JP3086953B2 - Processing method of silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for forming an image on a silver halide photographic light-sensitive material, and more particularly to a method for forming an image on a printing light-sensitive material having rapid processing suitability.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has been steadily increasing. For this reason, the number of processed silver halide photographic materials has been increased, and it has been required to speed up the development processing, that is, to increase the processing amount within the same time.

The above tendency is also seen in the printing plate making field. That is,
Due to the rapid increase in the immediacy and the number of times of information, it is necessary to carry out printing plate making operations in a short delivery time and in a larger amount. In order to satisfy the demands of the printing plate making industry, it is necessary to promote simplification of the printing process and to process the printing plate making film more quickly.

However, shortening the processing time is not preferable because deterioration of residual colors and residual color unevenness occur.

[Object of the invention]

In order to solve the above problems, an object of the present invention is to provide, for example, a processing time of up to 45% for development, fixing, washing, and / or stabilization.
It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material having a good residual color and having no residual color unevenness even when an ultra-rapid processing within a second is performed.

[Configuration of the invention]

The object of the present invention is to provide a sensitizing dye represented by the following general formula [Ia] and a sensitizing dye represented by the following general formula [Ib]. A silver halide photographic light-sensitive material characterized in that the material is processed using an automatic processor with a line speed of 1500 mm / min or more, with a processing time of up to 45 seconds until development, fixing, washing, and / or stabilization. Achieved by the processing method.

In the formula, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, and R ₁₁ , R ₁₂ , R ₂₁ and R _{22 22} represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group, respectively.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Phenyl group, benzyl group, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. X ₁₁ and X ₂₁
Represents an anion. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂ are 0 or 1
Represents

 Hereinafter, the present invention will be described in detail.

The line speed in the treatment of the present invention is 1500 mm / min or more, preferably 1800 mm / min or more, more preferably 2000 mm / m.
more than in.

The processing time up to the developing, fixing, washing or / and stabilizing solution of the present invention within 45 seconds means that the film comes out of the fixing solution, washing solution and / or stabilizing solution after the leading edge of the film enters the developing solution. The time until the transfer is less than 45 seconds, and includes the time for the transfer from the developing solution to the fixing solution and the time for the transfer from the fixing solution to the washing solution.

The processing time for the development, fixing, washing and / or stabilizing solution of the present invention is preferably within 40 seconds.

In the present invention, it has been found that the object of the present invention can be achieved without increasing the processing line speed without shortening the processing line length and without causing the above problems.

Next, the general formulas [Ia] and [Ib] will be described.

[Wherein, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, a benzothiazole ring, a naphthothiazole ring,
Benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring, quinoline ring,
Examples include a 3,3-dialkylindolenin ring, a benzimidazole nucleus, and a pyridine ring.

These heterocycles are a lower alkyl group, an alkoxy group,
It may be substituted with a hydroxyl group, an aryl group, an alkoxycarbonyl group, or a halogen atom.

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Phenyl group, benzyl group, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. Y ₁₁ , Y ₁₂ , Y ₂₁ ,
One of Y ₂₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , and R ₂₆ is an acid group (for example, carbonyl group, sulfonyl group Etc.) or a group substituted with an acid group. X ₁₁ and X ₂₁ represent anions. When there is an acid group, m ₁₁ and m ₂₁ represent 0, and when there is no acid group, m ₁₁ and m ₂₁ represent 1. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂ represent 0 or 1.

Next, specific examples of the sensitizing dye represented by the general formula [Ia] or the general formula [Ib] of the present invention (hereinafter, referred to as the sensitizing dye of the present invention) are shown, but the present invention is not limited thereto. It is not something to be done.

The sensitizing dye of the present invention is contained in a silver halide photographic emulsion in an amount of preferably from 1 mg to 2 g, more preferably from 5 mg to 1 g, per mol of silver halide.

The sensitizing dye of the present invention can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount is the above content. Further, sensitizing dyes other than the sensitizing dye of the present invention can be used in combination.

The sensitizing dyes of the present invention are described in U.S. Patent No. 2503776, British Patent No. 742112, French Patent No. 2065662, Japanese Patent Publication No. 40-2346.
Can be easily synthesized with reference to the reference numbers.

The silver halide emulsion used in the light-sensitive material of the present invention is preferably silver chloride, silver chlorobromide or silver chloroiodobromide having a silver chloride content of 30 mol% or more. Silver chloride, silver chlorobromide or silver chloroiodobromide containing at least mol%. The silver halide grains may be obtained by any of an acidic method, a neutral method and an ammonia method.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. The particles may be particles formed mainly in the particles or particles mainly formed inside the particles.

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Patent 4,
183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, etc., and the Journal of
Photographic Science (J.Photgr.Sci). Two
By the method described in 1.39 (1973) documents, such as octahedral, tetradecahedral, create a particle having a shape such as dodecahedral, it can also be used this. Further, particles having a twin plane may be used.

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

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

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

In the present invention, a monodisperse emulsion is preferred. The monodispersed silver halide grains in the monodispersed emulsion are those in which 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 total weight of silver halide grains. Some are preferred, particularly preferably 70% or more, more preferably 80%
That is all.

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

(Three significant digits and the least significant digit are rounded off.) The particle size referred to here is the diameter of spherical silver halide grains, or the projected image of grains other than spherical. It is the diameter when converted to a circular image of the peripheral area.

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

Here, the average particle diameter and the standard deviation of the particle diameter are determined from ri defined above. Monodispersed emulsions are described in JP-A-54-48521,
Reference can be made to JP-A-58-49938 and JP-A-60-122935, and the like.

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

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, gold or another noble metal compound can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat.
No. 2,410,689, No. 2,278,947, No. 2,728,668, No. 3,6
No. 56,955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds and the like can be used, and specific examples thereof are U.S. Pat.Nos. 2,487,850, 2,419,974 and 2,419,974.
2,518,698, 2,983,609, 2,983,610, 2,692
No. 4,637. In order to sensitize precious metals, in addition to gold complex salts, periodic table of platinum, iridium, palladium, etc.
Complex salts of Group VII metals can be used, examples of which are U.S. Pat.Nos. 2,399,083 and 2,448,060, British Patent 618,06
It is described in No. 1.

The conditions such as pH, pAg, and temperature during chemical sensitization are not particularly limited, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is 5 to 11, particularly 7 to 9. It is preferable to keep. The temperature is preferably from 40 to 90 ° C, particularly preferably from 45 to 75 ° C.

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

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

In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3,3
Various stabilizers such as a, 7-tetrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole and the like can also be used.

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

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

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

The amount of gelatin on the photosensitive layer side of the photosensitive material of the present invention was 3.5 g / m ^2.
Or less, more preferably 3.0 g / m ² or less. More preferably, it is 2.8 g / m ² or less.

In the silver halide photographic material according to the present invention, the dye other than the sensitizing dye of the present invention which may be used in combination with the sensitizing dye of the present invention includes a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, Examples include holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemiosanol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, such as a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and the like. Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole A nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

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

Specific examples of the sensitizing dyes other than the sensitizing dyes of the present invention that are advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent 929,080 and U.S. Pat.
No. 31,658, No. 2,493,748, No. 2,503,776, No. 2,519,00
No. 1, No. 2,912,329, No. 3,656,956, No. 3,672,897,
3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, JP-B-44-14030, and 52-24844
And JP-A-48-73137 and JP-A-61-172140. Sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
9,201, 2,072,908, 2,739,149, 2,945,763
And British Patent No. 505,979, JP-B-48-42172, and the like, and a typical example thereof is a cyanine dye, a merocyanine dye or a complex cyanine dye. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
No. 234, No. 2,270,378, No. 2,442,710, No. 2,454,629
No. 2,776,280, JP-B-49-17725, JP-A-50-62
No. 425, No. 61-29836, No. 60-80841, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical examples.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Representative examples are U.S. Pat.Nos. 2,688,545, 2,977,229, 3,397,060, 3,5
22,052, 3,527,641, 3,617,293, 3,628,96
No. 4, 3,666,480, 3,672,898, 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
No. 507,803, JP-B-43-4936, JP-B-53-12375, JP
Nos. 52-110618 and 52-109925.

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

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

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

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

For further details of these specific examples and other methods of use, for example, U.S. Patent Nos. 3,954,474 and 3,982,947,
No. 4,021,248 or JP-B-52-28660 can be referred to.

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

The silver halide photographic light-sensitive material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.No. 2,960,404, JP-B-43-4939, West German Application Publication 1,9
04,604, JP-A-48-63715, Belgian patent 762,833
No. 3,767,410, the substances described in the specifications of Belgian Patent 588,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc.
Various hardeners such as aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinylsulfone-based, isocyanate-based, sulfonate-based, carbodiimide-based, mucochloric-based, and acyloyl-based hardeners, and ultraviolet absorbers Examples of the agent include compounds described in, for example, U.S. Pat. No. 3,253,921 and British Patent 1,309,349, particularly 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-
5'-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and the like can be mentioned. Further, coating aids, emulsifiers, improvers of permeability to processing solutions, etc., defoamers and surfactants used for controlling various physical properties of photosensitive materials are disclosed in British Patent Nos. 548,532 and 1,216,389. U.S. Pat.Nos. 2,026,202, 3,514,293, JP-B-44-26580
No. 43-17922, No. 43-17926, No. 43-3166, No.
48-20785, French patent 202,588, Belgian patent 773,
No. 459, anionic, cationic, nonionic or amphoteric compounds described in JP-A-48-101118 can be used, among which anionic surfactants having a sulfone group, For example, succinate sulfonates, alkylbenzene sulfonates, and the like are preferable. As antistatic agents, JP-B-46-24159, JP-A-48-89979, U.S. Pat.Nos. 2,882,157 and 2,972,535
No., JP-A-48-20785, JP-A-48-43130, JP-A-48-90391
No., JP-B-46-24159, JP-B-46-39312, and JP-B-48-43809
And JP-A-47-33627.

In the production method of the present invention, the pH of the coating solution is preferably in the range of 5.3 to 7.5. In the case of multi-layer coating, it is preferable that the pH of the coating liquid obtained by mixing the coating liquids of the respective layers at a coating amount ratio is in the range of 5.3 to 7.5 described above. If the pH is less than 5.3, the dura progresses slowly, which is not preferable, and the pH is 7.
If it is larger than 5, it is not preferable that the photographic performance is adversely affected.

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

In the light-sensitive material of the present invention, the constituent layers are slip agents, for example, higher aliphatic esters of higher aliphatic alcohols described in U.S. Pat. Nos. 2,588,756 and 3,121,060, casein described in U.S. Pat. Aliphatic calcium salt, UK Patent 1,313,384, U.S. Patent
It may include the silicon compounds described in 3,042,522 and 3,489,567. Liquid paraffin dispersions can also be used for this purpose.

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

In the implementation of the silver halide photographic light-sensitive material of the present invention,
For example, the emulsion layer and other layers can be formed by coating one or both sides of a flexible support generally used for photographic light-sensitive materials. Useful as a flexible support are films composed of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layer or α-olefin polymer. (Eg, polyethylene, polypropylene, ethylene / butene copolymer) or the like coated or laminated. The support may be colored using a dye or a pigment.
It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with an emulsion layer or the like. Undercoating treatment is described in JP-A-52-104913 and JP-A-59-1894.
No. 9, No. 59-19940, and No. 59-11941 are preferred.

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

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

The developing / fixing / washing / drying steps performed in the present invention for a development time of 20 seconds or less, preferably 15 seconds or less, will be described.

The developing agent used in the black-and-white developing solution used in the present invention has a dihydroxybenzene chain and 1
Most preferred are combinations of -phenyl-3-pyrazolidones. Needless to say, a p-aminophenol-based developing agent may also be contained.

As the difudroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Although there are 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

As a developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

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

The developing agent is preferably used usually in an amount of 0.01 mol / to 1.2 mol /.

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

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters.

Buffers such as JP-A-61-28708 (borate) and JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates may be used.

Additives other than the above components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethinol, methanol Organic solvents such as: 1-phenyl-5-mercaptotetrazole, mercapto compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benzes such as 5-methylbenztriazole It may contain an antifoggant such as a triazole compound, and further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hard water softener,
It may contain an amino compound described in 106244 or the like.

In the present invention, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used in the developer.

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

LFA Meson, "Photographic Processing Chemistry", Focal Press (1966
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,3
No. 64, JP-A-48-64933 and the like may be used.

In the present invention, the "development time" and the "fixing time" refer to the time from the time when the photosensitive material to be processed is immersed in the developing tank solution of the automatic developing machine to the time when the photosensitive material is immersed in the next fixing solution. It means the time from immersion to the next washing tank liquid (stabilizing liquid).

The term “washing time” refers to the time during which the sheet is immersed in the washing tank liquid.

Further, the "drying time" is usually 35 ° C to 100 ° C, preferably 4 ° C.
The drying zone to which the hot air of 0 ° C to 80 ° C is blown is installed in the automatic processing machine, but refers to the time in the drying zone.

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 fixing solution is an aqueous solution containing a thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate. Thiosulfuric acid ions and ammonium ions are essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent to be used can be appropriately changed, and is generally about 0.1 to 6 mol /.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, ammonium sulfate, potassium alum and the like.

Tartaric acid, citric acid or their conductors can be used alone or in combination of two or more in the fixing solution.
It is effective that these compounds contain 0.005 mol or more per fixing solution, particularly 0.01 mol / to 0.03 mol /.

Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

The fixing solution may optionally contain a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or nitric acid), a pH adjuster (eg, sulfuric acid), a chelating agent having a water softening property, The compounds described in JP-A-60-213562 can be included.

The fixing temperature and time are preferably from about 20 ° C to about 50 ° C for 6 seconds to 1 minute, more preferably from 30 ° C to 40 ° C for 6 seconds to 30 seconds, and still more preferably from 30 ° C to 40 ° C for 6 seconds to 15 seconds. It is.

When the fixer concentrate is replenished to the automatic processor by the method of the present invention together with water for diluting the photosensitive material as it is processed, it is most preferable that the fixer concentrate is composed of one agent. Is the same as in the case of the developer.

Fixing solution can be stably present as one agent at pH 4.5
And more preferably pH 4.65 or more. pH4.5
If it is less than 30, the thiosulfate is decomposed and finally sulfided, especially when the fixing solution is left for many years until it is actually used. Therefore, in the range of pH 4.5 or more, the generation of sulfurous acid gas is small and the working environment is improved. The upper limit of the pH is not so severe, but if the fixing is carried out at an excessively high pH, the membrane pH is increased even after washing with water, and the membrane swells and the drying load is increased. In the case of a fixing solution that hardens using an aluminum salt, the limit is a pH of 5.5 or less, which prevents precipitation and precipitation of the aluminum salt.

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

The supply amount of each concentrated solution to the treatment tank solution and the mixing ratio with the dilution water can be variously changed depending on the composition of the concentrated solution.
The total amount of each of these developing solution and fixing solution is preferably 50 ml to 1500 ml per 1 m ² of the photosensitive material.

In the present invention, the light-sensitive material is subjected to washing or stabilization after the current solution and fixing.

Any method known in the art can be applied to the washing or stabilizing treatment, and water containing various additives known in the art can be used as the washing water or the stabilizing solution. The use of water which has been subjected to antifungal means in the washing water or stabilizing solution, not only the possible water saving processing of the photosensitive material 1 m ² per 3 less replenishing rate, automatic processor installed in the piping is not required Further, the number of stock tanks can be reduced. That is, the preparation dilution water and the washing water or the stabilizing solution for the developing solution and the fixing solution can be supplied from one common stock tank, so that the automatic developing machine can be made more compact.

When water that has been subjected to antifungal means is used in combination with washing water or a stabilizing solution, the occurrence of scale can be effectively prevented.
0 to 3, preferably 0 to 1, water saving treatment can be performed per ² pieces.

Here, the case where the replenishment amount is 0 means that no replenishment is performed except for appropriately reducing the amount of the washing water in the washing tank due to spontaneous evaporation or the like. This refers to the case where the processing method is performed.

As a method for reducing the amount of replenishment, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material of the fixing solution is gradually processed in a clean direction, that is, the processing solution which is not contaminated with the fixing solution is successively contacted and processed. Washing is performed. According to this, unstable thiosulfate and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more remarkable stabilizing effect is obtained. The amount of washing water is much smaller than before.

When washing with a small amount of washing water, it is more preferable to provide a squeeze roller washing tank described in Japanese Patent Application No. 60-172968.

Further, part or all of the overflow liquid from the washing or stabilizing bath generated by replenishing the water subjected to the fungicide means to the washing or stabilizing bath according to the treatment is disclosed in JP-A-60-235133.
As described in the above item, the present invention can also be used for a processing solution having a fixing ability, which is the preceding processing step. By doing so, it is more preferable because the stock water can be saved and the waste liquid can be reduced.

As the antifungal means, an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion-exchange resin described in JP-A-61-131632 are used. Method for making pure water, Japanese Patent Application No. 60-253807, 60-295894
Nos. 61-63030 and 61-51396 can be used.

Furthermore, LEWest “Water Quality Criteria” Photo S
ci & Eng. Vol. 9 No. 6 (1965), MWBeach “Microbiolo
gical Growths in Motion-Picture Processing "SMPTE
Joural Vol.85, (1976) .RODeegan, “Photo Processi
ng Wash Water Biocides "J.Imaging Tech.Vol10, No.6
(1984) and JP-A-57-8542, JP-A-57-58143, and JP-A-57-58143.
-105145, 57-132146, 58-18631, 57-9
No. 7530, No. 57-132146, No. 58-18631, No. 57-97530
, A fungicide, a surfactant and the like described in JP-A Nos. 57-157244 and the like.

In addition, RTKreiman's J.Image, Tech10,
(6) Isothiazoline compounds described in 242 (1984), RESEARCH DISCLOSURE Vol. 205, Item 20526 (1981)
Compounds, described in Japanese Patent Application No. 61-51396, vol. 228, Item 22845 (April, 1983), and the like. Can be used in combination as a bacteriostatic agent (Microbiocide).

Further, specific examples of the fungicide include phenol, 4-chlorophenol, pentachlorophenol, cresol,
o-phenylphenol, chlorophen, dichlorophen, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoate, 2-
(4-thiazoline) -benzimidazole, benzoisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N- (fluorodichloromethylthio) -phthalimide, 2,4,4'-trichloro-
2'-hydroxydiphenyl ether and the like.

The water stored in the water stock tank after the antifungal means is diluted water of the processing solution stock solution such as the developer fixing solution and the amount thereof is preferably 0.01 to 10 g /, more preferably 0.1 to 5 g /.

Further, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of a cationic type, an anionic type, a nonionic type and a zwitterionic type may be used. Specific examples of surfactants include, for example, compounds described in “Surfactant Handbook” issued by Kogyo Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjusting the membrane pH (for example, combining borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) And aldehydes such as formalin. In addition, chelating agents, fungicides (thiazoles, isothiazoles, halogenated phenols,
Various additives such as a sulfanilamide and a benzotriazole), a surfactant, an optical brightener, and a hardener may be used, and two or more kinds of the same or different target compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster of the processing solution,
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 storability.

Washing or stabilizing bath temperature and time by the above method are 0
C. to 50.degree. C. for 6 seconds to 1 minute is preferable, but 15.degree. C. to 40.degree. C. for 6 seconds to 30 seconds is more preferable, and further 15.degree.
Seconds are preferred.

According to the method of the present invention, the photographic material which has been developed, fixed and washed is squeezed out of the washing water, that is, dried via a squeeze roller method. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions.
Usually, it may be about 5 seconds to 1 minute, but more preferably 40 ° C to 80 ° C.
C. for about 5 to 30 seconds.

In the present invention, the more excellent the effect that the drying time can be shortened as the swelling percentage in the photosensitive material is reduced.

According to the method of the present invention, the processing time of so-called Dry to Dry until development, fixing, washing and drying is performed within 100 seconds, preferably within 60 seconds, more preferably within 50 seconds.

Here, “dyr to dry” refers to the time from the moment when the tip of the photographic material to be processed enters the film insertion part of the automatic processing machine to the time when it is processed and the same tip comes out of the automatic processing machine. .

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by this.

Example 1 A silver nitrate aqueous solution and 2 mol per mol of silver halide were placed in a container heated at 40 ° C. containing gelatin, sodium chloride and water.
× 10 ^-6 mol of potassium hexachloroiridate and 4
Silver bromochloride particles containing 35 mol% of silver bromide (double-distribution) by adding a mixed aqueous solution of potassium bromide and sodium chloride to which × 10 ^-7 mol of potassium hexabromorhodate is added by a double jet method. 9%, cubic, particle size 0.25μm)
Was adjusted while maintaining the pH at 3.0 pAg 7.7, and after returning to pH 5.9, desalting was carried out by a conventional method.

This emulsion was sensitized with gold and sulfur to give
60 mg per mol of silver halide was added to
Further, 70 mg of 1-phenyl-5-mercaptotetrazone per mol of silver halide, 4-hydroxy-6-methyl-
After ripening was stopped by adding 1.2 g of 1,3,3a, 7-tetrazaindene and gelatin, 1 mol of silver halide was further added with 4 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin, After adding 2 g of styrene-maleic acid polymer and 3 g of high molecular weight polymer latex of ethyl acrylate, and adding 1-hydroxy-3.5 dichlorotriazine sodium salt and formalin as a hardening material, the polyethylene was subjected to subbing processing. The amount of silver was 3.5 g / m ² on a terephthalate support and the amount of gelatin was as shown in Table 1. Further, as a protective film, 10 g of potassium bromide and 1-decyl-
4 g of 2- (3-isopentyl) succinate-2-sodium sulfonate was added, 100 g of amorphous silica having an average particle size of 5 μm was added and dispersed, and the emulsion layer was adjusted so that the gelatin became 1.0 g / m ^2. A protective layer was applied at the same time.

On the other side of the coated surface, a gelatin solution containing the dye (a) was applied in advance so that the amount of gelatin became 3.8 g / m ² and the amount of the dye (a) became 100 mg / m ² .

The sample thus obtained was treated with a general roller type automatic developing machine under the following conditions using a developing solution and a fixing solution of the following general formula, and the residual color was evaluated.

The residual color was evaluated in 10 steps, with 10 being the best and 1-4 being unusable and 5 or more being the usable level.

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

When the development, fixing and washing times were changed at the same line speed, adjustment was made by changing the depth of the tank and the number of rollers.

Processing conditions (Process) (Temperature) (Time) Current image 35 ° C 12 seconds Fixed 34 ° C 12 seconds Rinse at room temperature 12 seconds Dry 50 ° C 10 seconds Developer formulation (Composition A) Pure water (ion exchange) Water) 150 ml disodium ethylenediaminetetraacetate 2 g diethylene glycol 50 g potassium sulfite (55% w / v aqueous solution) 100 ml potassium carbonate 50 g hydroquinone 15 g 5-methylbenzotriazole 200 mg 1-phenyl-5-mercaptotetrazole 30 mg potassium hydroxide Adjust the pH to 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3 -Pyrazolidone 700 mg The above-mentioned composition A and composition B were dissolved in 500 ml of water in the order of use when using a developer, and used after finishing to 1.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% w / v aqueous solution) 13.6ml (Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% w / v aqueous solution) 4.7 g Aluminum sulfate (aqueous solution with an Al ₂ O ₃ equivalent content of 8.1% w / v) 26.5 g Water when using the fixing solution The above composition A and composition B were dissolved in 500 ml in this order, and finished to 1 for use. The pH of the fixing solution was about 4.3.

[Effects of the Invention] According to the present invention, a method for processing a silver halide photographic light-sensitive material which has little residual color even when ultra-rapid processing is performed and does not cause deterioration in image quality can be provided.

Continuation of front page (56) References JP-A-63-228147 (JP, A) JP-A-62-235947 (JP, A) JP-A-63-151944 (JP, A) JP-A-61-129644 (JP, A) , A)

Claims (1)

(57) [Claims] 1. A silver halide photographic material containing at least one sensitizing dye represented by the following general formula [Ia] and at least one sensitizing dye represented by the following general formula [Ib]: A method for processing a silver halide photographic light-sensitive material, wherein the processing time until development, fixing, washing with water, and / or stabilization is within 45 seconds using an automatic developing machine having a line speed of 1500 mm / min or more. . [Wherein, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a nonmetallic atom group required to complete a 5- or 5-membered nitrogen-containing heterocyclic ring, and R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group, respectively. R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom,
Substituted or unsubstituted alkyl, alkoxy, phenyl, benzyl, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle. R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. X ₁₁ and X ₂₁ represent anions. If there is an acid group, m ₁₁ and m ₂₁ are 0
When there is no acid group, m ₁₁ and m ₂₁ represent 1. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂ represent 0 or 1. ]