JPH03278049A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a high contrast and to decrease unequal development by incorporating respectively one kind of a specific tetrazolium compd. and specific compd. into the silver halide photographic sensitive material. CONSTITUTION:Respective one kind of the tetrazolium compd. expressed by formula I and the compd. expressed by formula II are incorporated into the silver halide photographic sensitive material. In the formula I, R1 to R3 respectively denote a hydrogen atom or substituent; X<theta> denotes anion./ In the formula II, X, Y, Z denote a hydrogen atom or 1 to 30C substd. or unsubstd. alkyl group, alkenyl group, alkoxy group, alkoxy carbonyl group, etc.; M denotes an alkaline metal atom or ammonium group; (a) denotes an integer from 1 to 3; l, m, n denote integers from 0 to 3. The silver halide photographic sensitive material which has the high contrast and can decrease the nonuniformity of image density by the nonuniform development at the time of development is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has a high contrast and is free from uneven image density due to uneven development during development. Uniform This invention relates to a silver halide photographic material with reduced so-called development unevenness.

[Background of the invention]

The photoengraving process using silver halide photographic light-sensitive materials involves the process of converting a continuous tone original into a halftone image, that is, the process of converting a continuous tone density change into a halftone dot image having an area proportional to the density. and a step of converting the halftone dot image obtained in this step into a better halftone dot image, that is, a turning step.

It is essential that the photosensitive materials used in these processes have high contrast in order to obtain good halftone dot quality.

Conventionally, the method for obtaining such characteristics is to develop a photosensitive material consisting of a silver chlorobromide emulsion with relatively fine grains, a narrow particle distribution, and a high silver chloride content using an alkaline hydroquinone developer with a very low sulfite ion concentration. A processing method, the so-called lithographic development method, is known.

However, when this method is used, the storage stability is extremely poor due to the low concentration of sulfite ions in the developer, and the development speed is slow due to the use of hydroquinone as a single agent, making rapid processing impossible. .

Therefore, high contrast can be obtained by processing with a so-called PQW or MQ type developer, which contains a super-additive developing agent that has good storage stability and can be processed quickly, and contains a relatively high concentration of sub-VT# salt. The development of new photosensitive materials is desired.

One of the things related to this new photosensitive material is Japanese Patent Publications No. 59-17825, No. 59-17818, No. 59-
No. 17819, No. 59-17820, No. 59-178
No. 21, No. 59-17826, No. 59-17822, etc. disclose silver halide photographic materials containing a tetrazolium compound.

The method of processing a photosensitive material containing these tetrazolium compounds with a superadditive developer to obtain a silver image with high contrast can be said to be an extremely innovative technique compared to conventional techniques.

However, when the gradation of silver halide photographic light-sensitive materials is made to have very high contrast, slight unevenness in development,
For example, the density changes slightly due to uneven diffusion of developing agents and uneven diffusion of development inhibitors such as Br ions.
There was a problem that it was not suitable for use. The phenomenon of rBr drugJ in the above-mentioned Lith development method is also an example of this.

Methods for improving rBr drugJ in lithographic development include: (1) reducing the Br content in the silver halide composition of the lithographic photosensitive material;

(2) A method of using an amine compound in a light-sensitive material is known, but this method causes desensitization and increased fog, and its effects are insufficient. Furthermore, since the photosensitive material containing the above-mentioned tetrazolium compound also has a development speed about three times that of lithography, unevenness in development due to high contrast may become more severe depending on the processing conditions.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a silver halide photographic material that has high contrast and reduces unevenness in image density due to uneven development during 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, the silver halide photographic material being represented by the following general formula (1). This is achieved by a silver halide photographic material containing at least one tetrazolium compound and at least one compound represented by the following general formula (II).

General Formula [I] In the formula, R,, R1 and R1 each represent a hydrogen atom or a substituent, and xe represents an anion.

General formula CI[] During the ceremony, X.

1 2 is 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, an aryl group, a hydroxyl group, a mercapto group, a carboxyl group, or -CONHR. -5O, NHR, and R4 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. fi, m, and n represent integers of θ to 3.

The present invention will be explained in detail below.

First, in the above general formula [1], preferable examples of the substituents represented by R8 to R1 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 group (e.g. acetyloxy), halogen atom (e.g. fluorine, chlorine, bromine, etc.), carbamoyl group, acylthio group (e.g. acetylthio), alkoxycarbonyl group (e.g. ethoxycarbonyl), carboxyl group, acyl group (e.g. acetyl) , a cyano group, a nitro group, a mercapto group, a sulfoxy group, and an aminosulfoxy group.

(above) (Examples of anions represented by e include halogen ions such as chloride ions, bromide ions, and iodide ions; acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid; and organic acids such as sulfonic acids and carboxylic acids. acid radicals, anionic activators, specifically lower alkylbenzenesulfonate anions such as p-toluenesulfone strict anions, p-dodecylbenzenesulfonate anions, higher alkylsulfate ester anions such as lauryl sulfate anions, and tetraphenyl. Boric acid anions such as poron, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxy sulfate anions, higher aliphatic anions such as stearin anions, Examples include polymers such as polyacrylic acid anions with acid groups attached.

Specific examples of the compounds represented by the general formula [I] used in the present invention are listed in Table 1 below.

-CH3 -CHs p-octt.

■-OCEi.

o-OCR.

■-CB.

-CH3 p-CB.

-OCHs s-OCH.

o-OCH.

I 11 H m-CJi
--C*HsI-12 Ei p-
CsHt p-C3H7I 13 H
p-OCxTo p-QC! HS ■-16 -17 -18 -19 p-OC. H. .

p-OCmHty~n p-C+*l(2s-n p-N(CHs)z p-OCH.

p-QC,l,,-n p-CIxH□-n p-N(CH3)* ■-23 -crt -cn ■-27 p-OCR.

-OCR3 fl-CttoosOso,e The tetrazolium compound used in the present invention is described in, for example, Chemical Revie
It can be easily synthesized according to the method described in WS Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula (1) used in the present invention is about 1-g to about 10 g per mole of silver halide contained in the silver halide photographic material of the invention, preferably about 10 layers. It is used in a range of 1 g to about 2 g.

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

The tetrazolium compound represented by the general formula [I] of the present invention may be used in an amount of about 1 mg or more, preferably about 10-g or more, per mole of silver halide contained in the silver halide photographic material of the present invention. Preferably, amounts up to about 2g are used.

The tetrazolium compounds represented by the general formula [I] 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 ■ ■ ■ ■ ■ ■ ■ ■ ■ 11 ■ 13 ■ 10 ■ 12 ■ 14 ■ 15 ■ 17 ■ 19 ■ 21 ■ 16 ■ 18 ■ 20 ■ = 22 ■ -23 f-24 In the above general formula rI[) The amount of the naphthalene sulfonic acid-based activator additive is from 1g to 10g, preferably from 1018 to 12g per mole of halogenated #.

Next, the silver halide emulsion used in the light-sensitive material of the present invention includes conventional halides such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any material used in silver emulsions can be used, and 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 op.
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. 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, 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 r is 60% or more of the weight of all 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 frequency ni of particles having particle size ri
The particle size r when the product n1Xri'' of and ris is maximum
Define i.

(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 4852 as defined above.
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 without chemical sensitization as a so-called prismatic emulsion, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
eliklan et al. or H. Frleser, ed.
Die
Grundlagen der Photography
ischen Prozesse with Silbe
rhalogeniden%Akademichche
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, specific examples of which are described in U.S. Pat. No. 1,574.944.
No. 2,410.689, No. 2,278,947, No. 2,728.668, and No. 3,656.955. 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. .97
No. 4, No. 2,518,698, No. 2,983.609
No. 2,983.610 and No. 2,694.637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in group II of the periodic table, such as platinum, iridium, and palladium, can be used.
, 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 pHlpkgs temperature during chemical sensitization, but the pH value is preferably kept at 4 to 9, especially 5 to 8, and the pAg value is preferably kept at 5 to 11, especially 7 to 9. preferable. Also, the temperature is 40 to 90°C, especially 45°C.
~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-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as 1,000-onythyl,
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, 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, 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, Sochi, indolenine nucleus, benzindolenine nucleus, indole A benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a 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 in ordinary negative-working silver halides.

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-
' to about 5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-' to 2 moles of sensitizing dye per mole of I\silver halide.
It is preferred to use a concentration of X 10-' 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 sensitizing dyes 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. 2,519.001, No. 2
, No. 912.329, No. 3,656゜956, No. 3,
No. 672,897, No. 3,694.217, No. 4,
025.

No. 349, No. 4,046,572, British Patent No. 1,24
2.588, Special Publication No. 44-14030, No. 52-2
No. 4844, JP-A-48-73137, JP-A No. 61-17
Examples include those described in No. 2140 and the like.

Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat. No. 1,939.201 and U.S. Pat.
No. 2.908, No. 2,739.149, No. 2,945
．． No. 763, British Patent No. 505.979, Special Publication No. 1973-
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in Japanese Patent No. 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 include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 9836 and No. 6040841.

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, 3,769.301, 3,814,
No. 609, No. 3,837゜862, No. 4,026.7
07, British Patent No. 1,344.281, British Patent No. 1,507
．． No. 803, Special Publication No. 43-4936, No. 53-123
No. 75, JP-A-52-110618, JP-A No. 52-109
No. 925, etc.

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 preventing eradication and halide. 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 of these variants 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 has 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, 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. Hardening agents include aldehyde-based, epoxy-based, Various hardeners and ultraviolet absorbers such as ethyleneimine, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl hardeners include, for example, U.S. Pat. No. 3,253,92.
1, British Patent No. 1.309.349, especially 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',
Examples include coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and various physical agents for photosensitive materials. British patents 54g and 532 describe surfactants used to control properties.
No. 1,216.389, U.S. Patent No. 2,026.2
No. 02, No. 3,514.293, Special Publication No. 44-265
No. 80, No. 43-17922, No. 43-17926, No. 43-3166, No. 48-20785, French Patent No. 202.588, Belgian Patent No. 773.459, JP-A-48-101118, etc. It is possible to use anionic, cationic, nonionic or amphoteric compounds described in , among which anionic surfactants having a sulfone group, such as succinic acid ester sulfonates, alkylbenzene sulfonates, etc. is preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159
No., JP-A-48-89979, U.S. Patent No. 2.882,
No. 157, No. 2,972.535, Japanese Unexamined Patent Publication No. 1972-20
No. 785, No. 48-43130, No. 48-90391
There are compounds described in Japanese Patent Publication No. 46-24159, Japanese Patent Publication No. 46-39312, Japanese Patent Publication No. 48-43809, and Japanese Patent Publication No. 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 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 pn is larger 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 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, Belgian Patent No. 62
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, and U.S. Pat. , 079,257, and polycarbonates described in U.S. Pat. No. 3,022,169.

In the light-sensitive material of the present invention, the constituent layers include slipping agents, such as 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. 3,04
2.522 and 3,489.567, etc. may also be included.

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 Volume 8176 I tem
17643 (December 1978) and Volume 187 It
em18716 (November 1979), and in carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers are formed on a flexible support commonly used in photographic light-sensitive materials. It can be constructed by coating on one or both sides. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or a-olefin polymers. (For example, paper coated or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. 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 undercoat treatment is according to JP-A-52-104913.
The treatments described in Japanese Patent No. 59-18949, No. 59-19940, and No. 59-18949 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.

The developing agent used in the black and white developer used in the present invention has a dihydroxybenzene chain and 1-
Most preferred is a combination of phenyl-3-pyrazolidones. Of course, a p-amine phenol 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, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred.

As a developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, l-7enyl-4. Examples include <-dimethyl-3-pyrazolidone, l-7enyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and l-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

The p-aminophenol-based developing crude drugs used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)cridine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc. Among them, N-methyl-p-
Aminophenols are preferred.

The developing agent is usually 0. It is preferably used in an amount of O1 mol/12 to L2 mol/Q.

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/g or more, particularly 0.4 mol/Q or more. Further, the upper limit is preferably up to 2.5 mol/Ω.

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.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator.

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 cellosolvercol, nitinol, methanol: 1
- Fog of mercapto compounds such as phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, benztriazole compounds such as 5-methylbenztriazole, etc. It may contain an inhibitor, and if necessary, a color toning agent, a surfactant,
It may also contain an antifoaming agent, a water softener, an amino compound described in JP-A-56-106244, and the like.

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.

Other than this. F. A. “Photographic Processing Chemistry” by Messon, published by Focal Press (
(1966), pp. 226-229, U.S. Patent No. 2.

No. 193,015, No. 2,592,364, JP-A-4
Those described in No. 8-64933 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.

Furthermore, "drying time" refers to the time the machine is in the drying zone, which is usually equipped with a drying zone where hot air of 35°C to 100°C, preferably 40°C to 80°C, is blown. means.

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

The fixer is an aqueous solution containing thiovLrlk salt and has a pH of 3.
, 8 or more, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and heptammonium 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 fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol/12
It is.

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

The fixing solution can be made by using tartaric acid, citric acid, or conductors thereof alone or in combination of two or more thereof.

Those containing 0.005 mol or more of these compounds per fixer iff are effective, especially 0.005 mol or more per fixer iff. O1 morph m-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. sulfite, birL salt), pH buffering agents (e.g. acetic acid, nitric acid),
It can contain a pH adjuster (for example, Wa sulfur), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-213562.

The fixing temperature and time are preferably 6 seconds to 1 minute at about 0°C to about 50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, and still more preferably 6 seconds to 15 seconds at 30°C to 40°C. Seconds.

When the fixer concentrate is refilled in the automatic processor in the method of the invention with water to dilute it as the light-sensitive material is processed, the fixer concentrate (most preferably comprised of a λl agent) is the same as for the developer.

The fixer solution can exist stably as a l 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 sulfided, especially if the fixer is left for a long period of time before 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 fixation is carried out at too high a pH, the pH of the membrane will be high even after subsequent washing with water, and membrane swelling will increase, resulting in a large drying load, so the upper limit is around pH 7. 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 1: θ ~ 8. The total amount of each of the developing solution and fixing solution is preferably from 50 IIQ to 1500 μa per 1 m'' of the photosensitive material.

In the present invention, the photosensitive material is developed, fixed, and then subjected to water washing or stabilization 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 1 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 the washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
It is possible to save water by 0 to 3 β, preferably 0 to 1 g1.

Here, when the replenishment amount is 0, no replenishment is performed 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 "reservation 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.

Patent application FIii6 (1-
It is more preferable to provide a squeeze roller cleaning tank as described in No. 172968.

Furthermore, a part or all of the over-70 liquid from the washing or stabilizing tower, which is generated by replenishing the washing or stabilizing bath with water treated with anti-mold means, is used 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, EJest Water Qualit
y Cr1teria” Photo Sci & En
g, Vol, 9No, 6 (1965), M, W-
Beach″Microbiological Gro
wths in Motion-Picture Pr
ocessing"SMPTE Journal Vo
l, 85. (1976) - R.O., Deegan,
“Photo Processing Wash W
aterBiocides” J, Iwaaging
TechJol 10. No. 6 (1984) and Japanese Patent Application Publication Nos. 57-8542, 57-58143, and 58-
No. 105145, No. 57-132146, No. 58-1
No. 8631, No. 57-97530, No. 57-1572
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 44 and the like can also be used in combination.

Furthermore, for the washing bath, R, T, Kreiman @J, Im
age, Tech10, (6) 242 (1984)
RESEARC, an inthiazoline compound described in
HDISCLOSURE Volume 205, Item 2052
6 (May 1981), isothiazoline compounds described in Volume 228, Item 22845 (
Inthiazoline compounds described in Japanese Patent Application No. 1983-51396 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
O-7 dinylphenol, chloro7ene, dichloro7ene, formaldehydol aldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-(4-thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl -dimethylammonium-chloride%N-(fluorodichloromethylthio)-7talimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and the like.

The water treated with antifungal measures and stored in the water stock tank is diluted with water for diluting the stock solution of the processing solution such as the developer/fixer, and the amount thereof added is preferably 0.01-10g/Q, more preferably 0.1-10g/Q. It is 5g/12.

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 pa (e.g. pH 3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphorous salt, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as formalin (used in combination with acids, etc.) and formalin. In addition, various additives such as chelating agents, bactericidal agents (thiazole type, inthiazole type, halogenated phenol, sul-7anilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardening agents may be used. Often, two or more of the same or different desired compounds may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

Water washing or stabilization bath temperature and time by the above method is 0℃
6 seconds to 1 minute at ~50°C is preferred, but 6 seconds to 1 minute at 15°C to 40°C
The heating time is more preferably from seconds to 30 seconds, and even more preferably from 6 seconds to 15 seconds at 15°C to 40°C.

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 0°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 preferably at 40°C.
~80°C for about 5 seconds to 30 seconds.

In the present invention, the line speed is 1500+m/si.
n or more, preferably 1800 mm/sin or more, more preferably 2000 mm/sin 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 from 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 area of the processor to the moment the leading edge emerges from the processor after being processed. .

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Example 1 In the presence of water-soluble iridium 2 X 10-' mol/silver 1 mol and water-soluble rhodium 4 Silver chlorobromide particles containing 30 mol % of silver 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-6-methyl-1,
Add Ig of 3,3a,7-chitrazaindene, add compounds of general formulas (1) and (II) as shown in Table 2, and add n-
600 g of sodium dodecylbenzenesulfonate,
2 g 1 lr JL of styrene-maleic acid copolymer was coated onto a polyethylene terephthalate film. At that time, use l- as a spreading agent so that the gelatin amount is 1.0g/■
Decyl-2-(3-isopentyl)succinate-2-
A hardening protective layer containing 30 g/2 of sodium sulfonic acid and 25 mg/2 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. 10 is the best level, 1-4 is unusable, and 5 or higher 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 solution Asahikata (composition A) Pure water (ion-exchanged water) 150 g A Disodium salt of ethylenediaminetetraacetic acid 2 g Diethylene glycol 50 g Potassium sulfite (55% w/v aqueous solution) 100 tQ Potassium carbonate 50 g Hydroquinone
15g 5-methylbenzotriazole 200ssl-phenyl-5-mercaptotetrazole 0mg Potassium hydroxide, amount to bring the pH of the solution to 10.4 Potassium silver bromide 4.5g (composition) Pure water (ion-exchanged water) 3 parts Diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 25a + g acetic acid (90% aqueous solution) 0.3m<25-nitroindazole llomgl-phenyl-3
- Pyrazolidone 7001 g When using a developer, the above composition A1 set ff1B was dissolved in the order of 500 g of water and finished to Ml.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w/v aqueous solution) 24
0■a Sodium sulfite 179
Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% W/V
Aqueous solution) 13.6m (2 (composition) Pure water (ion exchange water > 17-〇 Sulfuric acid (50% w/v aqueous solution) 4.79
Aluminum sulfate (A (I2oz equivalent content: 8.1% v/v aqueous solution)
When using the 26.59 fixer, it was dissolved in 500 μQ of water in the order of the above composition A1 and finished to 112 before use. This fixing CH, ■■ Horse cH (CtHx) C & αα collection MtCH (CxHg>C4Ha 0INa [Effects of the Invention] According to the present invention, the halftone image quality is excellent even with ultra-quick processing,
Moreover, it was possible to provide a method for processing silver halide photographic materials with less uneven development.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide photographic light-sensitive material comprising a tetrazolium compound represented by the following general formula [I]. A silver halide photographic material containing at least one compound and at least one compound represented by the following general formula [I]. General formula [I] ▲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^Θ represents an anion. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables etc. Represents a carbonyl group, a substituted or unsubstituted amino group, an aryl group, a hydroxyl group, a mercapto group, a carboxyl group, or -CONHR_4, -SO_2NHR_4, where R_4 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, alkenyl group, 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. ]