JPH02167542A - Processing of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a picture image contg. scarce after color even in a case of performing a rapid processing by performing the processing within 45sec from development, fixing, washing with water to stabilization of a photosensitive material contg. a specified dye and an anionic surface active agent, in an automatic developing device having >=1,500mm/min line speed capacity. CONSTITUTION:A silver halide photographic sensitive material contg. a dye expressed by the formula I and an anionic surface active agent in at least one layer of the photosensitive material, and the material is processed within 45sec. from development, fixing, to washing with water or stabilization in an automatic developing device having >=1,500mm/min line speed capacity. In the formula I, each R1-R6 is a (substituted)alkyl group; each Z1 and Z2 is a group of nonmetal atoms necessary for forming a benzo- or naphtho-condensed ring, wherein each R1-R6 and Z1-Z2 is a group permitting a dye molecule to have at least 4 acid groups; L is a methine group; X is an anion. Thus, a silver halide photographic sensitive material is processed with scarce generation of after color even in a case of extremely rapid processing.

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 method for processing printed photosensitive materials having rapid developability.

[Conventional technology]

In recent years, the consumption of silver halide photographic dyes has continued to increase. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of processing within the same amount of time.

The above trend can also be seen in the printing plate making field.

In other words, as the immediacy and number of times information is rapidly increasing, it has become necessary to handle a larger volume of printing plate-making work even with shorter delivery times. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly.

However, it has been found that shortening the length of the processing line in order to shorten the processing time causes deterioration of residual color and unevenness of residual color, which is not desirable.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a method for processing silver halide photographic materials that leaves little residual color even when ultra-rapid processing is performed.

[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 and a back layer on the opposite side of the support. At least one layer contains at least one dye represented by the following general formula [■] and at least one anionic surfactant, and the line speed is 150.
This was achieved by a processing method characterized in that the processing time from development, fixing, washing and/or stabilization processing is within 45 seconds using an automatic developing machine with a speed of 0 mm/min or more.

General formula CI) Rt Rt (X)O
n−+ [wherein, R+, R2, R3, R4, Rs and R
6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and Zl and Z2 represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted benz fused ring or naphtho fused ring, respectively. . However, Rl, R2
+R3, R4+R5, Ra, Z and Z2 represent groups which allow the dye molecule to have at least 4 acid groups. L represents a substituted or unsubstituted methine group,
indicates an anion. n is 1 or 2, and 1 when the dye forms an internal salt].

The present invention will be explained in detail below.

The line speed in the process of the present invention is 1500mm/
min or more, preferably 1800 mm/min or more, more preferably 2000 mm/min or more. Processing time for developing, fixing, washing with water and/or stabilizing solution of the present invention is 4
Within 5 seconds means that the time from when the leading edge of the film enters the developer until it comes out of the fixer, washing water, and/or stabilizing solution is within 45 seconds, and from each solution until it goes to blowing. Includes migration time. In the present invention, it has been found that by increasing the processing line speed without shortening the length of the processing line and processing the photosensitive material of the present invention, the object of the present invention can be achieved without causing the above-mentioned problems. did. Incidentally, the preferable processing time is 40 seconds or less.

Next, general formula CI) will be explained.

General formula [,1) where R1, R2, Rs, Rt, Rs, R
6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and Zl and Z2 each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring. .

However, R,, R2, R1+R4, Rs+R6+Z l+
At least four of the groups represented by Z2 have acid substituents (e.g. sulfonic acid groups or carboxylic acid groups),
Particular preference is given to a group which allows the dye molecule to have 4 sulfonic acid groups.

In the present invention, a sulfonic acid group means a sulfo group or a salt thereof, and a carboxylic acid group means a carboxyl group or a salt thereof.

Examples of salts include alkali metal salts such as Na, ammonium salts, and organic ammonium salts such as triethylamine, tributylamine, and pyridine.

L represents a substituted or unsubstituted methine group, and X represents an anion. Specific examples of the anion represented by XO include halogen ion (C(2,Br),I)-toluenesulfonic acid ion, ethyl sulfate ion, and the like.

n represents 1 or 2, and is 1 when the dye forms an inner salt.

The alkyl groups represented by R+, R2, R3, Rt, Rs, and Ra are preferably lower alkyl groups having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, n-furobyl group,
n-butyl group, isopropyl group, n-pentyl group, etc.)
represents a substituent (e.g. sulfonic acid group, carboxylic acid group,
hydroxyl group, etc.).

More preferably, R and R1 are lower alkyl groups having 1 to 5 carbon atoms having a sulfonic acid group (e.g., 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, etc.)
represents.

2. Substituents of the benzo-fused ring or naphtho-fused ring formed by the nonmetallic atom group represented by 22 include a sulfonic acid group, a carboxylic acid group, a hydroxyl group, a halogen atom (for example, F 2 , CQ, Br, etc.), a cyano group, Substituted amino groups (e.g. dimethylamine group, diethylamino group, ethyl-4
-sulfobutyl group, di(3-sulfopropyl)amino group, etc.), or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms bonded to the ring directly or via a divalent linking group (e.g. methyl group, ethyl group, propyl group, butyl group (substituents are preferably sulfonic acid group, carboxylic acid group, hydroxyl group, etc.), and divalent linking groups are, for example, -〇-, -NHCO-, -NHSO2-, -NHCO
O-, -NHCONH--coo-, -co-, -5o
2- etc. are preferred.

The substituent for the methine group represented by L has 1 to 5 carbon atoms.
Substituted or unsubstituted lower alkyl groups (e.g. methyl group, ethyl group, 3-hydroquinepropyl group, benzyl group, 2-sulfoethyl group, etc.), halogen atoms (e.g. F
, CQ, Br), substituted or unsubstituted aryl groups (e.g. phenyl group, 4-chlorophenyl group, etc.),
Lower alkoxy groups (eg, methoxy group, ethoxy group, etc.) are preferred.

The substituents of the methine group represented by a ``cross'' may be bonded to each other to form a 6-membered ring (for example, a 4,4-dimethylcyclohexene ring) containing three methine groups.

Specific examples of the dye compound represented by formula CI) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

[■ l〕

[■ 2] [I 3] [■ 4] [I 5] l-61 [I 7] [I 8] [■ 13] 14] [■ o3e O3K [1 16] [■ 9] [■ lO] [ I 11] [1 12] [■ 17] [■ 18] [■ 19] [■ 20] [■ 21] Cl-25) [I 23] [I 24] The dyes represented by the general formula [■] , absorption maximum is at wavelength 730
~850 nm, Journal of the Chemical Society (J, Chem, Soc, 189
(1933) and US Pat. No. 2,895,955.

The above-mentioned dyes can be used in a suitable solvent (e.g. water, alcohol (e.g. methanol, ethanol, etc.), methyl cellosolve, etc.).
or a mixed solvent thereof) and added to the coating solution for a hydrophilic colloid layer of the present invention.

/m2, in particular in the range from lo-2 g/m2 to 0.2 g/m2.

The dye represented by formula CI) of the present invention is particularly effective for the purpose of preventing irradiation, and when used for this purpose, it is mainly added to the emulsion layer.

The dyes of this invention are also particularly useful for antihalation purposes, where they are added to the backside of the support or to a layer between the support and the emulsion layer.

The dyes of this invention are also useful as dyes to impart safelight safety, in which case they are added to layers above the emulsion layers.

In addition, the amount of gelatin on the side containing the dye of the present invention is 3.9
g/m2 or less, more preferably 3.5 g/m2 or less, and the anionic surfactant used in the present invention has a hydrophobic part and a hydrophilic part in its molecule, and at least the solution is It is not particularly limited as long as it shows a decrease in surface tension.

The anionic surfactants particularly preferably used in the present invention include the following formulas (IIA), (IIB: l
, CIIC) and l:IID).

General formula (I[A) R+ OCOCH2 R2-0CO-CH-R.

Formula (I[B) R, -0CO-CH2 R5-OCO-CH R, -0CO-CH-R.

General formula (IIC) General formula (IID) is not limited to these.

[Compound example]

In the above formula, Rl, R2, R4+Rs, R6, Rs, Rh
and Rlo may be the same or different, and each represents a halogen atom, such as an alkyl group such as chlorine or bromine, such as a methyl, ethyl, butyl, isobutyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, octadenyl group, etc. It may be linear or branched, and preferably has 1 to 32 carbon atoms. These alkyl groups may be substituted with any substituent such as a halogen atom, such as a chlorine atom or a bromine atom, or an allyl group, such as a phenyl group or a naphthyl group. Also, R3 and R7
represents an alkali metal salt of a carboxyl group, a sulfo group, and a phosphonic acid group. nl and R2 represent integers of 1 to 3.

Specific compounds represented by the general formulas (IIA) to ClID:] are illustrated below, and the compounds of the present invention C, H,
,0OC-CH2 C+ OH2100CCl(So,NaC,+(,,0
OCCI(2C142C,11,,0OCCH+Cl-1-3O3NaC21
15 CH, (CH2), -〇〇〇-CH2 CH3(CH2), -0CO-CH CH3(CI(2)+-0CO-CH-3o, Na2H
5. The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. 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. A preferred example is a cube having the +1001 plane as the 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 an octahedron, a tetrahedron, a dodecahedron, etc. can be prepared by the method described in the literature 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 r is the frequency ni of particles having particle size ri.
The particle size r when the product n1Xri3 of and r13 is maximum
Define 1.

(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 diameter and particle diameter standard deviation shall be determined from ri 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 primitive emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
elikman et al. or edited by H. Frleser.
e Grundlagen der Photogra
phischen Prozesse mit SiI
berhalogeniden, Akademicc
he Verlagsgesellschaft, 19
68) 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. Examples of reduction sensitizers include stannous salts, amines, hydrazine derivatives, formamidisulfinic acid,
Silane compounds etc. can be used, and specific examples thereof include U.S. Pat. Nos. 2,487,850 and 2,419,974
No. 2,518,698, No. 2,983,609, No. 2,983,610, and No. 2,694,637. In addition to gold complex salts, for noble metal sensitization,
Complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used; specific examples thereof are given in U.S. Pat.
No. 99.083, No. 2,448,060, British Patent 6
18.061 etc.

In addition, there are no particular restrictions on conditions such as pH, pAg, temperature, etc. during chemical sensitization, but the pH value is 4 to 9, especially 5 to 8.
is preferred, and the pAg value is preferably maintained at 5-11, particularly 7-9. Further, the temperature is preferably 40 to 900C1, particularly 45 to 75C.

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-133a
Various stabilizers can also be used, including 7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.

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

l) In the silver halide photographic light-sensitive material according to the present invention,
Furthermore, a sensitizing dye may be 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, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole 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, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus , benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Melonanine dyes or complex 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-24 dione nucleus, rhodanine nucleus, thiobalhyalic 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-
' to about 5 X 10-' moles of sensitizing dye are preferred, particularly from 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.

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. 3,6
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 thereof include cyanine dyes, melonanine dyes, and composite cyanine dyes such as those described in No. 8-42172. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
No. 0,378, No. 2,442,710, No. 2,454
, No. 629, No. 2,776.280, Special Publication No. 1977-1
No. 7725, JP-A No. 50-62425, 6]-29
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 836 and No. 60-80841.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization purposes. Typical examples are U.S. Patent No. 2688.545, U.S. Pat.
No. 7,060, No. 3,522.052, No. 3,527
, No. 641, No. 3.617293, No. 3,628,9
No. 64, No. 3, No. 666, No. 480, No. 3,672,
No. 898, No. 3,679,428, No. 3.70337
No. 7, No. 3,769,301, No. 3,814.609
No. 3, No. 837862, No. 4,026,707, British Patent No. 1,344.28], No. 1.507.80
No. 3, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Publication No. 110618/1982, Japanese Patent Publication No. 52-109925
It is stated in the number 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, sudyryl 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 pentthiazolium salts, nitroindazoles, triazoles, benzotriazoles,
benzimidazoles (especially nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1
-7enyl-5-mercaptotetrazole), mercaptopyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially Many compounds known as stabilizers can be added, such as 4-hydroxy substituted (1,3,3a,7)tetrazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is K. Mees, The Theory of Photographic Processes.
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 has U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, 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)benzotriacyl, 2-
(2'-Hydroxy-3',5'-di-tert-butylphenyl)penztriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-phthylphenyl)-5-
Examples thereof include chlorobenzo) lyazole, 2-(2'-hydroquine-3', 5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, and the like. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are described in British Patent No. 54.
8, 532, 1; 216,389, U.S. Patent 2
, No. 026,202, No. 3,514,293, Special Publication No. 44-26580, No. 43-17922, No. 43-
No. 17926, No. 43-3166, No. 4g-2078
No. 5, Color Circle Patent No. 202.588, Belgian Patent No. 77
Anionic, cationic, nonionic, or amphoteric compounds described in No. 3,459, JP-A-48-101118, etc. can be used, but among these, anionic surface active compounds having a sulfonic group are particularly suitable. Agents such as succinic acid ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as an antistatic agent,
-24159, JP 48-89979, JP 2,882.157, JP 2,972,535, JP 48-20785, JP 48-43130, JP 48
-90391, Special Publication No. 46-24159, 4G-
No. 39312, No. 48-43809, JP-A-47-3
There are compounds described in each publication of No. 3627.

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 matting 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, or inorganic particles such as carbonates of cadmium, zinc, etc., starch described in U.S. Patent No. 2,322,037, Belgian Patent No. 62
Starch derivatives described in No. 5,451 or British Patent No. 981,198, polyhyphenyl 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 polycarbonate as described in US Pat. No. 3,022,169 may be included.

In the light-sensitive material of the present invention, the constituent layers include slipping agents, such as U.S. Pat.
Higher aliphatic higher alcohol esters as described in US Pat. No. 3,295.979, casein as described in U.S. Pat.
．． Higher aliphatic calcium salts as described in No. 263, 722, British Patent No. 1,313,384, U.S. Patent No. 3,042
, No. 522, and No. 3,489,567.

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

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem1.
7643 (December 1978) and volume 187■te
m18716 (November 1979),
The relevant locations are summarized in the table below.

In carrying out the silver halide photographic material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials. 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 σ. −Olefin polymer=
(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 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 each publication of No. 8949 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 7enyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.

The dihydroquine benzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 23-dichlorohydroquinone, 2.5-dichlorohydroquinone, 2.3 dibromohydroquinone, and 2,5-dimethylhydroquinone. Among them, hydroquinone is particularly preferred.

As the developing agent for I-phenyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl-4,4-dimedyl-3-pyrazolidone, 1-phenyl-4-methyl-
Examples include 4-hydroquinemethyl-3-pyrazolidone and 1-7enyl-44-dihydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminephenol, N-(β-hydroxyethyllp-aminophenol, N-(4-hydroquinphenyl)glycine, 2
-Methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminephenol is preferred.

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

As a preservative for sulfite used in the present invention, sulfite
potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sulfite. The amount of sulfite is preferably 0.2 mol/Q or more, particularly 0.4 mol/Q or more. Also, the upper limit is 2.5 mol 10. It is preferable to set it up to.

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 10 to 12.

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

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (eg, saccharose, 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 gelicol, nitinol, methanol, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimitasole-5-sulfonic acid I・Mercapto compounds such as lithium salts, 5-2L
- May contain antifoggants such as indazole compounds such as loindasol, penztriazole compounds such as 5-megolbenztriazole, and further include color toning agents, surfactants, antifoaming agents, water softeners, Japanese Patent Application Publication No. 5
The amino compound described in No. 6-106244 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, amine compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, F.A. Meson's “Photographic
``Brosecin Chemistry'', published by Focal Press (
1966), pages 226-229, US Patent No. 2193
No. 015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1986-64
Those described in No. 933 and others may be used.

In the present invention, "developing time" and "fixing time j" respectively mean
The time from when the photosensitive dye 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 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 1. The automatic processing machine is equipped with a drying sink onto which hot air, preferably 40° C. to 80° C., is blown.

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 thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 5.5.

Examples of the fixing agent include sulfur 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 fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 moles.
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 0.0005 mol or more of these compounds per fixer solution 1a are effective, especially 0.005 mol or more per fixer solution 1a. O1 mol/Q, ~003 mol10. is particularly effective.

Specifically, there are 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), p.
It can contain an H adjuster (for example, sulfuric acid), 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 about 206°C to about 50°C for 6 seconds to 1 minute, more preferably 30°C to 40°C for 6 seconds to 30 seconds, and still more preferably 30°C to 40°C for 6 seconds. ~
It is 15 seconds.

When the fixer concentrate is replenished into the automatic processor in the method of the present 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 for the developer.

The fixer solution can stably exist 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 or 5, the thiosulfate will decompose and eventually become sulfurized, 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 1:0 to 8. It is preferable that the total amount of these developer and fixing solution is 50 m12 to 1500 m12 per 1 m2 of photosensitive feed.

In the present invention, the photosensitive material is exposed to air, 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 processor. This makes it possible to further reduce the number of stock tanks. 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.
Water saving treatment of 0 to 3a1, preferably O to IQ1, can be performed per 2.

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.
, Be-ach “Microbiological
Growths in Motion-Picture
“Processing” SMPTE Journal
l Vol, 85. (1976) R, O, Deegan.
, “Pboto Processing Wash
Water Biocides” J, 1maging
Techvol 10. No. 6 (1984) and Japanese Patent Application Publication Nos. 57-8542, 57-58143, and 58
-105145, 57-132146, 58-
No. 18631, No. 57-97530, No. 57-157
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 244 and 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
ARCHDISCLO3URE Volume 205, Item 2
Isothiazoline compounds described in 0526 (May issue, 1981), Volume 228, Item 2284
The isothiazoline compounds described in Japanese Patent Application No. 1986-5] No. 396, etc. can also be used together as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-phenylphenol, chloro7ene, dichlorophene, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-(
4-Thiazoline)benzimidazole, benzisothiazoline-3one, dodecyl-benzyl-dimethylammonium chloride, N-(fluorodichloromethylthio)phthalimide, 244'-1-dichloro-2-fuhytroquine diphenyl ether, and the like.

The water treated with antifungal 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 0.01 to 10 g/12. More preferably 0.
■~5g/Ω.

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, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and formalin. In addition, various additives such as chelating agents, bactericidal agents (deazole type, inthiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardening agents, etc. may be used. , two or more of the same or different desired compounds may be used in combination.

Mata, ammonium chloride as a membrane pH adjuster for processing solutions,
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°
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 a temperature of about 40°C to about 100°C, and the drying time can be changed appropriately depending on the surrounding conditions, but it is usually about 5 seconds to 1 minute, more preferably 4 minutes.
It is about 5 seconds to 30 seconds at 0°C to 80°C.

In the present invention, an even more excellent effect is exhibited in that the lower the swelling percentage of the photosensitive feed, 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 within 100 seconds, preferably within 60 seconds, and more preferably within 5 seconds.
It is to be processed within 0 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 (Preparation of coating solution for back lower layer) After dissolving 500 g of gelatin in 8Q water, the dye of the present invention was added as shown in Table 1, and 20 g of saponin as a surfactant was added as shown in Table 1. 20 g of a copolymer of butyl acrylate and vinylidene chloride as a polymer latex, 2.5 g of a styrene-maleic anhydride copolymer as a thickener, and 2 g of glyoxal as a hardening agent were added.

(Preparation of Back Upper Layer Coating Solution) After dissolving 400 g of gelatin in 600 ml of water, polymethyl methacrylate with an average particle size of 4 μm was added as a matting agent for 2 hours, and 3 g of those shown in Table 1 were added as a surfactant.

(Preparation of coating solution for emulsion layer) In a solution containing gelatin, sodium chloride, and water kept at 40°C, an aqueous silver nitrate solution, 2XIO'mol of potassium hexachloroiridate per mol of silver halide, and 4X10 A mixed aqueous solution of potassium bromide and sodium chloride containing hexabromorodium salt of Cubic crystal, grain size (L25μm
) was prepared while maintaining pH 3.0 and pAg 7.7, and p
After the H value was returned to 5.9, desalting was performed by a conventional method.

This emulsion was sensitized with gold and sulfur, 60 mg of sensitizing dye (a) was added per mole of silver halide, and 70 mg of ■-phenyl-5-mercaptotetrazole and 4-hydroxy -6=methyl-1,3
, 3a, 1.2 g of 7-tetrazaindene and gelatin were added to stop the ripening, and then 4 g of hydroquinone was added.
, 3L of potassium bromide, 59g of saponin, 29g of styrene-maleic acid polymer as a thickener, 3g of ethyl acrylate polymer latex, formalin and sodium 1-hydroxy-35-dechlorotriazine as hardeners. Prepared by adding salt.

Sensitizing dye (a) (Preparation of protective film for emulsion layer) Potassium bromide log was added to an aqueous solution of 500 g of gelatin, and sodium 1-decyl-2-(3-impentyl)succinate-2-sulfonate was added as a spreading agent. 1% aqueous solution of 1% was added, and 10% of amorphous silica with an average particle size of 5 μm was added
0g was added and dispersed to prepare.

Thickness 100/1m after undercoating using the above coating liquid
The back lower layer and upper layer were simultaneously coated on the polyethylene terephthalate base with the amount of gelatin shown in Table 1, and then on the side opposite to the back layer, the silver amount was 3.8 g/m2, and the gelatin emulsion layer was 1. .5g/m2, protective film layer 1, Og/m2
The emulsion layer and the protective layer were coated at the same time.

The samples thus obtained were processed using a developing solution and a fixing solution having the following compositions in an ordinary roller type automatic developing machine under the following conditions, and residual color was evaluated.

The residual color was evaluated in 10 grades. 10 is the best;
Levels 1 to 4 are unusable, and levels 5 and above are usable.

From Table 1, it can be seen that the products of the present invention have good residual color.

In addition, when changing the line speed while maintaining the same processing time, adjust the depth of the tank and the number of rollers.

(Development processing conditions) (Process) (Temperature) (Time) Development
38°0 12 seconds fixing, washing and drying 36°C Normal temperature 50°C 10 seconds 8 seconds 10 seconds (a) CH8 C8H,,5O2NHCH2CH2CH2-NΦjiCH3 CII2CI12COOe The lower layer and upper layer in Table 1 are back layers, respectively.

The surfactants used for comparison are shown below.

Developer composition (composition A) Pure water (ion-exchanged water) 150 m (1-functional ethylenediaminetetraacetic acid disodium salt g) Diethylene glycol 50 g Potassium sulfite (55% w/v aqueous solution) 100 n+Q.

Potassium carbonate 50g Hydroquinone 15g 5-methylbenzotriazole 200mg 1-phenyl-5-mercaptotetrazole 0mg Potassium hydroxide Amount to adjust pH to 11.5 after use Potassium bromide 3g (composition B) Pure water (ion exchange water) 3mQ diege Ren glycol 50g diethylamino-1
,2-propanediol 5g ethylenediaminetetraacetic acid disodium salt 5mg Acetic acid (90% aqueous solution) 0.3m+2
5-=ll clondazole 110 mg tophenyl-3-birasoliton 500 mg When using a developer, the above compositions A and B were dissolved in 500 mfl of water in that order and used after finishing to I+2.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w/v aqueous solution) Boric acid 6 g Sodium citrate trihydrate 8 g Acetic acid (90% w/v aqueous solution)
1,3.6mQ (composition B) Pure water (ion exchange water) L7mQ sulfuric acid (
50% w/v aqueous solution) 4.7 g aluminum sulfate (AQxO3 equivalent content 8.1% w/v aqueous solution) 26
．． 5g For use as a fixer, add the above composition A1 and composition B in 500m+2 water.
It was dissolved in the following order and finished to IQ and used. This fixer p
H was about 4.3.

〔Effect of the invention〕

According to the present invention, it has been possible to provide a processing method that causes less residual color and the like even when ultra-rapid processing is performed.

40m12 sulfite lium 7g

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 and a back layer on the opposite side of the support. One layer contains at least one dye represented by the following general formula [I] and at least one anionic surfactant, and is developed and fixed using an automatic developing machine with a line speed of 1500 mm/min or more. A treatment method characterized in that the treatment time up to water washing and/or stabilization treatment is within 45 seconds. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. and Z_2 each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted benz fused ring or naphtho fused ring. However, R
_1, R_2, R_3, R_4, R_5, R_6, Z_
1 and Z^2 indicate groups that allow the dye molecule to have at least 4 acid groups. L represents a substituted or unsubstituted methine group, and X^■ represents an anion. n is 1
or 2, and 1 when the dye forms an intramolecular salt. ]