JPH03287158A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance dot image quality by incorporating at least one kind of each specified compound and processing the photosensitive material in a developing time of <= 20 sec by using the automatic developing machine speci fied in line speed. CONSTITUTION:The silver halide photographic sensitive material is processed in a developing time of <=20 sec by using the automatic developing machine having a line speed of 1500 mm/min, and it contains at least one of tetrazolium compounds represented by formula I and at least one of the compounds represented by formula II, and in formula I, each of R1 - R3 is H or a substitu ent and X is an anion, and in formula II, each of X, Y, and Z is H, 1 - 30 C optionally substituted alkyl or alkenyl, or the like; M is an alkali metal atom or the like; and each of (a) (l), (m), and (n) is 1, 2 or 3, thus permitting dot image quality to be enhanced even by the ultrarapid processing and uneven development to be reduced.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials,
More specifically, the present invention relates to a rapid processing method for printed photosensitive materials.

[Conventional technology]

In recent years, in the field of printing and photoengraving, printed matter has become increasingly colored and complex. For this reason, demands for improved and stable quality of silver halide photographic materials for printing (hereinafter referred to as printing materials), which are intermediate media for printing, are increasing year by year. Hitherto, in order to ensure high quality, ``Funatsuryo'' printing sensitive materials have been given suitability for so-called "lithography" processing. However, in "Lith development", it is mechanically impossible to contain a high concentration of sulfite ion, which is a preservative, in the developing solution, and as a result, the stability of the developing solution is extremely poor. , and that the development time is long is a well-known fact among those skilled in the art.

As a technique for solving the instability of "Lith development" and obtaining a high-contrast image comparable to "Lith development" processing, several attempts can be found disclosed in patent documents. For example: A technique for obtaining high-contrast images using a tetrazolium compound is disclosed in JP-A-52-18317 and JP-A-53-177.
No. 19, No. 53-17720, No. 57-132137
No. 58-173737, No. 59-79244,
It is disclosed in No. 61-117535 and the like. However, when trying to shorten the development processing time using the technique using the above-mentioned tetrazolium compound, a) deterioration of halftone dot quality occurs;
b) Problems such as development unevenness occur.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material using a tetrazolium compound with excellent halftone dot quality even when subjected to rapid processing in which the development process takes less than 20 seconds. An object of the present invention is to provide a method for processing silver halide photographic materials. Another object of the present invention is to provide a processing method that reduces the occurrence of uneven development.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide photographic material has the general formula [I
] and the following general formula [I
It is distantly related by a processing method characterized by containing at least one compound each represented by [I] and processing within 20 seconds using an automatic developing machine with a line speed of 1500 mm/min or more. .

General formula [I] It represents a substituent, and Xe represents an anion.

General formula [II] In the formula, x, y, z are a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a substituted or unsubstituted amino group, or an aryl group. R1 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, or an aryl group.

M represents an alkali metal atom or an ammonium group. a
represents an integer from 1 to 3. 12. m and n represent integers of 1 to 3.

As a method for rapid processing, for example, shortening the processing line may be considered, but this may lead to problems such as deterioration of uneven development, and increasing the line speed as in the present invention solves the problem of rapid processing. What will be solved is something that cannot be easily imagined.

The details of the present invention will be further explained below.

As a method for rapid processing, for example, shortening the processing line may be considered, but this may lead to problems such as deterioration of uneven development, and increasing the line speed as in the present invention solves the problem of rapid processing. What will be solved is something that cannot be easily imagined.

The details of the present invention will be further explained below.

First, in the general formula [11], preferable examples of the substituents represented by RI to R8 include alkyl groups (e.g. methyl,
ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino group, acylamino group (e.g. acetylamino), hydroxyl group, alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.) ), acyloxy groups (e.g. acetyloxy), halogen atoms (e.g. fluorine, chlorine, bromine, etc.), carbamoyl groups, acylthio groups (e.g. acetylthio), alkoxycarbonyl groups (e.g. ethoxycarbonyl), carboxyl groups, acyl groups (e.g. acetyl ), cyano group, nitro group, mercapto group, sulfoxy group, and aminosulfoxy group.

Examples of the anion represented by XQ include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, and acid groups of organic acids such as sulfonic acid and carboxylic acid. , anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, and higher alkyl sulfate esters such as lauryl sulfate anions. anions, borate anions such as tetraphenylpolone, dialkyl sulfosacinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxy sulfate anions, and higher grades such as stearate anions. Examples include polymers with acid groups attached, such as aliphatic anions and polyacrylic acid anions.

Specific examples of the compounds represented by the general formula [I] used in the present invention are listed in Table 1 below, and Compound No. of the present invention.

-1 -2 -3 -4 -5 6- 7- -9 -10 -11 ■-12 -13 -14 I(5 -16 -17 -18 ■-19 ■-20 −21 knee 22 -23 -24 ■-25 -26 table 2 -CH3 Ku-CH3 o-CI(.

p-CH.

-OCH3 m-OCt13 o-OCR.

-OCH3 1)-C2H6 -C2Hs 1) C3H7 p-OC21(5 -OCH3 -OCH3 p-OCsH+ + p-OC6H+ 7-n p-C+2H25-n p-N(CI(3)2 -NH2 -OH m-01( -CQ -CI2 -CH3 -OCH3 3 -CH3 m-CH.

o-CH.

p-CO.

-OCH3 -OCR3 -OCH3 -OCR3 1)-C2H5 m-C2H.

1) C3H7 p-OC2H.

-ocn3 p-OC2H5 -OCH3 p-OCaH+y　n p-C+2H25-n 11-N(CH3)2 -NH2 -OH m-0)1 -ca -CQ p-CH.

-oco3 The tetrazolium compound used in the present invention is described in, for example, Chemical Review (Chemical Revue).
It can be easily made into synthetic leather according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula [■] used in the present invention is about 1 mg to about 10 g, preferably about 1 mg to about 2 g, per mol of silver halide contained in the silver halide photographic material of the present invention. Used within the range of

The tetrazolium compound used in the present invention is described in, for example, Chemical Review (Chemical Review).
s) It can be easily made into synthetic leather according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula [■] of the present invention is about 1 mg to about 10 g, preferably about 10 mg to about 2 g per mole of silver halide contained in the silver halide photographic light-sensitive material of the present invention. It is preferable to use the range up to .

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

Next, general formula [II] A specific example of a compound represented by List.

Exemplary compounds ■ ■ -2 1-9 ■ 0 ■ ■ 4 ■ 1 ■ 2 ■ -6 ■ 3 ■ 4 1 2 ■ 5 ■ 6 ■ 3 ■ 4 Naphthalene sulfo represented by the above general formula [II] ■ 7 ■ 8 The additive amount of the acid-based activator is 1 mg or more and up to 10 g, preferably 10 mg or more and up to 2 g per mole of silver halide. For the silver halide emulsion, any silver halide used in ordinary silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. is 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 a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr, S
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as Ci), 21.39 (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, monodispersed 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 r is 60% or more of the weight of all silver halide grains. Some are preferred, particularly preferably 5 6 is 70% or more, more preferably 80% or more.

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

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

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 monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle size and particle size standard deviation are determined from rl defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

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 Die G.
Rundlagen der Photography
schen Prozesse mit Silver
Halogeniden, Akademicche
Verlagsgesellschaft, 1968
) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds 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. Pat. No. 1,574,944.
No. 2,410,689, No. 2,278.947, No. 2,728,668, and No. 3,656.957.85. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,419.
, No. 974, No. 2,518,698, No. 2,983,
No. 609, No. 2,983,610, No. 2,694,6
It is described in No. 37. For noble metal sensitization, use the periodic table of all complex salts, platinum, iridium, palladium, etc.■
Complex salts of group metals can be used; specific examples thereof include U.S. Pat. No. 2,399,083, U.S. Pat.
It is described in British Patent No. 618.061 and the like.

Further, there are no particular restrictions on the conditions such as pH, pAg, temperature, etc. during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is 5 to 11. In particular, it is preferable to keep it between 7 and 9. Also, the temperature is 40 to 9°C, especially 4
5-75°C is preferred.

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-■phenylte I.razole, 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, 90.

In the silver halide photographic material according to the present invention, a sensitizing dye may be further added and used in combination.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol 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, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei, such as tetrazole nuclei and pyridine nuclei, and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, such as indolenine nuclei, benzindolenine nuclei, and indole nuclei. , benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

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 for ordinary negative-working silver halide.

In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.

Approximately 1.0% of sensitizing dye per mole of silver halide. OX 10-
5 to about 5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-5 to 2 X moles of sensitizing dye per mole of silver halide.
Preferably, a concentration of 10-' molar is used.

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 1 2 .

That is, examples of the sensitizing dye used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Patent No. 2,231,658, US Patent No. 2,493.748, and US Pat. No. 2,519,001, No. 2
, No. 912.329, No. 3.656956, No. 3,6
No. 72,897, No. 3,694,217, No. 4,02
No. 5゜349, No. 4,046,572, British Patent No. 1,
No. 242,588, Special Publication No. 44-14030, No. 52
-24844, JP-A-48-73137, JP-A-61-
Examples include those described in No. 172140 and the like. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, US Pat. No. 1, No. 939.201, US Pat.
No. 072,908, No. 2,739.149, No. 2,9
No. 45.763, British Patent No. 505,979, Special Publication No. 4
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in Japanese Patent No. 8-42172. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
No. 70,378, No. 2,442,710, No. 2,45
No. 4,629, No. 2,776.280, Special Publication No. 1977-
No. 17725, JP-A-50-62425, JP-A No. 61-2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 9836 and No. 60-80841.

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 Nos. 2,688,545, 2,977.229, and 3
, No. 397.060, No. 3,522,052, No. 3,
No. 527.641, No. 3,617,293, No. 3,6
No. 28,964, No. 3,666.480, No. 3,67
No. 2,898, No. 3,679,428, No. 3,703
゜377, 3,769.3 old number, 3,814,6
09 No. 3, 837.

No. 862, No. 4,026,707, British Patent No. 1,34
No. 4.281, No. 1,507,803, Special Publication No. 1973-
No. 4936, No. 53-12375, JP-A-52-11
No. 0618, No. 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, oxanol dyes; hemioxanol 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), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially l
-phenyl-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 Many compounds known as stabilizers can be added, such as 4-hydroxy substituted (1,3,3a,7)tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, and the like.

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 Process, 3rd edition, 1966), citing the original literature.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 82.947, No. 4,021,248 or Tokuko Sho 5
The description in No. 2-28660 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.

5 6 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, Belgian Patent No. 762,833, US Patent No. 3
, No. 767.410 and Belgian Patent No. 588,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, Various hardeners and ultraviolet absorbers such as ethyleneimine type, active halogen type, vinyl sulfone type, incyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc., and ultraviolet absorbers include, for example, U.S. Patent No. 3,253, 92
No. 1, British Patent No. 1,309,349, etc., particularly 2-(2'-hydroxy-5
-tertiary butylphenyl)benzotriazole, 2-(2'
-Hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3'-
Tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5
Examples include '-di-tert-butylphenyl)-5-chlorobenzotriazole. Further, as coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548,532, British Patent No. 1, No. 216,389, U.S. Pat. No. 2,026.20
No. 2, No. 3,514,293, Special Publication No. 44-2658
No. 0, No. 43-17922, No. 43-17926,
No. 43-3166, No. 48-20785, Color Circle Patent No. 202,588, Belgian Patent No. 773,459,
Anionic, cationic, nonionic or amphoteric compounds described in JP-A-48-101118 etc. can be used, and among these, anionic surfactants having a sulfonic group, such as succinic acid Ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as antistatic agents, Japanese Patent Publication No. 46-24159, Japanese Patent Application Laid-Open No. 48-89979, and U.S. Patent No. 2,882,1
No. 57, No. 2,972,535, Japanese Unexamined Patent Publication No. 48-207
No. 85, No. 48-43130, No. 48-90391, Special Publication No. 46-24159, No. 46-39312,
There are compounds described in JP-A-48-43809 and JP-A-47-33627.

7 8 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 the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within 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 cloaking agents, such as silica described in Swiss Patent No. 330,158, glass powder described in Color Circle Patent No. 1,296,995, and British Patent No. 1.
, 173.181; inorganic particles such as alkaline earth metals or carbonates such as 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. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330, 158,
Organic particles such as polyacrylonitrile as described in US Pat. No. 3,079,257 and polycarpoint as described in US Pat. No. 3,022,169 can be included.

In the photosensitive material of the present invention, the constituent layers include slipping agents, such as those described in US Pat. No. 2,588,756 and US Pat.
higher aliphatic higher alcohol esters as described in No. 1, casein as described in U.S. Pat. No. 3,295.979, higher aliphatic calcium salts as described in British Patent No. 1.263722,
British Patent No. 1,313,384, US Patent No. 3,042,
522 and 3,489,567.

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

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 I tem
17643 (December 1978) and Volume 187 It
Described in em18716 (November 1979)
), SONO 2 0 In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers may be coated on one or both sides of a visible support commonly used in photographic light-sensitive materials. be able to. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers. (
Examples include paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer, or the like. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating treatment is as per JP-A-52-104913 and JP-A-52-104913.
No. 9-18949, No. 59-19940, No. 59-1
The treatments described in the 994 publications are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The development time in the present invention is within 20 seconds, preferably 15 seconds.
Describe the development, fixing, washing, and drying processes that take less than seconds.

1 2 The developing agent used in the black and white developer used in the present invention has dihydroxybenzene chains and l-
Most preferred is a combination of phenyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2.3 dibromohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

As the developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, l-phenyl-4,4dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-
Examples include 4-hydroxymethyl-3-pyrazolidone and l-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is usually 0.01 mol/ff-1.2 mol/12
of! It is preferably used in

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.2 mol/a or more, particularly 0.4 mol/a or more. The upper limit is preferably 2.5 mol/Q.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 1o to 12.

The alkaline agents used to set the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium 34 carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, nitinol, methanol; mercapto such as l-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may also contain antifoggants such as indazole compounds such as 5-nitroindazole, penttriazole compounds such as 5-methylbenztriazole, and furthermore, if necessary, color toning agents, surfactants, and antifoaming agents. , water softener, JP-A-56-1
The amine compound described in No. 06244 may also be included.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press (1
No. 966, pp. 226-229, U.S. Pat.
．． No. 015, No. 2,592,364, Japanese Unexamined Patent Publication No. 1973-6
Those described in No. 4933 may also be used.

In the present invention, "development time" and "fixing time" respectively mean
The time from when the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution, and the time from when it is immersed in the fixing tank solution until it is immersed in the next washing tank solution (stabilizing solution). say the time

Further, "washing time" refers to the time during which the product is immersed in the washing tank liquid.

In addition, "drying time" is usually 35°C to 100°C, preferably 5 6 or 40°C to 80°C. This refers to the time you are in the zone.

The development temperature and time are about 25 DEG C. to 50 DEG C. for 15 seconds or less, preferably 30 DEG C. to 40 DEG C. for 6 seconds to 15 seconds.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 mol/Q.

The fixer may also contain water-soluble aluminum-lamb salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

The fixing solution may include tartaric acid, citric acid, or four of them, either alone or in combination.

Those containing 0.005 mol or more of these compounds per fixer solution are effective, especially 0.005 mol or more per fixer solution. O1 mol/Q~0.03
Mol/a is particularly useful.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain preservatives (e.g., sulfites, bisulfites), pH buffering agents (e.g., acetic acid, nitric acid), pH adjusters (e.g., sulfuric acid), chelating agents with water softening ability, and patent applications. The compound described in No. 60-213562 may be included.

Fixing temperature and time are approximately 20°C to approximately 50°C for 6 seconds to 1
Minutes are preferred, but 6 seconds to 30 seconds at 30°C to 40°C are more preferred, and still more preferably 6 seconds to 15 seconds at 30°C to 40°C.

When the fixer concentrate is replenished into the automatic processor in the method of the invention with water to dilute it as the light-sensitive material is processed, it is most preferred that the fixer concentrate is composed of one part. is the same as the developer case.

The fixer solution can stably exist as an agent at pH 4,
5 or more, more preferably pH 4.65 or more. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfurized, especially if the fixer is left unused for a long period of time until it is actually used.

Therefore, when the pH is in the range of 4.5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of pH is not so strict, but if fixing is done at too high a pH, the pH of the membrane will be high even after subsequent washing with water, the membrane will swell, and the drying load will increase, so pi (up to 7) is the limit. Fixing solutions that use aluminum salts to harden films have a pH limit of 5.5 to prevent precipitation of aluminum salts.

In the present invention, either the developing solution or the fixing solution may be a so-called working solution that does not require dilution water as described above (that is, it is replenished as an undiluted solution).

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 0 to 8 l. The total amount of the developer and fixing wave trough is preferably from 50 mff to 1500 mQ per m2 of the photosensitive material.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being fixed by wind wave treatment.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water for washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to less than 3Q per m2 of photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. Furthermore, the number of stock tanks can be reduced.

That is, the solution dilution water and washing water or stabilizing solution for the developer and fixer can be supplied from a common single layer stock tank, making it possible to further downsize the automatic developing machine.

If anti-mildew water is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
0-312 per m2. Preferably, water saving treatment of 0 to 190 Ql can be performed.

Here, when the replenishment amount is O, there is no replenishment at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservoir water" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material in the fixer will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, part or all of the overflow liquid from the washing or stabilizing bath generated by replenishing the washing or stabilizing bath with water treated with anti-mold means is disclosed in Japanese Patent Application Laid-open No. 60-23.
As described in Japanese Patent Application No. 5133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-295894, No. 61-6
The method using the antibacterial agent described in No. 3030 and No. 61-51396 can be used.

Furthermore, L, E, West “Water Qual
ity Cr1teria Photo Sci & E
ng, Vol, 9No. 6 (1965), M.W.
, Beach “Microbiological G
rows in Motion-Picture
“Processing” SMPTE Journal
l Vol, 85. (1976).

R.O. Deegan, “Photo Proce
ssing Wash Water Biocides”
J, 1maging Tech, Vol 10. No
, 6 (1984) and 1 2 and JP-A Nos. 57-8542, 57-58143, 5g-105145, 57-132146, 5
No. 8-18631, No. 57-97530, No. 57-1
Antibacterial agents and anti-inflammatory agents described in No. 57244 etc.
A surfactant or the like can also be used in combination.

Furthermore, for the washing bath, R.T. Kreiman, J.I.
mage, Techlo, (6) 242 (19
84), an inthiazoline compound described in RESE
ARCHDISCLO5URE Volume 205, Item 2
Isothiazoline compounds described in 0526 (May issue, 1981), Volume 228, Item 2284
5 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used together as microbiocides.

Furthermore, specific examples of anti-pissing agents include phenol, 410 lophenol, pentachlorophenol, cresol, 0
-Phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-(4
-thiazoline) benzimidazole, benzisothiazoline-3one, dodecyl-benzyl-dimethylammonium chloride phthalimide, 2,4,4'-trichloro-2
'-Hydroxydiphenyl ether, etc.

The water that has been treated with anti-mold measures and stored in the water stock tank is diluted with water for diluting the undiluted solution of the processing solution such as the developer/fixer, and the amount thereof added is preferably 0. Ol~10g/Q, more preferably 0.1
~5g10. It is.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pH (e.g. pH 3
~8) Various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polyester) Typical examples include aldehydes such as formalin (used in combination with carboxylic acids, etc.) and formalin. Other chelating agents, fungicides (thiazole type, inthiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.)
Various additives such as surfactants, optical brighteners, hardeners, etc. may be used, and two compounds of the same or different types may be used.
More than one species may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. as a membrane pFl adjusting agent to the processing solution in order to improve image storage stability.

Water washing or stabilization bath temperature and time by the above method is 0°
Preferably 6 seconds to 1 minute at 15°C to 40°C
℃ for 6 seconds to 30 seconds, more preferably 15℃~
6 to 15 seconds at 40°C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is carried out at about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 1 minute, but more preferably 4
It is about 5 seconds to 30 seconds at 0°C to 80°C.

In the present invention, the line speed is 1500 mm/mi.
n or more, preferably 1,800 mm/min or more, more preferably 2,000 mm/min or more.

In the present invention, an even more excellent effect is exhibited in that the lower the swelling percentage of the photosensitive material, the shorter the drying time thereof.

According to the method of the present invention, the so-called dry-to-dry processing time for development, fixing, washing, and drying is 1
Within 00 seconds, preferably within 60 seconds, more preferably within 50 seconds
It should be processed within seconds.

Here, "dry to dry" refers to the time from the moment the leading edge of the photosensitive material to be processed enters the film insertion section of the automatic processor to the moment the leading edge emerges from the processor after being processed.

5 6 [Example 1] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 EAg was adjusted to 120 mV in the presence of water-soluble iridium 2 x 10-6 mol/silver 1 mol and water-soluble rhodium 4 x 10-' mol/silver 1 mol while controlling the pH to 3.0, and the odor Silver chlorobromide grains containing 30 mol % of silver oxide were obtained. The particles were cubic crystal particles with an average particle size of 0.24 μm and a distribution width of 11%. After gold sensitization and sulfur sensitization, an ortho-sensitizing dye was added, and 4-hydroxy-6methyl-1.
3. Add Ig of 3a, 7-chitrazaindene, add compounds of general formula [I] and (II) as shown in Table 2, and add n-
600mg of sodium dodecylbenzenesulfonate,
2 g of styrene-maleic acid copolymer was added and coated on a polyethylene terephthalate film. At that time, l-decyl-2-(3-isopentyl)succinate-2-sul.
A hardening protective layer containing 30mg/m2 of sodium phonate and 25mg/m2 of formalin as a hardening agent was applied in multiple layers.

The obtained sample was subjected to stepwise exposure to tungsten light through a commercially available normal contact screen (gray negative 150L), and then, using a developer and a fixer having the following composition,
The samples were processed using an ordinary roller type automatic developing machine under the conditions shown in Table 2, and the halftone dot quality was evaluated. In addition, it was exposed to light so that the density was 1.0 to 1.3 and processed in the same way,
Development unevenness was evaluated. In addition, the halftone dot quality and development unevenness are
The evaluation was divided into O stages. IO is the best level, 1 to 4 is unusable, and 5 or more is usable.

From Table 3, it can be seen that the film of the present invention has good halftone dot quality and few black spots, and also has good development unevenness.

When changing the development time at the same line speed, the depth of the tank and the number of rollers were adjusted.

Developer formulation (composition A) Pure water (ion-exchanged water) 150 mQ7 8 Ethylenediaminetetraacetic acid disodium salt 2 g diethylene glycol 50 g Potassium sulfite (55% w/v aqueous solution) 100 mQ.

Potassium carbonate 50g Hydroquinone 15g 5-methylbenzotriazole 200111g -Phenyl-5-mercaptotetrazole 0111g Potassium hydroxide, amount to bring the working solution's PO to 1004 Potassium silver bromide 4.5g (composition) Pure water (ion-exchanged water) 3m <1 Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 + n (25-nitroindazole 110 mg It was melted and finished to IQ for use.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 2
40mff sodium sulfite 1
79 Sodium acetate trihydrate 6.5g
Boric acid 6° Sodium citrate dihydrate 2g Acetic acid (90% w
/v aqueous solution) 13.6mff (composition) Pure water (ion exchange water) 17mQ sulfuric acid (50% v/v aqueous solution) 4.7g
Aluminum sulfate (A12202 equivalent content: 8.1% w/v aqueous solution)
When using 26.5g fixer, add the above set f! to 500+nQ of water! Dissolve A and composition B in this order, 10. It was finished and used. This fixation 9 0 Comparative compound (A) CH2C00 (JI2CH (C211a) C, 1ieC
IIC00CH2C)l(C2Ha)C+Il.

SO, Na I 3 Table [Effects of the Invention] The present invention provides excellent halftone image quality even with ultra-quick processing.
Silver halide photographic feel with less uneven development 2

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide photographic material comprising a tetrazolium compound represented by the general formula [I]. and a processing method comprising at least one compound each represented by the following general formula [II], and the processing is carried out in a developing time of 20 seconds or less using an automatic developing machine with a line speed of 1500 mm/min or more. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2 and R_3 each represent a hydrogen atom or a substituent, and X^■ represents an anion. ] General formula [II] [In the formula, X, Y, and Z are a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a substituted or unsubstituted amino group , represents an aryl group, hydroxyl group, mercapto group, carboxyl group or -CONHR_4, -SO_2NHR_4, R_4 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group,
Represents an aryl group. M represents an alkali metal atom or an ammonium group. a
represents an integer from 1 to 3. l, m, and n represent integers of 0 to 3. ]