation, the pressure resistance is improved.

Preferred examples of the high contrast agent used in the present invention include tetrazolium compounds. Specific examples of the tetrazolium compound include general formulas [I] -1, [I] -2, and [I] described in JP-A-62-11253. ] -3.

 Where R_Five, R₇, R₈, R₉, R₁₂, R₁₃, R₁₄And R_FifteenIs Al
Kill groups (for example, methyl, ethyl, propyl,
Silyl group), allyl group, phenyl group (for example, phenyl
Group, tolyl group, hydroxyphenyl group, carboxyphen
Nyl, aminophenyl, mercaptophenyl,
Toxiphenyl group), naphthyl group (eg, α-naphthyl)
Group, β-naphthyl group, hydroxynaphthyl group, carbo
Xinaphthyl group, aminonaphthyl group, etc.) and heterocyclic group
(Eg thiazolyl, benzothiazolyl, oxazolyl
Ryl group, pyrimidinyl group, pyridyl group, etc.)
Represents a metal chelate or complex
May be a group that forms R₆~ R_TenAnd R₁₁Each
Allyl group, phenyl group, naphthyl group, heterocyclic group,
Kill groups (eg, methyl, ethyl, propyl,
Group, mercaptomethyl group, mercaptoethyl group, etc.),
Hydroxyl group, alkylphenyl group, alkoxyphenyl group,
Carboxyl group or its salt, carboxyalkyl group
(For example, methoxycarbonyl group, ethoxycarbonyl
Group), amino group (for example, amino group, ethylamino group,
Nilino group), mercapto group, nitro group and hydrogen atom
And D represents a divalent aromatic group;
E is an alkylene group, an arylene group, an aralkylene group
X represents a group selected from Represents an anion and n is 1
Or 2 is represented. However, the compound forms an inner salt
In this case, n is 1.

Next, specific examples of the cation portion of the tetrazolium compound used in the present invention are shown, but the cation portion of the compound that can be used in the present invention is not necessarily limited to these.

(T-1) 2- (benzothiazol-2-yl) -3
-Phenyl-5-dodecyl-2H-tetrazolium (T-2) 2,3-diphenyl-5- (4-t-octyloxyphenyl) -2H-tetrazolium (T-3) 2,3,5-triphenyl- 2H-tetrazolium (T-4) 2,3,5-tri (p-carboxyethylphenyl) -2H-tetrazolium (T-5) 2- (benzothiazol-2-yl) -3
-Phenyl-5- (o-chlorophenyl) -2H-tetrazolium (T-6) 2,3-diphenyl-2H-tetrazolium (T-7) 2,3-diphenyl-5-methyl-2H-tetrazolium (T- 8) 3- (p-hydroxyphenyl) -5
Methyl-2-phenyl-2H-tetrazolium (T-9) 2,3-diphenyl-5-ethyl-2H-tetrazolium (T-10) 2,3-diphenyl-5-n-hexyl-2
H-tetrazolium (T-11) 5-cyano-2,3-diphenyl-2H-tetrazolium (T-12) 2- (benzothiazol-2-yl) -5
-Phenyl-3- (4-tolyl) -2H-tetrazolium (T-13) 2- (benzothiazol-2-yl) -5
-(4-chlorophenyl) -3- (4-nitrophenyl) -2H-tetrazolium (T-14) 5-ethoxycarbonyl-2,3-di (3-
(Nitrophenyl) -2H-tetrazolium (T-15) 5-acetyl-2,3-di (p-ethoxyphenyl) -2H-tetrazolium (T-16) 2,5-diphenyl-3- (p-tolyl)- 2H-tetrazolium (T-17) 2,5-diphenyl-3- (p-iodophenyl) 2H-tetrazolium (T-18) 2,3-diphenyl-5- (p-diphenyl) -2H-tetrazolium (T- 19) 5- (p-Promophenyl) -2-phenyl-3- (2,4,6-trichlorophenyl) -2H-
Tetrazolium (T-20) 3- (p-hydroxyphenyl) -5
-(P-nitrophenyl) -2-phenyl-2H-tetrazolium (T-21) 5- (3,4-dimethoxyphenyl) -3
-(2-ethoxyphenyl) -2- (4-methoxyphenyl) -2H-tetrazolium (T-22) 5- (4-cyanophenyl) -2,3-diphenyl-2H-tetrazolium (T-23) 3- (P-acetamidophenyl) -2,
5-diphenyl-2H-tetrazolium (T-24) 5-acetyl-2,3-diphenyl-2H-
Tetrazolium (T-25) 5- (flu-2-yl) -2,3-diphenyl-2H-tetrazolium (T-26) 5- (thien-2-yl) -2,3-diphenyl-2H-tetrazolium (T- 27) 2,3-diphenyl-5- (pyrid-4-yl) -2H-tetrazolium (T-28) 2,3-diphenyl-5- (quinol-2)
Yl) -2H-tetrazolium (T-29) 2,3-diphenyl-5- (benzoxazol-2-yl) -2H-tetrazolium (T-30) 2,3-diphenyl-5-nitro-2H-tetrazolium (T −31) 2,2 ′, 3,3′-Tetraphenyl-5,5′-
1,4-butylene-di- (2H-tetrazolium) (T-32) 2,2 ', 3,3'-tetraphenyl-5,5'-
p-phenylene-di- (2H-tetrazolium) (T-33) 2- (4,5-dimethylthiazol-2-yl) -3,5-diphenyl-2H-tetrazolium (T-34) 3,5-diphenyl- 2- (triazine-
2yl-2H-tetrazolium) (T-35) 2- (benzothiazol-2-yl) -3-
(4-methoxyphenyl) -5-phenyl-2H-tetrazolium (T-36) 2,3-dimethoxyphenyl-5-phenyl-2H-tetrazolium (T-37) 2,3,5-tris (methoxyphenyl)- Two
H-tetrazolium (T-38) 2,3-dimethylphenyl-5-phenyl-2H-tetrazolium (T-39) 2,3-hydroxyethyl-5-phenyl-2H-tetrazolium (T-40) 2,3- Hydroxymethyl-5-phenyl-2H-tetrazolium (T-41) 2,3-cyanohydroxyphenyl-5-
Phenyl-2H-tetrazolium (T-42) 2,3-di (p-chlorophenyl) -5-phenyl-2H-tetrazolium (T-43) 2,3-di (hydroxyethoxyphenyl) -5-phenyl-2H- Tetrazolium (T-44) 2,3-di (2-pyridyl) -5-phenyl-2H-tetrazolium (T-45) 2,3,5-tris (2-pyridyl) -2H-tetrazolium (T-46) When a 2,3,5-tris (4-pyridyl) -2H-tetrazolium compound is used as a non-diffusible compound, a non-diffusible compound obtained by appropriately selecting a cation portion and an anion portion is used.

Examples of the anion part of the tetrazolium compound used in the present invention include halogen ions such as chloride ion, bromide ion and iodide ion, acid groups of inorganic acids such as sulfuric acid, nitric acid and perchloric acid, sulfonic acid, carboxylic acid and the like. Acid groups of organic acids, lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anion, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anion, higher alkyl sulfate anions such as lauryl sulfate anion, di- Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion; polyether alcohol sulfate anions such as cetyl polyethenoxy sulfate anion; higher fatty acid anions such as stearic anion; polyacrylic Examples thereof include polymers in which an acid radical is added to a polymer such as a ruthenate anion.

The non-diffusible tetrazolium compound according to the present invention can be synthesized by appropriately selecting the anion portion and the cation portion. The compound according to the present invention thus synthesized is, for example, 2,3,5-triphenyl-2H
A tetrazolium-dioctyl succinate sulfonate, etc., in which each soluble salt is dispersed in gelatin, and then both are mixed and dispersed in a gelatin matrix; May be dissolved in a suitable solvent (for example, dimethyl sulfoxide) and then dispersed in a gelatin matrix. When dispersion is difficult to be uniform, a method of emulsifying and dispersing with an appropriate homogenizer such as an ultrasonic wave or a Manton-Gaulin homogenizer may give good results. Further, it is also possible to finely disperse in a high boiling point solvent such as dioctyl phthalate, protect the dispersion, and disperse in a hydrophilic colloid layer.

The silver halide emulsion used in the light-sensitive material of the present invention includes silver halides such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, and silver chloroiodobromide. Any of those used can be used, and preferred is a silver chlorobromide containing 50 mol% or more of silver chloride as a negative-working mercury halide emulsion. The silver halide grains may be obtained by any of an acidic method, a neutral method and an ammonia method. The silver halide emulsion used in the present invention may have a single composition, or grains having a plurality of different compositions may be contained in a single layer or divided into a plurality of layers.

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Patent 4,
Nos. 183,756, 4,225,666, JP No. 55-26589, and JP-B-55-42737, etc., The Journal of Photographic Science (J.Photgr.Sci) .21. 39 (197
Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be produced by a method described in a document such as 3) and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

Emulsions having any grain size distribution may be used, and emulsions having a wide grain size distribution (referred to as polydisperse emulsions)
May be used, or an emulsion having a narrow particle size distribution (referred to as a monodisperse emulsion) may be used alone or as a mixture of several kinds.
Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

In the present invention, a monodisperse emulsion is preferred. As the monodispersed silver halide grains in the monodispersed emulsion, the weight of silver halide contained within a grain size range of ± 20% around the average grain size is 60% or more of the weight of all silver halide grains. Is preferred, particularly preferably 70% or more, more preferably 80%
That is all.

Here, the average particle size is the frequency ni of the particles having the particle size ri and
product ni × ri ³ and ri ³ defines a grain size ri when the maximum.

(Three significant figures, the smallest number is rounded off to the nearest whole number.) The particle size referred to here is the diameter of spherical silver halide grains, and the projection of spherical non-spherical grains. This is the diameter when the image is converted into a circular image having a peripheral area.

The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection. (The number of particles to be measured is 1000 or more indiscriminately.) Particularly preferred highly monodispersed emulsions of the present invention are: Is less than 20% of the distribution defined by
It is more preferably at most 15%.

Here, the average particle diameter and the standard deviation of the particle diameter are determined from ri defined above.

Monodisperse emulsions can be obtained with reference to JP-A-54-48521, JP-A-58-49938 and JP-A-60-122935.

The photosensitive silver halide emulsion is not subjected to chemical sensitization,
A so-called unripened (Primitive) emulsion can be used as it is, but usually it is chemically sensitized. For chemical sensitization, the Glafkides or Zelikman et al., Or HF
rieser edited by Die Grundlagen der Photographischen Prozesse mit
Silberhalogeniden, Akademische Verlagsgesellschaf
t, 1968).

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound, or the like alone or in combination Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Patent Nos. 1,574,944 and 2,41.
0,689, 2,278,947, 2,728,668, 3,656,955
No. As the reduction sensitizer, primary salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds and the like can be used, and specific examples thereof are U.S. Pat.Nos. 2,487,850, 2,419,974, and 2,
518,698, 2,983,609, 2,983,610, 2,694,6
No. 37. In order to sensitize precious metals, in addition to gold complex salts, periodic table VII of platinum, iridium, palladium, etc.
Complex salts of Group III metals can be used, and specific examples are described in U.S. Pat. Nos. 2,399,083 and 2,448,060 and British Patent 618,061.

The conditions such as pH, pAg, and temperature during chemical sensitization are not particularly limited, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is 5 to 11, particularly 8 to 10. It is preferable to keep. The temperature is preferably from 40 to 90 ° C, particularly preferably from 45 to 75 ° C.

The photographic emulsion used in the present invention is the above-described sulfur sensitized,
In addition to sulfur sensitization, a reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound or the like can also be used in combination.

As the photosensitive emulsion, the above-mentioned emulsions may be used alone, or two or more kinds of emulsions may be mixed.

In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3,3
Various stabilizers such as a, 7-tetrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole and the like can also be used. If necessary, a silver halide solvent such as thioether or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention may be formed by a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt during the process of forming and / or growing the grains. Alternatively, a metal ion can be added using a complex salt, and the metal ion can be contained inside the particle and / or on the particle surface.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. The removal of the salts can be performed according to the method described in Research Disclosure No. 17643.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye. 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 the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei such as a tetrazole nucleus and a pyridine nucleus, and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzylindolenine nucleus, an indole nucleus , A benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be used.

The sensitizing dye used in the present invention is used at the same concentration as that used for a normal negative-working silver halide emulsion. Especially,
It is advantageous to use a silver halide emulsion at a dye concentration that does not substantially reduce the intrinsic sensitivity of the emulsion. The sensitizing dye is preferably about 1.0 × 10 ^-5 to about 5 × 10 ^-4 mol per mol of silver halide, and more preferably about ⁴ × 10 ^-5 mol of sensitizing dye per mol of silver halide.
It is preferably used at a concentration of ^{-5 to} 2 x ^10-4 mol.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. As the sensitizing dye advantageously used in the present invention, more specifically, for example, the following can be mentioned.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent 929,080 and U.S. Pat.
No. 31,658, No. 2,493,784, No. 2,503,776, No. 2,519,00
No. 1, No. 2,912,329, No. 3,656,956, No. 3,672,897,
3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, JP-B-44-14030, and 52-24844
And JP-A-48-73137 and JP-A-61-172140. Sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
939,201, 2,072,908, 2,739,149, 2,945,7
No. 63, British Patent No. 505,979, JP-B-48-42172 and the like, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical examples. Further, sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions include, for example, U.S. Pat.
9,234, 2,270,378, 2,442,710, 2,454,629
No. 2,776,280, JP-B-49-17725, JP-A-50-62
No. 425, No. 61-29836, No. 60-80841, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical examples.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Representative examples are U.S. Pat.Nos. 2,688,545, 2,977,229, 3,397,060,
3,522,052, 3,527,641, 3,617,293, 3,62
8,964, 3,666,480, 3,672,898, 3,679,428
Nos. 3,703,377, 3,769,301, 3,814,609,
3,837,862, 4,026,707, UK Patent 1,344,281
No. 1,507,803, JP-B43-4936, 53-12375
And JP-A Nos. 52-110618 and 52-109925.

The silver halide photographic light-sensitive material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, salicyl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a reduction in sensitivity and generation of fog during the production process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-
5-mercaptotetrazole), mercaptopyridines, the above heterocycle having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinethione, azaindenes such as tetraazaindenes (particularly 4-hydroxy-substituted) (1,3,3a,
7) Many compounds known as stabilizers can be added, such as tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acid, and the like.

One example of a compound that can be used is K. Mees, The Theory of the Photographic Process (The Theory
of the Photographic Process, 3rd ed., 1966).

For further details of these specific examples and methods of using them, see, for example, U.S. Patent Nos. 3,954,474, 3,982,947,
No. 021,248 or JP-B-52-28660 can be referred to.

The silver halide photographic light-sensitive material of the present invention contains, in the photographic constituting layer, U.S. Pat.Nos. 3,411,911 and 3,411,912,
-5331 and the like.

The silver halide photographic light-sensitive material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.No. 2,960,404, JP-B-43-4939, West German Application Publication 1,9
04,604, JP-A-48-63715, JP-B-45-15462, Belgian patent 762,833, U.S. Pat.No. 3,767,410, Belky patent 558,143, such as styrene-sodium maleate copolymer And hardening agents such as dextran sulfate, aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinylsulfone-based, isocyanate-based, sulfonate-based, carbodiimide-based, mucochloric-based, and acyloyl-based hardeners. As a film agent and an ultraviolet absorber, for example, U.S. Pat.
No. 921, British Patent 1,309,349 and the like, particularly 2- (2'-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3'-tert-butyl-5'-
Butylphenyl) -5-chlorobenzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and the like. Further, coating aids, emulsifiers, improvers of permeability to processing solutions, etc., defoamers or surfactants used for controlling various physical properties of photosensitive materials are disclosed in British Patent Nos. 548,532 and 1,216,389. , U.S. Patent
2,026,202, 3,514,293, JP-B-44-26580, 4
3-17922, 43-17926, 43-13166, 48-20
785, French patent 202,588, Belgian patent 773,459
No., anionic, cationic, nonionic or amphoteric compounds described in JP-A-48-101118 can be used, and among these, anionic surfactants having a sulfone group, for example, Sulfonated succinate, alkylnaphthalene sulfonated, alkylbenzene sulfonated, and the like are preferable.

As antistatic agents, JP-B-46-24159, JP-A-48-89979, U.S. Pat.Nos. 2,882,157 and 2,972,535
No., JP-A-48-20785, JP-A-48-43130, JP-A-48-90391
No., JP-B-46-24159, JP-B-46-39312, and JP-B-48-43809
And JP-A-47-33627.

In the production method of the present invention, the pH of the coating solution is preferably in the range of 5.3 to 7.5. In the case of multi-layer coating, it is preferable that the pH of the coating liquid obtained by mixing the coating liquids of the respective layers at a coating amount ratio is in the range of 5.3 to 7.5 described above. pH 5.3
If it is smaller than that, the progress of the dura is slow and unfavorable,
If the pH is higher than 7.5, it is not preferable that the photographic performance is adversely affected.

In the light-sensitive material of the present invention, a matting agent, for example, silica described in Swiss Patent No. 330,158, French Patent 1,2,
Glass powder described in 96,995, inorganic particles such as alkaline earth metal or cadmium described in British Patent No. 1,173,181 and carbonates such as zinc; starch described in U.S. Pat. No. 2,322,037, Belky patent 625,451 or British Patent 981,198 No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, polyacrylonitrile described in U.S. Pat.No. 3,079,257, described in U.S. Pat.No.3,022,169 Organic particles such as polycarbonate.

In the light-sensitive material of the present invention, the constituent layers include a sliding agent, for example, higher aliphatic esters of higher aliphatic alcohols described in U.S. Pat. Nos. 2,588,756 and 3,121,060, casein described in U.S. Pat.No. 3,295,979, and higher grades described in British Patent 1,263,772. Aliphatic calcium salt, UK Patent 1,313,384, U.S. Patent
It may include the silicon compounds described in 3,042,522 and 3,489,567. Liquid paraffin dispersions and the like can also be used for this purpose.

Filter dyes or dyes used for various purposes such as prevention of irradiation include oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are West German Patent 616,007, British Patent 584,609, and German Patent 1,117,429,
JP-B-26-7777, JP-B-39-22069, JP-B-54-38129, JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, and JP-A-49-114420
49-129537, 50-28827, 52-108115, 57
No.-185038, U.S. Pat.Nos. 1,878,961, 1,884,035,
1,912,797, 2,098,891, 2,150,695, 2,27
4,782, 2,298,731, 2,409,612, 2,461,484
No. 2,527,583, 2,533,472, 2,865,752,
No. 2,956,879, No. 3,094,418, No. 3,125,448, No. 3,1
No. 48,187, No. 3,177,078, No. 3,247,127, No. 3,260,60
No. 1, 3,282,699, 3,409,433, 3,540,887,
3,575,704, 3,653,905, 3,718,472, 3,8
No.65,817, No.4,070,352, No.4,071,312, PB Report
No. 74175, Photographic Abstract (Phot
O.Abstr.) are those described in 1 28 ('21), and the like.

As the optical brightener, stilbene, triazine,
Pyrazoline-based, coumarin-based, and acetylene-based fluorescent whitening agents can be preferably used.

These compounds may be water-soluble or insoluble in the form of a dispersion.

Examples of the anionic surfactant include an alkyl carboxylate, an alkyl sulfonate, an alkyl benzene sulfonate, an alkyl naphthalene sulfonate, an alkyl sulfate, an alkyl phosphate, an N-acyl-alkyl taurine, and a sulfokisaku. Those containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group, a phosphate group, such as acid esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, and polyoxyethylene alkyl phosphate esters. Is preferred.

As the amphoteric surfactant, for example, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine oxides and the like are preferable.

Examples of the cationic surfactant include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring are preferred.

Nonionic surfactants include, for example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene) Glycol sorbitan esters,
Polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones),
Preference is given to glyceed derivatives (eg alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars and the like.

Matting agent, UK patent 1,005,713, US patent
1,939,213, 2,221,873, 2,268,662, 2,33
2,037, 2,376,005, 2,391,181, 2,701,245
Nos. 2,992,101, 3,079,257, 3,262,782,
3,516,832, 3,539,344, 3,591,379, 3,7
Organic matting agents described in 54,924, 3,767,448, etc., West German Patent 2,592,321, U.S. Pat.
No. 260,772, U.S. Pat.Nos. 1,201,905, 2,192,241,
3,053,662, 3,062,649, 3,257,206, 3,33
2,555, 3,353,958, 3,370,951, 3,411,907
Nos. 3,437,484, 3,523,022, 3,615,554,
3,635,714, 3,769,020, 4,021,245, 4,0
Inorganic matting agents and the like described in No. 29,504 and the like can be preferably used.

As an antistatic agent, British Patent No. 1,466,600, Research Disclosure 15840
No. 16258, No. 16630, U.S. Pat.No. 2,327,828, No.
2,861,056, 3,206,312, 3,245,833, 3,42
8,451, 3,775,126, 3,963,498, 4,025,342
And the compounds described in JP-A Nos. 4,025,4603, 4,025,691, and 4,025,704 can be preferably used.

Particularly preferred as an embodiment of the present invention,
As a tone control agent for promoting hardening described in, for example, Japanese Patent No. 210458, JP-A-62-139546, a tetrazolium compound, a polyethylene oxide derivative, a phosphorus quaternary salt compound, or a hydrazine compound is used.

In addition, a technique for improving the dimensional stability by incorporating a polymer latex into a silver halide emulsion layer and a backing layer is also known.
Can be used. These technologies are, for example,
No.-4272, No.39-17702, No.43-13482, U.S.
376,005, 2,763,625, 2,772,166, 2,852,3
Nos. 86, 2,853,457 and 3,397,988.

Gelatin is used as a binder of the light-sensitive material used in the present invention. Examples of the binder include gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and homo- or copolymers. A hydrophilic colloid such as a synthetic hydrophilic polymer can be used in combination.

As gelatin, coal-treated gelatin, acid-treated gelatin, oxygen-treated gelatin as described in Bulletin of Society of Java (Bull. Soc. Sci. Phot. Japan) No. 16, page 30 (1966) is used. Alternatively, a hydrolyzate or enzymatic degradation product of gelatin can be used. Examples of gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkyleon oxides, and epoxy compounds. Is used. Specific examples are U.S. Pat.Nos. 2,614,928 and 3,132,9
No. 45, No. 3,186,846, No. 3,312,553, British Patent 861,41
No. 4, No. 1,033,189, No. 1,005,784, JP-B-42-26845
No. etc.

The protein may be albumin, casein, the cellulose derivative may be hydroxyethylcellulose, carboxymethylcellulose, a sulfate of cellulose, or the sugar derivative may be sodium alginate, and the starch derivative may be used in combination with gelatin.

As the graft polymer of gelatin and another polymer, a homopolymer or a copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, and styrene is used as the gelatin. A grafted product can be used. In particular, a graft polymer of a polymer having some compatibility with gelatin, for example, a polymer such as acrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate is preferable. These examples are described in U.S. Pat.
Nos. 3,625, 2,831,767 and 2,956,884.

In the light-sensitive material of the present invention, various additives can be further used according to the purpose. These additives are described in more detail in Research Disclosure, Vol. 176, Item 17643.
(December 1978) and Vol. 187, Item 18716 (November 1979), and the relevant locations are summarized in the table below.

Examples of the support used in the light-sensitive material of the present invention include a paper laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer), a flexible reflective support such as synthetic paper, cellulose acetate, Examples include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports having a reflective layer provided on these films, and metals.

 Among them, polyethylene terephthalate is particularly preferred.

The undercoat layer that can be used in the present invention is disclosed in
JP-A-49-3972, JP-A-49-11118 and JP-A-52-1, undercoating layers in an organic solvent system containing polyhydroxybenzenes.
No. 04913, No. 59-19941, No. 59-19940, No. 59-18945
No. 51-112326, No. 51-117617, No. 51-58469
No. 51-114120, No. 51-121323, No. 51-123139
No. 51-114121, No. 52-139320, No. 52-65422
Nos. 52-109923, 52-119919, 55-65949
No. 57-128332, No. 59-19941, and the like.

In addition, the surface of the undercoat layer can be usually chemically or physically treated. Examples of the treatment include surface treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. .

The undercoat layer is distinguished from the coating layer according to the present invention, and there is no limitation on the coating time and conditions.

In the present invention, a filter dye or a dye can be used for various purposes such as prevention of halation. Dyes used include triallyl dyes, oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are described in West German Patent 616,007, British Patent 584,609, and 1,177,429.
No., JP-B-26-7777, 39-22069, 54-38129
No., JP-A-48-85130, JP-A-49-99620, JP-A-49-114420
Nos. 49-129537, 50-28827, 52-108115
Nos. 57-185038 and 59-2845, U.S. Pat.
No. 61, No. 1,884,035, No. 1,912,797, No. 2,098,891
No. 2,150,695, 2,274,782, 2,298,731,
2,409,612, 2,461,484, 2,527,583, 2,5
33,472, 2,865,752, 2,956,879, 3,094,41
No. 8, No. 3,125,448, No. 3,148,187, No. 3,177,078,
3,247,127, 3,260,601, 3,282,699, 3,4
09,433, 3,540,887, 3,575,704, 3,653,90
No. 5, 3,718,472, 3,865,817, 4,070,352,
The 4,071,312 Patent, PB Report No. 74175, Photographic Abstract (Photo.Abstr.) Are those described in 1 28 ('21), and the like.

In particular, these dyes are preferably used in a light-turned light-sensitive material, and it is particularly preferable that the dye is used so that the sensitivity to light at 400 nm is at least 30 times the sensitivity to light at 360 nm.

Further, in the practice of the present invention, an organic desensitizer having a positive sum of the anodic potential and the cathodic potential of a polarograph described in JP-A-61-26041 may be used.

The light-sensitive material of the present invention can be exposed to light using electromagnetic waves in a spectral region in which an emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (daylight), tungsten lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenon lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, and light emitting diode lights Any known light source such as light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like can be used. JP-A-62-
A favorable result can be obtained by attaching an absorption filter for absorbing a wavelength of 370 nm or less to a UV light source such as 210458 or using a UV light source having an emission wavelength of 370 to 420 nm as a main wavelength.

Exposure time is usually 1 millisecond to 1 second, which is usually used in cameras, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond using a cathode ray tube or a xenon flash tube. It is also possible to give exposures longer than one second. These exposures may be performed continuously or intermittently.

The present invention can be applied to various photosensitive materials such as for printing, X-ray, general negative, general reversal, general positive, and direct positive, but printing requiring extremely high dimensional stability is required. When applied to photosensitive materials for use, particularly remarkable effects can be obtained.

In the present invention, various development processes such as black-and-white, color, and reversal can be used for the development process of the photosensitive material by a known method. is there.

In the present invention, in addition to thiosulfate and sulfite, various acids, salts, fixing accelerators, wetting agents, surfactants, chelating agents, hardeners, etc. Can be contained. For example, thiosulfates, sulfites are potassium, sodium, and ammonium salts of these acids, and acids are sulfuric acid, hydrochloric acid, nitric acid,
Examples thereof include boric acid, formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid, citric acid, malic acid, and phthalic acid. Examples of the salts include salts of these acids such as potassium, sodium, and ammonium. As a fixing accelerator,
Nos. 45-35754, JP-A-58-122535, and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers described in U.S. Pat. Dextran ethers, crown ethers, diazabicycloundenecene, di (hydroxyethyl) butamine and the like. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the chelating agent include nitrilotriacetic acid and aminoacetic acid such as EDTA. As the hardener, chromium alum, potassium alum and other Al compounds can be contained.

In the present invention, the fixing solution preferably contains an Al compound in order to increase the hardening property of the light-sensitive material, and more preferably the content is 0.1 to 3 g / in terms of Al in the working solution.

The preferred concentration of sulfurous acid contained in the fixing solution is from 0.03 to 0.4 mol /, more preferably from 0.04 to 0.3 mol /.

The preferred pH of the fixer is from 3.9 to 6.5, at which pH the fixer gives favorable photographic performance, and the effect of the packaging material of the present invention is remarkable. The most preferred liquid pH is 4.2-5.3.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example 1 [Preparation Method of Emulsion (A)] A silver chlorobromide emulsion was prepared using the following solutions A, B and C.

<Solution A> Ossein gelatin 17g Polyisopropylene-polyethyleneoxy disuccinate sodium salt 10% ethanol aqueous solution 5ml Distilled water 1280ml <Solution B> Silver nitrate 170g Distilled water 410ml <Solution C> Sodium chloride 45.0g Potassium bromide 27,4g Rhodium trichloride trihydrate 28 μg Polyisopropylene oxydisuccinate sodium salt 10% ethanol solution 3 ml ossein gelatin 11 g distilled water 407 ml <solution D> 1% K ₃ RhBr ₆ 1 ml 25% KBr solution 999 ml <solution E> 1 % K ₂ [Ir (IV) Cl ₆ ] 0.75 ml Water 36.75 ml After keeping Solution A at 40 ° C., sodium chloride was added so that the EAg value became 160 mV.

Next, using a mixing stirrer described in JP-A-57-92523 and JP-A-57-92524, the solution B and the solution C were subjected to a double jet method.
Was added.

As shown in Table 1, the addition flow rate was gradually increased over the entire addition time of 80 minutes, and the addition was performed while the EAg value was kept constant.

Add container D into container being mixed at addition time of 10 minutes
(Amount of rhodium salt added was 2.8 × 10 ⁻⁸ mol per mol of silver halide).

The EAg value was changed from 160 mV 5 minutes after the start of the addition to an EAg value of 120 mV using a 3 ml / aqueous sodium chloride solution, and thereafter maintained at this value until the mixing was completed.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol / sodium chloride aqueous solution.

For the measurement of the EAg value, a metal silver electrode and a double junction type saturated Ag / AgCl reference electrode were used.
The double junction disclosed in JP-A-57-197534 was used. ).

A variable flow rate roller tube metering pump was used for adding the solutions B and C.

During addition, it was confirmed by observation with an electron microscope that no new grains were generated in the system due to sampling of the emulsion.

During the addition, add 3% to keep the pH of the system constant at 3.0.
It was controlled with an aqueous nitric acid solution.

After the addition of solution B and solution C, the emulsion was Ostwald-ripened for 10 minutes, then desalted and washed in a conventional manner, and then 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) was added. After dispersing by stirring for 30 minutes, 75
Adjusted to 0 ml.

[Method of preparing emulsion (B)]

Emulsion (A) was prepared in the same manner as for emulsion (A) except that 2 ml of solution D was added at an addition time of 60 minutes.

[Method of preparing emulsion (C)]

When the addition time is 10 minutes, 0.5 ml of the mixture of solution E (the amount of iridium salt added is 2.1 × 10 ^-7 mol per mol of silver halide) is sampled and added to the mixing vessel instead of solution D from the mixture. The emulsion was prepared in the same manner as in the emulsion (A), except that

[Method of preparing emulsion (D)]

Emulsion (C) was prepared in the same manner as for emulsion (C) except that 0.5 ml of solution E was added at an addition time of 60 minutes.

[Preparation method of emulsion (E)]

In the emulsion (A), the added amount of the aqueous rhodium salt was 0%.
The emulsion thus prepared was designated as Emulsion (E).

Emulsions (A) to (E) were each subjected to gold-sulfur sensitization, and sensitizing dye A was used as a stabilizer in an amount of 300 mg per mol of silver halide contained in the emulsion as 4-hydroxy-6-methyl-1, 3,3a, 7-Tetrazaindene was added, and sensitizing dye B was added in an amount of 100 mg per mole of silver halide contained in the emulsion.

Next, 800 mg of a tetrazolium compound represented by T-36 was added per mol of silver halide, 300 mg of sodium p-dodecylbenzenesulfonate, 2 g of a styrene-maleic acid copolymer polymer, and styrene-butyl acrylate-acrylic acid copolymer latex ( 15 g of an average particle size of about 0.25 μm).
-Coated on a subbed polyethylene terephthalate film base described in Example (1) of 19941. At this time, as shown in Table 2, the amount of gelatin was 10% of bis- (2-ethylhexyl) sulfosuccinate as a spreading agent.
mg / m ^2, formalin 15 mg / m ² as a hardener, were simultaneously coated a protective layer containing glyoxal 8 mg / m ^2.

These samples were exposed to a tungsten light source using a wedge and developed. The development processing was performed with the following developer and conditions. The amount of silver was analyzed by a fluorescent X-ray analyzer. However, the amount of silver after processing was represented by the amount of silver giving the maximum density.

Measurement of pressure resistance Regarding the pressure resistance, 95% of these samples were subjected to net photography, and then the exposed samples were bent at a constant pressure and developed. A sample having a large change in density due to pressurization was ranked 1 and a sample without a change in density was ranked 10 and evaluated on a 10-point scale.

 Rank 4 is a practically problematic level.

<Development processing conditions> (Process) (Temperature) (Time) (Tank capacity) Current image 35 ° C 15 seconds 20 Fixed 35 ° C 15 seconds 20 Rinse 18 ° C 10 seconds 15 Dry 40 ° C 10 seconds Each step is the next step It also includes the so-called Watari transport time up to Dry to dry time is 50 seconds.

 The results are shown in Table 3.

<Formulation of developer> (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to adjust pH of used solution to 10.4 Potassium bromide 4.5g (Composition B) Pure water (ion-exchanged water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 700 mg butylamine diethanolamine 15 g At the time of using a developing solution, it was dissolved in 500 ml of water in the order of the above-mentioned composition A and composition B, and used after finishing to 1.

<Composition A> (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% w / w aqueous solution) 13.6 ml (composition B) pure water water during use of the (ion-exchanged water) 17 ml sulfuric acid (50% w / w aqueous solution) 4.7 g aluminum sulfate (Al ₂ O ₃ in terms of content is 8.1% w / w aqueous solution) 26.5 g fixer The above composition A and composition B were dissolved in 500 ml in this order, and finished to 1 for use. The pH of the fixing solution was about 4.3.

Gamma is specified for densities from 0.3 to 3.0.

When the gamma is 5 or less, the thin lines are crushed and practically difficult.

Example 2 The same experiment as in Example 1 was performed, except that the tetrazolium compound (T-36) was changed to the following compound b, and the same effect as in Example 1 was obtained.

[Effects of the Invention] The present invention provides a silver halide photographic light-sensitive material having excellent pressure resistance, effectively developing silver in the light-sensitive material, and obtaining a high-contrast image even in ultra-rapid processing, and a processing method therefor. We were able to.

Continuation of the front page (56) References JP-A-60-91347 (JP, A) JP-A-63-115159 (JP, A) JP-A-63-184740 (JP, A) JP-A-63-306436 (JP) JP-A-2-20853 (JP, A) JP-A-64-73337 (JP, A) JP-A-2-69736 (JP, A) (58) Fields studied (Int. Cl. ⁶ , DB G03C 1/09 G03C 1/015 G03C 1/047 G03C 5/29

Claims (4)

(57) [Claims] In the silver halide grain formation step, at any time before adding 95% of the total silver nitrate addition amount, a water-soluble rhodium salt, a water-soluble iridium salt, a water-soluble osmium salt and a water-soluble ruthenium salt are selected. A silver halide photographic light-sensitive material comprising a support having thereon a silver halide photographic emulsion obtained by rush addition of at least one of the above. 2. The silver halide according to claim 1, wherein the weight ratio (Ag / gelatin) of silver and gelatin on the support on the side having the silver halide emulsion is 1.0 or more. Photosensitive material. 3. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is processed within a development processing time of 19 seconds. 4. The method for processing a silver halide photographic material according to claim 3, wherein the total processing time of Dry to Dry is 20 seconds to 60 seconds.