JPH0269736A - Silver halide photographic sensitive material and processing method - Google Patents

Abstract

PURPOSE:To allow the silver in the photosensitive material to be effectively developed even in an ultra-rapid processing and to obtain high-contrast images by specifying the ratio of the silver content in a hydrophilic colloidal layer on the side of a base where emulsion layers are included and the film thickness of the hydrophilic colloidal layer. CONSTITUTION:The ratio (silver content g/m<2>/film thickness mum) of the silver content in the hydrophilic colloidal layer on the side of the base where the emulsion layers are included and the film thickness of the hydrophilic colloidal layer is specified to >=0.7. The film thickness of the layers in this case refers to the total sum of the film thicknesses of >=1 layers of the hydrophilic colloidal layers on the side of the base where the photosensitive silver halide emulsion layers are included and this film thickness is not limited to the film thickness of the silver halide emulsion layers. The silver content is also defined as the total silver content of the respective layers if the above-mentioned layers are applied and provided in plural layers on the same side of the base. The silver in the photosensitive material is effectively developed in this way even in the ultra-rapid processing and the high-contrast image is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a negative-working silver halide photographic light-sensitive material, and more particularly to a light-sensitive material suitable for ultra-rapid processing and a processing method.

[Background of the invention]

In recent years, in order to cope with the increase in the amount and speed of information as part of the information industry, demands for rapid processing of silver halide photographic materials have become extremely strict even in the printing industry. On the other hand, in order to improve work ease and stability,
The so-called lithographic development, which has been commonly used in the development of conventionally printed photosensitive materials, has been replaced by rapid access development, which improves its shortcomings in stability. By incorporating the agent into the silver halide emulsion, it is possible to achieve high contrast equivalent to lithographic development, and
Development time of 0 to 30 seconds became possible. However, the above-mentioned requirements further include a strong requirement for development time of 20 seconds or less, and it goes without saying that a reduction in image quality is not acceptable. In printing, there is a power reduction operation, so it is not possible to simply reduce the amount of silver. Therefore, in order to achieve rapid processing and silver saving, it is important to develop silver halide in a short period of time without waste and utilize it effectively, and there is an extremely high demand for such silver halide photographic materials and processing methods. strong.

[Purpose of the invention]

In view of the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material and a processing method in which silver in the material can be effectively developed and high-contrast images can be obtained even in ultra-rapid processing. That's true.

[Structure of the invention]

The above object of the present invention is to provide a negative silver halide photographic material comprising at least one photosensitive silver halide emulsion layer coated on a support, which is hydrophilic on the side containing the emulsion layer relative to the support. Achieved by a negative-working silver halide photographic material characterized in that the ratio of the amount of silver in the hydrophilic colloid layer to the thickness of the hydrophilic colloid layer (silver amount g/m2/film thickness μm) is 0.7 or more. Ru.

The above negative silver halide photographic light-sensitive material has a development time of 19 seconds or less, and a total dry-to-dry processing time of 20-60 seconds.
It is characterized by being processed in seconds.

Detailed Description of the Present Invention In the present invention, Dry to Dry refers to the total time from when the leading edge of a photosensitive material is inserted into an automatic developing machine, through development, fixing, washing with water, and drying until the leading edge emerges from the automatic developing machine. It is. In other words, the total length of the processing line (m) including various crossing sections divided by the line conveyance speed (m/see)
), and is characterized in that the value is 60 seconds or less.

Further, the layer thickness in the aspect of the present invention refers to the total thickness of one or more hydrophilic colloid layers on the side containing the photosensitive silver halide emulsion layer with respect to the support,
The thickness of the silver halide emulsion layer is not limited.

In addition, when a plurality of layers are coated on the same side of the support, the amount of silver is defined based on the total amount of silver in each layer. In the present invention, photosensitive silver halide grains having an average grain size of 0.05 to 0.5 μm are used on one side of the support. Here, the average particle size is, in the case of spherical particles,
In the case of particles having a shape other than spherical, the diameter is the diameter when the projected image is converted into a circular image with the same area. It is preferable that 60% or more of the total number of particles have a particle size within ±IO% of the average particle size.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, and silver chloroiodobromide. Silver chlorobromide containing 50 mol% or more of silver chloride as a negative-working mercury halide emulsion can be used.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having {1001 planes as crystal surfaces.

Also, U.S. Patent Nos. 4,183.756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., The Journal of Photographic Science (J, Photogr.Sc.
i), 21. Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in documents such as 39 (1973) and used.

Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

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

In the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in a monodisperse 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 total weight of silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size 7 is the particle size ri when the product n1Xri3 of the frequency of particles having particle size ri and ri3 is maximum.
Define.

(3 significant digits, minimum 4 to 5 decimal places.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the diameter in the case of grains with shapes other than spherical. This is the diameter when the projected image is converted into a circular image with a circumferential area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodispersed emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less. belongs to.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above.

Monodispersed emulsions are disclosed in JP-A-54-48521 and JP-A-58-49.
It can be obtained by referring to No. 938 and No. 60-122935.

Although the photosensitive silver halide emulsion can be used as a so-called unripe (Pr1mltive) emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
elikman et al. or H. Frleser, ed.
Die
Grundlagen der Photography
ischen Prozesse wait SiLb
erhalogeniden, Akade+aisc
he Verlagsgesellschaft, 1
968) can be used.

That is, a sulfur sensitization method using a sulfur-containing metal compound or activated gelatin that can react with silver ions, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. It can be used as As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include US Pat. No. 1,574.944,
It is described in No. 2,410.689, No. 2,278.947, No. 2,728.668, and No. 3,656°955. Examples of reduction sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds etc. can be used, and specific examples thereof are U.S. Pat.
No. 2,518.698, No. 2,983.609, No. 2,983.610, and No. 2,694.637. For noble metal sensitization, in addition to total complex salts,
Complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used, and specific examples thereof include U.S. Pat.
No. 399,083, No. 2,448,060, British Patent No. 618.061, etc.

In addition, there are no particular restrictions on the conditions such as pHSpAg and a degree during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is preferably maintained at 5 to IL, especially 8 to 1O. is preferred. Further, the temperature is preferably 40 to 90°C, particularly 45 to 75°C.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control 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 are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

In the silver halide photographic material according to the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, and the like. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, benzindolenine nucleus, indole nucleus, benzoxil nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable.These nuclei may be substituted on a carbon atom.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. can be applied.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in a normal negative-working 710 silver gemide emulsion. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion. Approximately 1 sensitizing dye per mole of silver halide.

OX 10-' to about 5 X 10-' moles are preferred;
Approximately 4 x 10 sensitizing dyes per mole of silver halide in the frame
It is preferred to use a concentration of -' to 2 x 10-4 molar.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. More specific examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, examples of the sensitizing dye used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231.658, US Pat.

No. 776, No. 2,519.001, No. 2,912.3
No. 29, No. 3,656°956, No. 3,672.89
No. 7, No. 3,694.217, No. 4,025°349
No. 4,046,572, British Patent No. 1,242,5
No. 88, Special Publication No. 14030/1973, No. 52-2484
No. 4, JP-A-48-73137, JP-A No. 61-17214
Examples include those described in No. 0. As sensitizing dyes used in green-sensitive silver norogenide emulsions, for example, U.S. Pat.
, No. 908, No. 2,739,149, No. 2,945.
No. 763, British Patent No. 505.979, Special Publication No. 48-4
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 2172 and the like. Furthermore, the sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions include:
For example, U.S. Patent Nos. 2,269,234 and 2,270,
No. 378, No. 2,442.710, No. 2,454.6
No. 29, No. 2,776.280, Special Publication No. 1977-177
No. 25, JP-A-50-62425, JP-A No. 61-2983
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 6, No. 60-80841, and the like.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Typical examples are U.S. Patent No. 2,688.545;
No. 977.229, No. 3,397,060, No. 3,5
No. 22,052, 3, 527.

No. 641, No. 3,617,293, No. 3,628.9
No. 64, No. 3,666゜480, No. 3,672,89
No. 8, No. 3,679,428, No. 3,703°377
No. 3,769.301, No. 3,814,609, No. 3,837゜862, No. 4,026.707,
British Patent No. 1,344.281, British Patent No. 1,507,803
No., Special Publication No. 43-4936, No. 53-12375,
It is described in JP-A-52-110613, JP-A-52-109925, etc.

The silver halide photographic 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 preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, 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 decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles,
benzimidazoles (especially nitro- or halogen-substituted), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-7enyl-5-
mercaptotetrazole), mercaptopyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy substituted 1, 3, 3a,
7) Many compounds known as stabilizers can be added, such as tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is in The Theory of the Photographic Process, by K. Mees.
Theory of the Photography
ic Processs, 3rd edition, 1966), citing the original literature.

For more detailed examples of these and how to use them, see, for example, U.S. Pat.
No. 947, No. 4,021,248 or Special Publication No. 1972-
The description in No. 28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention contains U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, Special Publication No. 45-15462, Belgian Patent No. 7
62.833, U.S. Pat. No. 3,767.410, and Belgian Patent No. 558.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc.; Various hardeners and ultraviolet absorbers such as aldehyde, epoxy, ethyleneimine, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl, and ultraviolet absorbers include Patent No. 3,253.921, British Patent No. 1,309.34
Compounds described in each No. 9 etc., especially 2-(2'-
Hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5', di-
tertiary butylphenyl)benzotriazole, 2-(2-
Hydroxy-3'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl).
Examples include 5-chlorobenzotriazole. Furthermore, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent Nos. 548 and 532; 1. ．． 216.389
No. 2,026.202, U.S. Patent No. 3,514.2
Each of No. 93, Special Publication Showa 44-? , No. 6580, 43-
No. 17922, No. 43-17926, No. 43-131
No. 66, No. 48-20785, Buddhist Temple Patent No. 202.
588, Peruvian Patent No. 773,459, and JP-A-48-101118, anionic, cationic, nonionic, or amphoteric compounds can be used, but these Among these, anionic surfactants having a sulfone group, such as succinic acid ester sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, and the like are particularly preferred.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
JP 48-89979, U.S. Patent No. 2,882.15
No. 7, No. 2,972.535, Japanese Unexamined Patent Publication No. 48-2078
No. 5, No. 48-43130, No. 48-90391,
There are compounds described in Japanese Patent Publications Nos. 46-24159, 46-39312, 48-43809, and 47-33627.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.3 to 7.
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that p)I of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is in the above range of 5.3 to 7.5. If the pH is less than 5.3, the progress of hardening is undesirable, and if the pH is greater than 7.5, it is undesirable because it adversely affects photographic performance.

In the light-sensitive material of the present invention, the constituent layers include matting agents, such as silica described in Swiss Patent No. 330.158, glass powder described in French Painting Patent No. 1,296,995, and British Patent No. 1.
, 173,181; inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; starch as described in U.S. Pat. No. 2,322.037;
Starch derivatives described in No. 5,451 or British Patent No. 981.198, polyvinyl alcohol described in Japanese Patent Publication No. 3643/1983, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330.158, and US Pat. , 079.257, and polycarbonate described in U.S. Pat. No. 3,022,169.

In the photosensitive material of the present invention, the constituent layers may contain slipping agents, such as those described in U.S. Pat.
higher alcohol esters of higher aliphatics as described in U.S. Pat. No. 3,295.979, casein as described in U.S. Pat. , U.S. Patent No. 3,042
, No. 522, and No. 3,489.567.

Dispersions of liquid paraffin and the like can also be used for this purpose.

Filter dyes or dyes used for irradiation prevention and other purposes include oxanol dyes,
Contains 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 include West German Patent No. 616.007, British Patent No. 584.609,
No. 117,429, Special Publication No. 26-7777, No. 39-
No. 22069, No. 54-38129, Japanese Unexamined Patent Publication No. 1983-8
No. 5130, No. 49-99620, No. 49-1144
No. 20, No. 49-129537, No. 50-28827
No. 52-108115, No. 57-185038, U.S. Pat. No. 1,878.961, Id.

No. 884.035, No. 1,912.797, No. 2,0
No. 98.891, No. 2゜150.695, No. 2,27
No. 4.782, No. 2,29L731, No. 2゜409.
No. 612, No. 2,461.484, No. 2,527,5
No. 83, No. 2゜533.472, No. 2,865.75
No. 2, No. 2,956.879, No. 3゜094.418
No. 3,125.448, No. 3,148,187, No. 3゜177.078, No. 3,247.127,
3,260.601, 3゜282.699, 3,409.433, 3,540.887, 3
゜575.704, 3,653.905, 3,
No. 718.472, No. 3゜865.817, No. 4,0
No. 70,352, No. 4,071,312, PR Report No. 74175, Photographic Abstract (Photo, Abstr,) l 28 (
21) etc.

As the optical brightener, stilbene-based, triazine-based, pyrazoline-based, coumarin-based, and acetylene-based optical brighteners can be preferably used.

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

Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-alkyl taurines, and Those containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl phosphate esters. is preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides.

Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. etc. are preferred.

Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts), glyceed derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars etc. are preferred.

As matting agents, British Patent No. 1,055.713, U.S. Patent No. 1,939,213, U.S. Patent No. 2,221.873, U.S. Patent No. 2,268,662, U.S. Patent No. 2,332,037,
2,376.005, 2,391.181, 2,701,245, 2,992.101, 3
, 079°257, 3,262.782, 3,
No. 516.832, No. 3,539゜344, No. 3,5
No. 91,379, No. 3,754.924, No. 3, 7
67.

Organic matting agent described in No. 448 etc., West German patent 2
, No. 592.321, British Patent No. 760,775, No. 1
, 260.772, U.S. Pat. No. 1,201.905,
2,192,241, 3゜053.662, 3,062,649, 3,257.206, 3
゜322.555, 3,353.958, 3,
No. 370,951, No. 3゜411.907, No. 3,4
37.484, 3,523,022, 3゜61
5.554, 3,635,714, 3,769
．． No. 020, No. 4゜021.245, No. 4, 029
, No. 504, etc. can be preferably used.

As an antistatic agent, British Patent No. 1,466.6QO,
Research Disclosure+ -(Research
Disclosure) No. 15840, No. 16258
No. 16630, U.S. Patent No. 2,327,828,
2,861.056, 3,206.312, 3,245.833, 3,428.451, 3
, No. 775.126, No. 3,963,498, No. 4,
No. 025,342, No. 4,025.463, No. 4,0
Compounds described in No. 25,691, No. 4,025.704, etc. can be preferably used.

Particularly preferred as an embodiment of the present invention is JP-A-62-
210458, JP-A No. 62-139546, and the like, a tetrazolium compound, a polyethylene oxide derivative, a phosphorus quaternary salt compound, a hydrazine compound, or the like is used as a tone control agent that promotes high contrast.

Further, it is also possible to use a technique in which a polymer latex is contained in a silver halide emulsion layer or a backing layer to improve dimensional stability. These techniques, for example,
No. -4272, No. 39-17702, No. 43-134
No. 82, U.S. Patent No. 2,376.005, U.S. Patent No. 2,763
．． No. 625, No. 2,772.166, No. 2,852.
No. 386, No. 2,853.457, No. 3,397.9
It is described in No. 88, etc.

Gelatin is used as the binder for the photosensitive material used in the present invention, but synthetic materials such as gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and single or copolymers may also be used. Hydrophilic colloids such as hydrophilic polymer substances can also be used in combination.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bulletin Op Society of Japan (Bull, Soc, Sci, Phot, Ja)
Oxygen-treated gelatin as described in Pan) No. 16, page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The one obtained by doing so is used. Specific examples are U.S. Pat. Nos. 2,614,928 and 3,132.
, No. 945, No. 3,186,846, No. 3,312,
553, British Patent No. 861,414, British Patent No. 1,033.
No. 189, No. 1,005,784, Special Publication No. 1977-2
It is described in No. 6845, etc.

Proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxyl methyl cellulose, and cellulose sulfate esters, and sugar derivatives such as sodium alginate and starch derivatives may be used in combination with gelatin.

Examples of the graft polymer of gelatin and other polymers include gelatin and derivatives such as acrylic acid, methacrylic acid, their esters and amides, and single (homo) or copolymer of vinyl yarns such as acrylonitrile and styrene. A grafted graft can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
No. 63,625, No. 2,831,767, No. 2,95
No. 6,884, etc.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and volume 187■t
em18716 (November 1979), and the relevant parts are summarized in the table below.

2. Sensitivity enhancer 3. Spectral sensitizer supersensitizer 4. Brightener 5. Antifogging agent and stabilizer 6. Light absorber, filter dye UV absorber 7. Anti-stain agent 8. Dye image stabilization Same as above, page 648 right column - pages 23-24 page 649 right column 24 pages 24-25 page 649 right column pages 25-2G 649 right column - 650 left column page 25 right column page 650 left - right column page 25 9, Hardener page 26 651
Page left column 10, binder page 26
Same as above 11, Plasticizer/Lubricant Page 27 650 Right column 12, Coating aid/Surfactant
Pages 26-27 Same as above 13, Static inhibitor
Page 27 Same as above Support used in the photosensitive material of the present invention I This is a flexible reflective support such as paper or synthetic paper laminated with α-olefin polymer (e.g. polyethylene, polypropylene, ethylene/butene copolymer), etc. Films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, flexible supports with reflective layers on these films, metals, etc. included.

Among them, polyethylene terephthalate is particularly preferred.

As the undercoat layer that can be used in the present invention,
9-3972, etc., subbing layer in an organic solvent system containing polyhydroxybenzenes, JP-A-49-1111
No. 8, No. 52-104913, No. 59-19941, No. 59-19940, No. 59-18945, No. 5
No. 1-112326, No. 51-117617, No. 51
-58469, 51-114120, 51-1
No. 21323, No. 51-123139, No. 51-11
No. 4121, No. 52-139320, No. 52-654
No. 22, No. 52-109923, No. 52-11991
9, No. 55-65949, No. 57-128332, No. 59-19941, and the like.

Further, the surface of the undercoat layer can usually be chemically or physically treated. Such treatments include surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated 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 are no restrictions on coating timing or conditions.

In the present invention, dyes can be used as filter dyes or dyes for various purposes such as preventing halation.

Dyes that can be 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 include West German Patent No. 616,007, British Patent No. 584.609, British Patent No. 1,177.429, Japanese Patent Publication No. 1987-7777, and British Patent No. 1,177.429.
No. 9-22069, No. 54-38129, Japanese Unexamined Patent Publication No. 1973
-85130, 49-99620, 49-11
No. 4420, No. 49-129537, No. 50-288
No. 27, No. 52-108115, No. 57-18503
No. 8, No. 59-24845, U.S. Patent No. 1,878.9
No. 61, No. 1,884,035, No. 1,912.79
No. 7, No. 2,098,891, No. 2,150.695
No. 2,274.782, No. 2,298,731, No. 2,409,612, No. 2,461.484,
No. 2,527,583, No. 2,533,472, No. 2,865.752, No. 2,956,879, No. 3
, No. 094.418, No. 3.125.448, No. 3,
148.187, 3,177.078, 3,2
47.127, 3,260.601, 3,28
No. 2.699, No. 3,409.433, No. 3,540
．． No. 887, No. 3,575.704, No. 3,653.
No. 905, No. 3,718,472, No. 3,865.8
No. 17, No. 4,070.352, No. 4,071,31
No. 2, PB Report No. 74175, Photographic Abstract (Photo, Abstr,)
128 ('21) etc.

In particular, it is suitable to use these dyes in light-sensitive materials that have a sensitivity of 360 nm to 400 nm light.
It is particularly preferable to use it so that the sensitivity to nm light is 30 times or more higher.

Furthermore, when carrying out the present invention, Japanese Patent Application Laid-Open No. 61-2604
An organic desensitizer in which the sum of the anode potential and the cathode potential of the polarograph described in No. 1 is positive can also be used.

The light-sensitive material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenonark lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, Any known light source can be used, such as light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. Also, JP-A-62
Preferable results can also be obtained by using an IIV UV light source such as No. 210458, which is equipped with an absorption filter that absorbs wavelengths of 70 nffl or less, or by using a UV light source whose main emission wavelength is from 370 to 420 nm.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, the 100 nanosecond to 1 microsecond exposure time using a cathode ray tube or xenon flash tube. It is also possible to provide exposures longer than 1 second. These exposures may be performed continuously or intermittently.

The present invention can be applied to various photosensitive materials such as those for printing, X-ray, general negative, general reversal, general positive, and direct positive.

In the present invention, in addition to thiosulfate and sulfite, the fixing solution that can be used for geography includes various acids, salts, fixing accelerators, wetting agents, surfactants, chelating agents, hardening agents, etc. can be contained.

For example, thiosulfates and sulfites include the potassium, sodium, and ammonium salts of these acids; acids include sulfuric acid, hydrochloric acid, nitric acid, halic acid, formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid; Examples include citric acid, malic acid, phthalic acid, etc. Salts include potassium,
Examples include salts such as sodium and ammonium. As the fixing accelerator, Japanese Patent Publication No. 45-35754, Japanese Patent Application Laid-open No. 58
-122535, thiourea derivatives described in 58-122536, alcohols having a triple bond in the molecule, thioethers described in U.S. Pat. No. 4,126.459, or cyclodextran ethers that free anions, crown Examples include ethers, diazabicycloundecene and di(hydroxyethyl)butamine. Examples of wetting agents include alkanolamines and alkylene glycols. Examples of chelating agents include nitrilotriacetic acid, aminoacetic acids such as EDTA, and potassium, sodium, and ammonium salts of these acids.

Examples of the fixing accelerator include thiourea derivatives described in Japanese Patent Publication No. 45-35754, Japanese Patent Application Publication No. 58-122535, and Japanese Patent Application Publication No. 58-122536, alcohols having a triple bond in the molecule, and U.S. Pat. No. 4,126.459. Examples include the thioethers described in the above issue, cyclodextran ethers that liberate anions, crown ethers, diazabicycloundecene, di(hydroxyethyl)butamine, and the like.

Examples of wetting agents include alkanolamines and alkylene glycols. Examples of chelating agents include aminoacetic acids such as nitrilotriacetic acid and EDTA. As a hardening agent, chromium alum, potassium alum, A (2 compounds), etc. can be contained.

In the present invention, the fixer preferably contains an Aff compound in order to improve the hardness of the photosensitive material, and when the content is 0.1 to 3 g/12 in terms of Aff in the solution used, preferable.

The preferred concentration of sulfite contained in the fixer is 0.03 to 0.
The amount is 4 mol/Q, more preferably 0.04 to 0.3 mol/Q.

The preferred pH of the fixer is 3.9 to 6.5;
The fixer gives favorable photographic performance, and the effect of the packaging material of the present invention becomes significant. The most preferable liquid pH is 4.
It is 2 to 5.3.

〔Example〕

Examples of the present invention will be described in detail below, but it goes without saying that the present invention is not limited thereto.

Example 1 Silver nitrate aqueous solution, common salt, and sodium bromide aqueous solution are simultaneously mixed in a gelatin aqueous solution to generate silver halide particles,
A photographic emulsion was prepared by desalting in a conventional manner. This emulsion was chemically sensitized by a conventional method, and 6-
Methyl-4-hydroxy-1,3,3a,7-chitrazaindene was added. Additionally, phenyl-5-mercaptotetrazole, 5-methylbenzotriazole, nonylphenyloxypolyethylene glycol, acrylic acid-
Add butyl methacrylate polymer latex, then add tetrazolium compound (A) at 1.3% per mole of silver.
9, saponin and sodium dodecylbenzenesulfonate were added, and then acrylic acid-butyl methacrylate polymer latex and styrene-styrene as a thickener were added.
An emulsion coating solution was prepared by adding 280 mg of an aqueous maleic acid copolymer and coated onto a 100 μm thick polyethylene terephthalate film base coated with polymer latex. At this time, a bill splitting protective film layer was simultaneously applied.

The amount of silver and the thickness of the hydrophilic colloid layer are shown in Table 1.

These samples were exposed to light through a glass wedge using a light room printer P627FM (manufactured by Dainippon Screen), and processed under the following processing conditions using a developer and a fixer having the compositions shown below. The amount of silver was analyzed using a fluorescent X-ray analyzer. However, the amount of silver after processing is indicated by the amount of silver in the area that gives maximum density. The thickness of the hydrophilic colloid layer was measured using a swelling degree measuring device (manufactured by Shinto Denshi).

Developer prescription (composition A) Pure water (ion exchange water) 150ml
2 Ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 509 Potassium sulfite (55% W/V aqueous solution) 100mQ Potassium carbonate 50g Hydroquinone 1591-Phenyl-5
・Mercaptotetrazole 30mg potassium hydroxide
Amount of potassium bromide to bring the pH of the solution to 10.4
4.59 (composition) Pure water (ion exchange water) 3m12
Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90
% aqueous solution) 0.3ml121-phenyl-3-pyrazolidone 500111
Sodium 92-mercapto-penzimidazole-5-sulfonate 5011
19, when using a developer, dissolve the above composition A and composition B in the order of 500 + nfl water and apply IQ. It was finished and used.

Fixing liquid prescription (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 23
0mQ Sodium Sulfite 9.5
9 Sodium acetate trihydrate 15.99
Boric acid 6.79 Sodium citrate dihydrate 2g Acetic acid (90
%W/W aqueous solution) 8.1a+Q(
Composition) Pure water (ion exchange water) 17I1112 Sulfuric acid (50% W/W aqueous solution) 5.
89 aluminum sulfate (aqueous solution with an Al1,0. content of 8.1% W/W)
When using the 26.59 fixer, it was dissolved in 500a+12 of water in the order of composition A and composition, finished to la, and used. The pH of this fixer was about 4.3.

C Rapid development processing conditions〕 (Process) (Temperature) (Time) (Tank capacity)
Development 35°C 15 seconds 20 (4
0Q) Fixation 34°C 15 seconds
2012 water washing 18℃ 10 seconds
10 (20Q) drying 40°C1
0 seconds 204 The results are shown in Table 1.

As is clear from Table 1, when the ratio between the amount of silver and the thickness of the hydrophilic colloid layer is 0.7 or more, more than 90% of the applied silver is effectively developed, and a high-contrast image with a gamma of 6 or more is obtained. It can be seen that it gives

Example 2 In Example 1, the following sensitizing dye (
A sample was prepared by adding B). A tungsten lamp was used for exposure through a glass wedge. Other than that, the same experiment as in Example I was conducted, and the same effects as in Example 1 could be obtained.

I゛・、Have」・7ノ ゛＼knee／ Table 1 is difficult.

〔Effect of the invention〕

According to the present invention, it has been possible to provide a silver halide photographic material and a processing method in which silver in the material can be effectively developed and high-contrast images can be obtained even in ultra-rapid processing.

Claims (3)

[Claims] (1) In a negative-working silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer coated on a support, in a hydrophilic colloid layer on the side containing the emulsion layer with respect to the support. A negative-working silver halide photographic material, characterized in that the ratio of silver content to the thickness of the hydrophilic colloid layer (silver content g/m^2/film thickness μm) is 0.7 or more. (2) A processing method characterized by developing the negative-working silver halide photographic material according to claim 1 within a developing time of 19 seconds. (3) In the method for processing a negative-working silver halide photographic light-sensitive material according to claim 2, the DrytoDry processing time is 20 minutes.
A method for processing a silver halide photographic material, characterized in that the processing time is 60 seconds.