JPH1062917A - Processing method for black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the variation of photographic performance such as dot quality, white spots or white-on-black letter forming performance by processing a black-and-white silver halide photographic sensitive material contg. a quat. onium compd. with a developing soln. contg. ascorbic acid and a specified compd. SOLUTION: A black-and-white silver halide photographic sensitive material contg. a quat. onium compd. as well as a silver halide emulsion having >=60mol% silver chloride content is processed with a developing soln. of pH8.5-10 contg. ascorbic acid or its deriv. and a compd. represented by formula I or II. In the formula I, B is H, CH2 COOM, etc., M is H, a cation, etc., when B is H, each of A1 -A9 is H, hydroxyl, etc., and when B is CH2 COOM, etc., n3 =0, each of A1 , A8 and A9 is H and each of A2 -A5 is H, hydroxyl, etc. In the formula II, each of A11 -A14 is COOM or hydroxyl, each of R1 -R4 is H, lower alkyl, etc., each of n11 -n14 is an integer of 0-2 and X' is 2-6C alkylene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a black-and-white silver halide photographic material, and more particularly to a method for processing a black-and-white silver halide photographic material suitable for printing plate making.

[0002]

2. Description of the Related Art In order to produce excellent printed matter, it is necessary to faithfully reproduce a desired halftone dot on a photosensitive material for printing plate making. Is included. Further, in recent years, in the field of printing plate making, improvement of halftone dot quality has been required. For example, in a method called FM screening which is composed of a high-definition printing of 600 lines / inch or more and a random pattern of uniform minimum points, there is a problem. , 25 μm or less. These are Ar laser, He-
When performing an exposure with an image output machine equipped with a laser light source such as a Ne laser or a semiconductor laser, a so-called plate-making scanner, or a return operation of exposing a transparent halftone image original with a printer, a target minute halftone dot is used. Must be faithfully reproduced. Therefore, it is necessary that the photosensitive material for printing plate making has a high gradation. For example, a method using a hydrazine derivative as a high contrast agent as described in US Pat. No. 4,269,929 is known. I have.

[0003] In general, a photosensitive material for printing plate making (hereinafter, also simply referred to as a photosensitive material) is exposed to at least a developing unit,
It is processed by an automatic processor having a fixing section, a washing section or a stabilizing bath section, and a drying section. When these photosensitive materials are processed by an automatic developing machine, they are usually processed while replenishing a developing solution with a developing replenisher. In recent years, there has been a demand for reduction of photographic waste liquid due to increasing interest in the environment, and one of the means is to reduce the replenishment amount of the processing liquid.

[0004] In recent years, attention has been focused on improving the working environment, particularly on shortening working hours. In the printing and plate making industry, there is an increasing demand for a reduction in working time. Therefore, conventionally, the entire processing time from development to drying of a photosensitive material (Dry
Although the “to Dry” is 90 seconds or more, it is strongly desired to further shorten the time.

[0005] When rapid processing is performed on such fine halftone dots while reducing the replenishment amount and faithful reproduction is performed, it is necessary that the development processing be stable.

[0006] In order to stabilize the development process, it is required to reduce the deterioration of the developer by air oxidation. As one of the methods, it is useful to lower the pH of the developer.

[0007]

In the high contrast technology using a hydrazine derivative as described above, when the pH of the developer is lowered to 10 or less, the high contrast is not sufficient, and the use of a developer having a pH of 10 or less is not sufficient. Japanese Patent Application Laid-Open No. 6-1026 discloses a technique for achieving high contrast.
A method using a compound such as a pyridinium salt described in No. 33 is known.

However, when a pyridinium salt compound is used for a light-sensitive material and the running processing is performed with a reduced replenishing amount using a developer having a pH of 10 or less, photographic performance varies. In particular, when trying to reproduce a minute point of 25 μm or less, there has been a problem that a change in dot quality and a pinhole-shaped failure in the dot, that is, deterioration of white spots, occur. Also, in the case of the reverse photosensitive material, there is a problem that the reproducibility of a character original in a halftone dot, that is, a variation in so-called blank character performance is large. In addition, if the processing is performed with the processing time shortened, the fluctuation of the photographic performance is further increased.

The present invention has been made in view of the above-mentioned circumstances, and the first object of the present invention is to provide a method for producing a black-and-white halogenated solution even when the running process is performed while the replenishing rate is greatly reduced with a developer having a pH of 10 or less. It is an object of the present invention to provide a processing method of a silver photographic light-sensitive material, in particular, a light-sensitive material for printing plate making, which has little fluctuation in photographic performance such as halftone dot quality, white spots, and blank character performance.

Another object of the present invention is to provide a black-and-white silver halide photographic material even when running processing is carried out with a developing solution having a pH of 10 or less while greatly shortening the processing time.
In particular, it is an object of the present invention to provide a processing method in which a photographic performance such as a halftone dot quality, a white spot, and a blank character performance is less changed in a photosensitive material for printing plate making.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to provide a black-and-white silver halide photographic material having an emulsion layer containing a silver halide emulsion having a silver chloride content of 60 mol% or more on a support at pH 8. In processing with 5 to 10 developers,
When at least one layer of the black-and-white silver halide photographic material is 4
Black-and-white silver halide photographic material which is processed with a developer containing a secondary onium compound and at least one of ascorbic acid or a derivative thereof and the compound represented by the above general formula (1) or (2) A solid processing using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing bath, and a drying section, wherein the developer contains the compound represented by the general formula (S). Processing while replenishing the developing replenisher prepared from the developer, processing while replenishing the developing replenisher at 30 ml or more and 250 ml or less per 1 m ² of the photosensitive material, and drying the photosensitive material after the development enters the drying zone. Total processing time to exit (Dry
to Dry) in 10 seconds or more and 80 seconds or less.

According to the present invention, a quaternary onium compound is contained in a black-and-white silver halide photographic material such as for printing plate making having an emulsion layer containing a silver halide emulsion having a silver chloride content of 60 mol% or more, and ascorbic acid Or a derivative thereof and a developing solution containing at least one compound represented by formula (1) or (2) at a pH of 8.5 to 10 to obtain a solution per m ^{2 of} photosensitive material. Low replenishment such as developer replenishment volume of 30 ml or more and 250 ml or less, total processing time (Dry to Dry) 10 seconds or more 8
Even if rapid processing such as 0 seconds or less is performed, stable photographic performance can be obtained.

The present invention will be described below item by item.

<< Photosensitive Material >> The quaternary onium compound used in the present invention is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in the molecule, and is preferably a compound represented by the general formula (P). .

[0015]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Further, R _{1 to} R ₄ may be linked to each other to form a ring.

The substituent represented by R _{1 to} R ₄ includes an alkyl group (methyl group, ethyl group, propyl group, butyl group,
Hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (piperidinyl group, piperazinyl group) , Morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group,
Sulfolanyl group), an amino group and the like.

The ring which may be formed by connecting R _{1 to} R ₄ to each other includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are hydroxyl groups,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

[0021] X ^- include anions represented by the halogen ion, sulfate ion, nitrate ion, acetate ion, and inorganic and organic anions, such as p- toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0023]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

B _P represents a divalent linking group, and m is 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and examples of the substituent include A ¹ , A ² , A ³ , A ⁴
And the substituents mentioned as the substituents for A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0028] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0029]

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In the triphenyltetrazolium compound represented by the general formula [T], the substituents R ₁ , R ₂ ,
R ₃ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value for the phenyl group is described in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. The group having a particularly preferable negative sigma value is, for example, a methyl group (σP = −0.17 or less, a σP value in any case) and an ethyl group (−). 0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which is useful as a substituent of the compound of the general formula [T].

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium compound will be shown below, but it should not be construed that the invention is limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be synthesized according to Chemical Reviews 55 p. 3
35-483 can be referred to.

The addition amount of these quaternary onium compounds is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver halide. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

The quaternary onium compound may be used alone,
More than one species may be used in combination. It may be added to any of the constituent layers of the light-sensitive material, but preferably at least one of the constituent layers on the side having the silver halide emulsion layer.
Layer and further added to the silver halide emulsion layer and / or the layer adjacent thereto.

The halogen composition of the silver halide emulsion used in the light-sensitive material according to the present invention has a silver chloride content of 60 mol% or more. Preferably, a silver chlorobromide containing 60 mol% or more of silver chloride, silver chloroiodobromide containing 60 mol% or more of silver chloride or a silver halide emulsion having a composition of silver chloride is used.

The average grain size of the silver halide is preferably 0.6 μm or less, more preferably 0.5 to 0.05 μm. Here, the particle size means the particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size.
For details of the method for determining the average particle size, see C.I. E. FIG. K.
Mees & T. H. By James: The theor
y of the photographic pro
ses, Third Edition, pp. 36-43 (Mcmi, 1966)
Llan, Inc.).

The shape of the silver halide grains is not limited, and may be any of tabular, spherical, cubic, tetradecahedral, octahedral and other shapes. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

Among the above tabular grains, tabular grains having a (100) plane having 90 mol% or more of silver chloride as a main plane can be used, and these are described in US Pat. No. 5,264,264.
No. 337, 5,314,798, 5,320,9
No. 58 and the like, and the desired tabular grains can be easily obtained.

In the present invention, the silver halide emulsion comprises VIII
It is preferable to contain at least one metal selected from group III transition metals and rhenium. Examples of the Group VIII transition metal include iridium, rhodium, ruthenium, and osmium. Rhodium, ruthenium, and osmium are preferable for promoting high contrast. In order to perform high-speed exposure with a light source such as a laser beam, iridium is preferably used. When added to the particles, the metal can be coordinated with halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl, phenanthroline or a combination of these compounds. .

As an example of these, for example, K ₂ [RuC
l ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO)
Cl ₄ (SCN)], K ₂ [RuCl ₅ (H ₂ O)], and the like. The Ru part can be represented by replacing it with Rh, Os and Ir.

These metals can be added at any time during the period from silver halide grain formation to coating, but preferably during silver halide grain formation, physical ripening and / or chemical ripening. More preferably, it is added during the formation of silver halide grains. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion.

These transition metals are preferably added in the range of 10 ^-10 mol to 10 ^-2 mol, more preferably 10 ^-8 mol to 10 ^-3 mol, per mol of silver halide. In addition, zinc during physical aging and chemical aging,
Metal salts such as lead, thallium, rhenium, palladium, platinum and the like can also be allowed to coexist.

The silver halide emulsion is preferably chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. As the noble metal sensitizer, a gold compound, a platinum compound, a palladium compound, or the like can be preferably used. Among them, a gold compound is more preferable.

Combinations of these chemical sensitizers include, for example, a combination of a sulfur sensitizer and a noble metal sensitizer, a combination of a selenium sensitizer and a noble metal sensitizer, a reduction sensitizer and a noble metal sensitizer. And the combination. In the present invention, it is preferable to sensitize by adding at least one gold compound.

These chemical sensitizers can be added at any time during the preparation of a silver halide emulsion, but are preferably added after the formation of silver halide grains and before coating. The addition amount of the chemical sensitizer is 1 per mol of silver halide.
It is preferable to add in the range of 0 ^-9 mol to 10 ^-3 mol. When a gold compound is used, it is preferable to add 0.1 to 1 times mol of the group VIII transition metal salt and the rhenium metal salt.

The silver halide emulsion can be spectrally sensitized to a desired wavelength by using a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.

The light-sensitive material according to the present invention contains various compounds known as antifoggants or stabilizers for the purpose of preventing fogging during the manufacturing process, storage or photographic processing, or stabilizing photographic performance. Can be added.

For the photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer, inorganic or organic hardeners, coating aids, antistatic, improvement of slipperiness, emulsification / dispersion, prevention of adhesion, improvement of photographic properties, etc. Various surfactants may be used for the purpose of.

It is advantageous to use gelatin as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion used in the present invention may contain a dispersion of a water-insoluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability and the like.

The light-sensitive material according to the present invention preferably has at least one conductive layer on a support. Typical methods for forming the conductive layer include a method using a water-soluble conductive polymer and a hydrophobic polymer curing agent, and a method using a metal oxide. For these methods, for example, the method described in JP-A-3-265842 can be used.

When the swelling percentage of the light-sensitive material processed in the present invention is 250% or less, 30% or more, preferably 180% or less, 50% or more, the effects of the present invention can be further exhibited. The swelling percentage here means that the photosensitive material is 3%.
After incubation at 8 ° C. and 50% RH for 3 days, the thickness (d0) of the hydrophilic colloid layer was measured, the photosensitive material was immersed in distilled water at 21 ° C. for 3 minutes, and again the thickness (d0) of the hydrophilic colloid layer was measured. ) Is measured and the ratio of the swelling is represented from the swelled thickness. That is, swelling percentage = (d−d0) / d × 100.

In the silver halide emulsion and the backing layer, various chemical sensitizers, color toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, ultraviolet absorbers, irradiation Inhibiting dyes, heavy metals, matting agents and the like can be further contained by various methods. Further, the silver halide emulsion and the backing layer may contain a polymer latex.

The support used for the light-sensitive material may be either permeable or non-permeable, but is preferably a permeable plastic support. As the plastic support, a support made of a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (eg, triacetate cellulose, etc.), a polystyrene compound, or the like is used. Among them, a support (hereinafter abbreviated as SPS) made of a polyethylene terephthalate film and a stretched film made of a styrene-based polymer having a syndiotactic structure or a composition containing the same is particularly preferable.

SPS is a homopolymer whose constituent units are composed of SPS units having syndiotactic stereoregularity. A small amount, for example, 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less. The second
The SPS modified by the component is also included. Examples of the second component include olefin monomers such as ethylene, propylene, butene and hexene, diene monomers such as butadiene and isoprene, cyclic olefin monomers, cyclic diene monomers and methyl vinyl methacrylate, maleic anhydride, and polar vinyl monomers such as acrylonitrile. Including.

The thickness of the support is preferably 50 μm
To 250 μm, particularly preferably 70 μm to 200 μm.

In the present invention, the compounds described below are preferably contained in the constituent layers of the silver halide photographic material.

(1) Compound having an acid group: Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (2) Acidic polymer JP-A-6-186659, page (10) [0036]
(3) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (4) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (5) Hydrazine derivative and nucleation promoting agent JP-A-7-128814, page (8), page [0028] to
(23) Compound described in [0079] (6) Redox compound JP-A-4-245243, pages 235 (7) to 250
Compound described on page (22) The above-mentioned additives and other known additives are described, for example, in RD No. 17643 (December 1978), N
o. No. 18716 (November 1979) and the same No. 30
8119 (December 1989).

<< Processing >> In the present invention, ascorbic acid or a derivative thereof is contained in the developer, and the pH of the developer is stable at 8.5 to 10. As ascorbic acid or a derivative thereof, a compound selected from the following formulas (A) and (Aa) is preferably used.

[0073]

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In the formula, R ₁ and R ₂ each represent an alkyl group, an amino group, an alkoxy group or an alkylthio group, which may have a substituent, and R ₁ and R ₂ are bonded to each other to form a ring. May be formed. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

Among the compounds represented by the general formula (A), a compound represented by the following general formula (Aa) wherein R ₁ and R ₂ are bonded to each other to form a ring is preferred.

[0076]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, or a sulfo group, a carboxyl group, an amide group, or a sulfonamide group, and Y ₁ represents O or S is represented, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the general formula (A) or the general formula (Aa) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms. As the amino group, an unsubstituted amino group or An amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. As a group which can be substituted, a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group,
Preferred examples of the substituent include a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or (Aa) are shown below, but the invention is not limited thereto.

[0080]

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[0081]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

In combination with the above developing agents of ascorbic acid or erythorbic acid, 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (eg, o-aminophenol, p-aminophenol, N
It is preferable to use an auxiliary developer such as -methyl-o-aminophenol, N-methyl-p-aminophenol, and 2,4-diaminophenol. In this case, 3-
The developing agents such as pyrazolidones and aminophenols are preferably used in an amount of 0.001 to 1.4 mol per liter of the developing solution. The amount of ascorbic acid or erythorbic acid used is about 0.05 to 1 mol per liter of developer.

In the present invention, it is preferable that polyhydroxybenzenes such as hydroquinone and methylhydroquinone are not substantially used from the viewpoint of environment and performance.

Specific examples of the compound represented by formula (1) or (2) are shown below, but it should not be construed that the invention is limited thereto.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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The feature of the compound represented by formula (1) or (2) is that it is biodegradable. These are preferably used in an amount of 10 ^-6 to 10 ^-1 mol per liter of the developer.

In the present invention, in order to carry out rapid processing with a lower developing replenishment amount, the following general formula (S)
It is preferable to add a compound represented by the following formula.

Formula (S) Z ₁ -SM _{1 In the} formula, Z ₁ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ₂ group, a —COOM
_At least one selected from the group consisting of _two groups (here, M ₂ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonium group Tsuka,
It represents those substituted with at least one substituent selected from this group. M ₁ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

In the general formula (S), the alkyl group represented by Z ₁ preferably has 1 to 30 carbon atoms, and particularly has 2 to 20 carbon atoms, such as a linear, branched or cyclic alkyl group. It may be a group and may have a substituent in addition to the above substituents. The aromatic group represented by Z ₁ preferably has 6 carbon atoms.
To 32 monocyclic or condensed rings, which may have a substituent in addition to the above substituents. The heterocyclic group represented by Z ₁ is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and contains 1 to 6 heteroatoms in one ring independently selected from nitrogen, oxygen and sulfur. And may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. Among the compounds represented by the general formula (S), a compound in which Z ₁ is preferably a heterocyclic group having two or more nitrogen atoms.

The ammonium group is preferably a group having 2 carbon atoms.
0 or less and the substituent is a substituted or unsubstituted straight chain,
It has a branched or cyclic alkyl group (methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group, etc.), substituted or unsubstituted phenyl group, and naphthyl group.

Further, among the compounds represented by formula (S), more preferred are compounds represented by the following formula (Sa).

[0107]

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In the formula, Z represents an unsaturated 5-membered or 6-membered heterocyclic ring having a nitrogen atom (a pyrrole ring, imidazole ring, pyrazole ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc.). a required group, a compound having at least one -SM ₁ or thione group and a hydroxyl _{group, -COOM 1, -SO 3 M 1} ,
It has at least one substituent selected from the group consisting of a substituted or unsubstituted amino group and a substituted or unsubstituted ammonium group. In the formula, R ¹¹ and R ¹² represent a hydrogen atom, -S
M ₁ group, halogen atom, alkyl group (including one having a substituent), alkoxy group (including one having a substituent), hydroxyl group, —COOM ₁ , —SO ₃ M ₁ , alkenyl group (substituent include those with), amino group (including those having a substituent) include those having a carbamoyl group (substituent), a phenyl group (including those having a substituent), with R ¹¹ and R ¹² A ring may be formed. The ring that can be formed is a 5- or 6-membered ring, preferably a nitrogen-containing heterocycle. M ₁ is the same as M ₁ defined for the compound represented by formula (S). Preferably, Z is a group that forms a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the aforementioned -SM ₁ or a thione group. As the substituent, a halogen atom ( For example, fluorine, chlorine, bromine),
Lower alkyl groups (including those having a substituent, preferably those having 5 or less carbon atoms such as methyl group and ethyl group);
A lower alkoxy group (including those having a substituent; methoxy, ethoxy, butoxy, etc., preferably having 5 or less carbon atoms) and a lower alkenyl group (including those having a substituent; preferably having 5 or less carbon atoms); ), Carbamoyl group, phenyl group and the like. Furthermore, the general formula (Sa)
In the above, compounds represented by the following general formulas A to F are particularly preferred.

[0109]

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In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each represent a hydrogen atom, —SM ₁ , a halogen atom, a lower alkyl group (including those having a substituent, and a carbon atom such as a methyl group or an ethyl group). Number 5
The following are preferred. ), Lower alkoxy groups (including those having a substituent, preferably those having 5 or less carbon atoms), hydroxy group, -COOM ₂ , -SO ₃ M ₃ , lower alkenyl groups (including those having a substituent). Carbon number 5
The following are preferred. ), Amino group, a carbamoyl group, a phenyl group, at least one of which is -SM _1. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group and may be the same or different. In particular, a substituent other than -SM ₁ is hydroxy _{group, -COOM 2, -SO 3 M 3} , preferably has a water-soluble group such as an amino group. The amino group represented by R ₁ , R ₂ , R ₃ and R ₄ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group,
Preferably it is an unsubstituted ammonium group.

Specific examples of the compound represented by formula (S) are shown below, but it should not be construed that the invention is limited thereto.

[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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The amount of the compound represented by the general formula (S) is preferably 10 ^-6 to 10 ^-1 mol, more preferably 10 ^-5 to 10 ^-2 mol per liter of the developer. Is preferred.

Examples of the sulfite and metabisulfite used as a preservative include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite.
The sulfite is used in an amount of 0.05 mol / l or more, preferably 0.1 mol / l or more.

An alkali agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Preferably. As the pH buffering agent, carbonate is preferable, and the amount of addition is preferably 0.5 mol or more and 2.5 mol or less, more preferably 0.75 mol or more and 1.5 mol or less per liter.
If necessary, dissolution aids (eg, polyethylene glycols, their esters, alkanolamines, etc.),
Sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants,
Antifoaming agents, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole,
Benzothiazoles, tetrazoles, thiazoles and the like, chelating agents other than the compound represented by the general formula (1) or (2) according to the present invention (for example, ethylenediaminetetraacetic acid or an alkali metal salt thereof, nitrilotriacetic acid salt, Polyphosphate, etc.), development accelerators (for example, US Pat. No. 2,30
No. 4,025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent can be added. The pH of the developer is preferably adjusted to 8.5 or more and 10 or less. More preferably, the pH is 9.0.
It is 9.9 or less.

In the present invention, in order to perform rapid processing with a lower development replenishment amount, it is preferable that the development replenisher is processed with a developer prepared from a solid processing agent.

Here, the solid processing agent refers to a solid formed by forming two or more components constituting the developer, and a single solid containing all the developing components or a solid containing two or more developing components. May be configured. In the solid processing agent, at least one type of solid formed from at least two or more compounds may be used, and a single substance other than the formed solid may be used. Preferable solid processing agents include powders prepared by spray-drying, granules formed by extrusion-drying or granulation (extrusion granulation, fluidized-bed granulation, tumbling granulation) (average particle size of 0). .1mm to 10mm
In particular, 90% of the particle size of the front particles is ± 40% of the average particle size.
), Compression-molded tablets. Particularly preferred forms are granules and tablets. The solid processing agent may contain compounds necessary for molding such as a binder and a lubricant.

The solid processing agent is preferably one in which the processing agent component does not behave as a powder when dissolved, and for that purpose, a solid processing agent containing a compound of the following general formula [6] as a lubricant is preferable.

[0124]

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[Wherein X and Y are a halogen atom, a hydroxyl group,
It represents a sulfonic acid group or a carboxyl group, and R ₆₁ and R ₆₂ represent a hydrogen atom or a hydroxyl group. n represents an integer of 3 to 10. As a preferable structure of the general formula [6], the following general formula [6-
a].

[0126]

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The specific examples of the compounds represented by the general formula [6-a] are shown below. These compounds have structural isomers and include these.

[0128]

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Of the above compounds, D of the structural isomer of 6-6
Mannitol and sorbitol are preferred. The amount of addition is about 0.2 to 50 g, preferably 0.5 to 20 g, and more preferably 0.5 to 10 g per liter of developer.

In order to reduce the amount of waste liquid, it is preferable to carry out the processing while replenishing a fixed amount of development in proportion to the area of the photosensitive material to be processed. The amount of replenishment for development is preferably from 30 to 250 ml, more preferably from 30 to 250 ml, per m ² of the photosensitive material.
00 ml. The development replenisher may be the same as the mother liquor of the developing machine in the tank of the automatic developing machine, or a different solution or a solid processing agent. The development replenishment amount referred to here is the replenishment amount of each solution when replenishing with the same solution as the developing mother liquor,
When replenishing the developing concentrate with a solution diluted with water, it is the total amount of each of the concentrated solution and water.When replenishing the solid developing solution with a solution in which the solid developing solution is dissolved in water, each solid processing agent volume and This is the total volume of water, or the total volume of each solid processing agent and water when replenishing the solid developing agent and water separately. When replenishing with a solid processing agent, the total volume of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water to be separately added is preferably used.

The temperatures of the developing solution, the fixing solution, the washing water and the stabilizing solution are preferably from 10 to 45 ° C., and the respective temperatures may be separately adjusted.

<< Automatic Developing Machine >> In the present invention, when processing is performed using an automatic developing machine, the entire processing time (Dryto dry) from the insertion of the leading end of the photosensitive material into the automatic developing machine to the discharge from the drying zone. ~ Time including all steps of development, fixing, bleaching, washing with water, stabilization, drying, etc.)
The time is preferably 80 seconds, more preferably 15 to 60 seconds, in order to meet the demand for shortening the processing time. If the total processing time is less than 10 seconds, satisfactory photographic performance may not be obtained due to desensitization or softening. In order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is 2 to 2.
Preferably, it is 22 seconds.

In order to remarkably exert the effects of the present invention,
Heat transfer material at 60 ° C or higher (heat roller at 60 to 130 ° C) or radiant object at 150 ° C or higher (tungsten, carbon, nichrome, zirconium oxide, yttrium oxide,
Drying with a mixture of thorium oxide, silicon carbide, etc., which emits heat by direct current generation, or which transmits thermal energy from a resistance heating element to a radiator such as copper, stainless steel, nickel, various ceramics, etc. to emit infrared rays) An automatic developing machine having a zone in which it is formed is preferred.

It is preferable that the heat roller has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side walls. Further, it is preferable that a gear is fixed to one end of the heat roller, and the heat roller is rotated in the transport direction by a drive unit and a drive transmission unit. It is preferable that a halogen heater connected to a temperature controller provided in the automatic developing machine be inserted into the roller of the heat roller.

In addition, in the present invention, an automatic developing machine employing the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. (2) upper left column to (3) upper left column (2) Washing water regenerating purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638, lower left column of page (2) to lower left column of page (5) (4) developing bath and fixing Rinse bath during bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(5) Water replenishment method: JP-A-1-281446, page 2 (lower left column to lower right column on page 2) (6) Method of detecting dry air temperature and humidity to control drying air of automatic developing machine: No. 1-315745, lower right column of page (2) to lower right column of page (7), and JP-A-2-108051
No. (2) lower left column to (3) lower left column (7) Silver recovery method of fixing waste liquid: JP-A-6-27623, page (4), "0012" to page (7), "0071".

[0137]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Support> (Synthesis of SPS) Styrene was added to 200 parts by weight of toluene.
The reaction was carried out at 96 ° C. for 8 hours using 00 parts by weight, 56 g of triisobutylaluminum and 234 g of pentamethylcyclopentadienyltitanium trimethoxide. After decomposing and removing the catalyst with a methanol solution of sodium hydroxide,
After washing three times with methanol, the target compound (SPS)
4 parts by weight were obtained.

(Preparation of SPS Film) Obtained SPS
Was melt-extruded from a T-die at 330 ° C. into a film and quenched and solidified on a cooling drum to obtain an uncentrifuged film. At this time, the take-up speed of the cooling drum was performed in two stages, and the unstretched film having a thickness of
After preheating at ℃ and longitudinal stretching (3.1 times), transverse stretching at 130 ° C (3.4 times) and heat fixing at 250 ° C. As a result, the bending elastic modulus of the support was 450 kg / m.
A biaxially stretched film having a thickness of m ² and a thickness of 100 μm was obtained.

(Undercoating of SPS Film) After silica was vapor-deposited on both sides of the SPS film, an undercoating layer containing styrene-glycidyl acrylate and tin oxide fine particles and subjected to antistatic treatment was formed.

<Preparation of Photosensitive Material> (Preparation of Silver Halide Emulsion A) An average thickness of 70 mol% of silver chloride and the balance of silver bromide of 0.05 using a double jet method.
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The obtained emulsion was silver / chloroiodobromide (90 mol% of silver chloride) having a core / shell type monodisperse (coefficient of variation: 10%) having a (100) plane as a main plane having an average thickness of 0.10 μm and an average diameter of 0.25 μm. , 0.2 mol% of silver iodobromide, the remainder being silver bromide). Then, JP-A-2-280139, 287
Desalting was performed using denatured gelatin G-8 (having the amino group in gelatin replaced with phenylcarbamyl) described on page (3).

The EAg after desalting was 190 mv at 50 ° C. 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻³ mol per mol of silver, potassium bromide and citric acid were added to adjust the pH to 5.6 and the EAg to 123 mV. After adding ^10-5 mol, 3 x 1 of inorganic sulfur was added.
0 ^-6 mol added to up sensitivity exits at temperature 60 ° C. chemically ripened.

After completion of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 3. ^-4 moles and gelatin were added.

(Preparation of Silver Halide Emulsion B) Using a simultaneous mixing method, 60 mol% of silver chloride and 2.5 mol% of silver iodide, the balance being silver bromide having an average thickness of 0.05 μm and an average diameter of 0.1 mol.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver.

The emulsion thus obtained had a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (average thickness: 0.10 μm, average diameter: 0.42 μm). 0.5 mol%, the balance consisting of silver bromide). Subsequently, desalting was performed using denatured gelatin G-8 (supra). The EAg after desalting was 180 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and 2 × 10 ⁻⁵ mol of chloroauric acid was added.
N'-trimethyl-N'-heptafluoroselenourea was added in an amount of 3 × 10 ^-5 mol and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After aging, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻⁴ mol, and gelatin was added.

(Preparation of a silver halide photographic light-sensitive material for a printing plate making scanner for a laser light source) On one undercoat layer of the above-mentioned support, a gelatin undercoat layer of the following formula 1 was prepared in an amount of 0.5 g / g. as will become m ^2, the following formulation 2 thereon
The silver halide emulsion layer 1 was prepared so that the silver amount was 1.5 g / m ² and the gelatin amount was 0.5 g / m ^2. 0.3 g / m ² , and further the formulation 4
The silver halide emulsion layer 2 was prepared so that the silver amount was 1.4 g / m ² and the gelatin amount was 0.4 g / m ² , and the following formulation 5 was further added.
Was applied simultaneously so that the amount of gelatin became 0.6 g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 6 was further coated with a hydrophobic polymer layer of the following formulation 7 so that the amount of gelatin was 0.6 g / m ² , and further a further formulation of the following A sample was obtained by simultaneously coating the backing protective layer No. 8 with the emulsion layer so that the amount of gelatin became 0.4 g / m ² .

Formulation 1 (Composition of Gelatin Undercoat Layer) Gelatin 0.5 g / m ² Solid dispersed fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Prescription 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Dye AD so that the silver amount becomes 1.5 g / m ² -8 solid dispersion fine particles (average particle size: 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² quaternary onium compounds in table 1 are shown the amount redox compounds: RE-1 20mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener ^{g 5mg / m 2 S-1} 0.7m / M ² 2-mercapto-6-hydroxy-purine 5 mg / m ² ethylenediaminetetraacetic acid (EDTA) 30 mg / m ² Colloidal silica (average particle size 0.05 .mu.m) 10 mg / m ² Formulation 3 (intermediate layer composition) Gelatin 0.3g / M ² S-1 2 mg / m ² Prescription 4 (Silver halide emulsion layer 2 composition) Silver halide emulsion B Sensitizing dye d-1 3 mg / m ² sensitization so that the silver amount would be 1.4 g / m ² . Dye 3 mg / m ² Compound H-1 5 mg / m ² Nucleation promoter Nb-1 40 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 20 mg / m ² Latex polymer f 0.5 g / M ² S-1 1.7 mg / m ² Formulation 5 (Emulsion protective layer composition) Gelatin 0.6 g / m ² Solid dispersion of dye AD-5 (average particle size 0.1 μm) 40 mg / m ² S-1 12mg / m ² Ma Soaking agent: monodisperse silica having an average particle size of 3.5 μm 25 mg / m ² nucleation accelerator Na-1 40 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener: K-1 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² Formulation 7 (hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid) = 97: 3) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: average particle size 5 μm Monodisperse polymethyl methacrylate 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² Dye k 20 mg / m ² HO (CH ₂ CH ₂ O) ₆₈ H 50 mg / m ² hardener: K-1 20 mg / m ²

[0150]

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[0151]

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[0152]

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[0153]

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After coating and drying, the surface resistivity on the backing side was 6 × 10 ¹¹ at 23 ° C. and 20% RH, the pH on the emulsion side was 5.5, and the degree of swelling was 175.

<Preparation of Processing Agent> (Preparation of Processing Solution) (1) Starting developer (HAD-S) (for 1 liter of working solution) Pure water 400 ml Compound of general formula (1) or (2) Amount Sodium sulfite 31.52 g Potassium carbonate 55 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzotriazole 0.27 g 1-Phenyl-5-mercaptotetrazole 0.03 g 1-Phenyl-4-hydroxymethyl-4-methyl- 3-Pyrazolidone (dimesone S) 1.1 g Ascorbic acid or its derivative Amount shown in Table 1 Diethylaminopropanediol 25 g Isoelite P (brine salt refined sugar) 20 g
Was adjusted to the value shown in Table 1.

(2) Preparation of Replenished Developing Tablet (HAD-JR) <Preparation of Granulated A Parts> (1 L of Liquid Used) Compound of General Formula (1) or (2) Amount shown in Table 1 Sodium sulfite 31 0.52 g 8-mercaptoadenine 0.09 g diethylene glycol 50 g 5-methylbenzotriazole 0.27 g 1-phenyl-5-mercaptotetrazole 0.03 g dimezone S 1.1 g ascorbic acid or a derivative thereof As shown in Table 1 Isoelite P (brine water) Minato sugar) 20 g Pine flow (trade name: Matsui Chemical) 40 g The above materials were mixed in a commercially available bandam mill for 30 minutes, and then granulated at room temperature for 10 minutes with a commercially available stirring granulator. Granulated material A dried at 40 ° C for 2 hours in a bath dryer
Got the parts.

<Preparation of Granulation B Parts> (for 1 liter of liquid used) 5 g of potassium carbonate D-mannitol (trade name: manufactured by Kao Corporation) 5 g of lithium hydroxide (starting the pH when the tablet is dissolved at a predetermined concentration) The above materials were mixed in a commercially available bandam mill for 30 minutes, and further granulated at room temperature for 10 minutes using a commercially available stirring granulator. C. for 2 hours to obtain a granulated B part having an average particle diameter of 4000 .mu.m and a repose angle of 30 degrees.

The above parts A and B are thoroughly mixed for 10 minutes, and the resulting mixture is mixed with a machine UDN DFE30.
Using a 40 tableting machine (manufactured by Masina Co., Ltd.), 25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² with the filling amount shown in Table 2 per tablet. .

(3) Starting Fixer (HAF-S) (for 1 liter of used solution) Pure water 120 ml Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 37.8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate / 18-hydrate 18 g Isoelite P (Saltwater refined sugar) 5 g 500 ml using 50% aqueous sulfuric acid solution and pure water (pH 4.0).
83). When used, 500 ml of pure water and 500 ml of the above concentrated liquid are mixed and used.

(4) Preparation of Supplementary Fixing Tablet <Preparation of Granulation A Parts> (for 1 L of liquid used) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium bisulfite 10 g Sodium acetate 40 g Isoelite P ( Salt water port refined sugar) 5 g Pine flow (trade name: manufactured by Matsutani Chemical Co., Ltd.) 8 g The above materials were mixed for 30 minutes in a commercially available bandam mill, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator, followed by granulation. The product is dried in a fluidized-bed dryer at 40 ° C. for 2 hours and granulated A
Got the parts.

<Preparation of Granulation B Parts> (1 liter of liquid used) 10 g of boric acid 3 g of tartaric acid 18 g of sodium hydrogen sulfate 18 g of aluminum sulfate / 18 hydrate 37 g of pine flow (trade name: manufactured by Matsutani Chemical Co., Ltd.) 4 g After mixing for 30 minutes in a bandam mill and further granulating at room temperature for 10 minutes with a commercially available stirring granulator, the granulated product was dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain granulated product B.
Got the parts.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the obtained mixture was used for the machine UD ・ DFE30 ・
Using a 40 tableting machine (manufactured by Masina Co., Ltd.), 25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compressing tablets at a filling amount of 11.0 g per tablet and 1.5 ton / m ² . .

(Automatic developing machine) GR-26 manufactured by Konica Corporation
An automatic developing machine modified from SR was used. In order to directly replenish tablets as a solid processing agent, the system was modified so that tablets could be fed one by one from the upper part of the automatic processor. Entire size (6
Development replenisher 1 per 10 × 508 mm) photosensitive material
And 40 ml of water, and one fixing replenisher and 40 ml of water. This replenishment amount is 130 ml / m for the developer.
² and 130 ml / m ² for the fixing solution.

The drying zone of the automatic developing machine has a far-infrared heater and a cover for covering the entire surface of the processing tank so that the processing liquid is not easily evaporated.

[0165] The fixing waste liquid is processed while returning the processing solution after silver recovery using the silver recovery apparatus described in Example 1 of JP-A-6-27623 to the fixing tank again. The treatment was carried out using a descaling preventer manufactured by K.K.

<Evaluation Method> The obtained light-sensitive material was heated at 55 ° C.
After storing for 3 days under the temperature and humidity conditions of RH 50%, the following exposure and development treatments were performed to evaluate the performance.

The processing was carried out under the above conditions, and the photographic performance at the start of running and after running after processing the photosensitive material by 100 m ² were compared. At that time, one unexposed sample and one whole-surface exposed sample were processed alternately so that the blackening ratio of the photosensitive material became 50%.

(Evaluation of halftone dot quality) Exposure was performed with a 16-μm random pattern halftone dot (FM screen) using SG-747RU (manufactured by Dainippon Screen Co., Ltd.) so as to change the halftone dot in a stepwise manner. Was. Small dots (5% target) of the halftone dot pattern were visually evaluated for dot quality using a 100-fold loupe. The highest rank was set to 5, and the ranks were lowered and evaluated to 4, 3, 2, and 1 according to the dot quality.

(White spots) The density of the blackened portions of the samples evaluated for the halftone dot quality was measured. The larger the value in the table, the smaller the white spots. If the value is less than 3.5, the white spots are conspicuous and at a level that does not endure practical use.

Note that the measurement of the dot area was performed using X-Rite 3
61T (manufactured by Nippon Lithographic Equipment Co., Ltd.) was used, and the concentration was measured using a Macbeth densitometer.

Table 1 shows the above results.

[0172]

[Table 1]

Example 2 (Preparation of silver halide photographic light-sensitive material sample for reversal of bright room) A silver halide content of 98 mol% and a silver bromide content of 2 mol% were obtained by a double jet method. And cubic silver chlorobromide particles were prepared. K ₃ Rh (H ₂ O) B during mixing
r ₅ was added 7 × 10 ^-5 mol per 1 mol of silver. Before the desalting step of removing soluble salts by a conventional method, 0.6 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added per mol of silver (hereinafter, referred to as “the salt”). Unless otherwise specified, the amount is based on 1 mol of silver).

The temperature of this emulsion was raised to 60 ° C.
mg and 0.75 mg of sodium thiosulfate were added.
60 minutes after adding I, 600 mg of TAI was further added and the temperature was lowered and set.

Then, a coating solution was prepared by adding an additive so as to be in the following amount per 1 m ^{2, and the} following emulsion layer coating solution and protective solution were sequentially coated on one surface of the subbed SPS support of Example 1. The lower layer liquid was simultaneously coated with the following backing coating liquid on the opposite surface.

<Emulsion coating solution> NaOH 0.5N solution 4.39 ml / m ² compound a 6.53 mg / m ² quaternary onium compound Amount shown in Table 2 Kirayasaponin 107 mg / m ² compound b 18.5 mg / m ² compound c 9.8 mg / m ² of gelatin latex 480 mg / m ² sodium polystyrenesulfonate 52.2 mg / m ² colloidal silica 20 mg / ^{m 2} <protective layer infranate> gelatin 0.5 g / m ² dye two of the solid dispersion (average particle size 0.1μm) 62.0mg / m ² citric acid 4.1 mg / m ² formalin 1.2 mg / m ² hardener: K-1 0.6mg / m ² sodium polystyrenesulfonate 11.0 mg / m ² <Protective layer upper layer solution> Gelatin 0.3 g / m ² compound E 18.0 mg / m ² Dye 48.4 mg / m ² Compound F 105.0 mg / m ² compounds g 1.25 mg / m ² amorphous silica (average particle size 1.63 μm) 15.0 mg / m ² amorphous silica (average particle size 3.5 μm) 21.0 mg / m ² citric acid 4.5 mg / m formalin 10 mg / m ² <backing coating solution> compound Chi 170 mg / m ² dye d 30 mg / m ² compound Li 45 mg / m ² compound j 10 mg / m ² Quillaja saponin in ² polystyrene sulfonate sodium 11.0 mg / m ² added inline 111 mg / m ² compound le 200 mg / m ² colloidal silica 200 mg / m ² compound o 35 mg / m ² compound follower 31 mg / m ² compound Ca 3.1 mg / ^{m 2} of polymethyl methacrylate acid polymer (average particle diameter 5.6 [mu] m) 28.9 mg / m ² glyoxal 10.1 mg / m ² citric acid 9.3 mg / m ² polystyrenesulfonate The following additional compounds those with sodium 71.1 mg / m ² in-line Yo 81 mg / m ² Compound data 88.2mg / m ² of calcium acetate 3.0 mg / m ² Hardener: K-1 10mg / ^{m 2}

[0177]

Embedded image

[0178]

Embedded image

[0179]

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The coating amount was 2.0 g / silver in the emulsion layer.
gelatin amount 1.2 g / m ² m ^{2, and} the amount of gelatin backing layer is uniformly coated so as to be 2.1 g / m ^2.

(Processing solution formulation) (5) Starting developer (TAD-S) (1 liter of working solution) Pure water 350 ml Compound of general formula (1) or (2) Amount shown in Table 1 Sodium sulfite 15.76 g KBr 2.5 g Potassium carbonate 32.84 g Potassium hydrogen carbonate 16.2 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzotriazole 0.5 g 1-Phenyl-5-mercaptotetrazole 0.02 g Dimezone S 2.7 g Ascorbic acid Or its derivative Amount shown in Table 1 It was dissolved according to the above-mentioned formulation and finished to 500 ml with pure water.
When used, 500 ml of pure water was mixed with the above-mentioned concentrated solution, and the pH of the used solution was adjusted to the value shown in Table 2.

(6) Preparation of Replenished Developing Tablet (TAD-JR) <Preparation of Granulated A Parts> (for 1 L of Liquid Used) Compound of General Formula (1) or (2) Amount shown in Table 1 Potassium carbonate 32 .84 g D-mannitol (trade name: manufactured by Kao Corporation) 5 g The above materials were mixed in a commercially available bandam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. Granulated material A dried at 40 ° C for 2 hours in a bath dryer
Got the parts.

<Preparation of Granulation B Parts> (for 1 liter of liquid used) Sodium sulfite 15.76 g KBr 2.5 g Potassium hydrogen carbonate 47 g 8-mercaptoadenine 0.06 g 5-methylbenzotriazole 0.5 g 1-phenyl- 5-mercaptotetrazole 0.02 g Dimezone S 2.7 g Ascorbic acid or its derivative Amount shown in Table 1 D-sorbitol 5 g 1-sodium 1-octanesulfonate 2 g The above materials were mixed in a commercially available bandam mill for 30 minutes, and further commercially available stirring. After granulating at room temperature for 10 minutes with a granulator, the granulated product was dried at 40 ° C. for 2 hours with a fluidized-bed dryer to obtain a granulated product B part.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the resulting mixture was mixed with a machine UDN DFE30.
Using a 40 tableting machine (manufactured by Masina Co., Ltd.), 10 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² at a filling amount shown in Table 3 per tablet. .

When used, 10 tablets were dissolved in pure water so that the volume became 1 liter.
H was adjusted.

<Evaluation Method> The obtained photosensitive material was heated at 55 ° C.
After storing for 3 days under the condition of temperature and humidity of 50% RH, the film was developed by the following exposure in the same manner as in Example 1 to evaluate the performance.

At that time, before the start of development, the photosensitive material was set at 200 m.
The photographic performance after the ^two treatments was compared. At this time, eight unexposed samples and two whole-surface exposed samples were processed alternately so that the blackening ratio of the photosensitive material became 20%.

(Image quality of cut characters) In order to evaluate the image quality of cut characters, an original “cut mask film / transparent pasting base / film of a line drawing positive image” having the structure described in FIG. 2 of JP-B-6-40207 is used. (Line drawing manuscript) / transparent paste base / halftone dot film (halftone manuscript) laminated in this order "is prepared, and the manuscript is brought into close contact with the emulsion surface of the photosensitive material sample. Image exposure was performed with a bright room printer P627FM using a discharge tube light source, and the quality of the blank characters after the development processing was evaluated in five ranks.

[0189] Draft character image quality 5 is an image quality capable of reproducing a 30 µm wide character when proper exposure is performed such that a 50% halftone dot area becomes 50% halftone dot area on the photosensitive material. Good character quality. Cut character quality 1
The term "image quality" means that only characters of 150 .mu.m or more can be reproduced when the same appropriate exposure is given, and it means poor quality of characters. 3 or more is a level that can withstand practical use.

(White spots) The density of the blackened portions of the samples for which the character image quality was evaluated was measured. The larger the value in the table, the smaller the white spots. If the value is less than 3.5, the white spots are conspicuous and at a level that does not endure practical use.

The measurement of the halftone dot area was performed using X-Rite 3
61T (manufactured by Nippon Lithographic Equipment Co., Ltd.) was used, and the concentration was measured using a Macbeth densitometer.

Table 2 shows the obtained results.

[0193]

[Table 2]

[0194]

According to the present invention, p is used to stabilize processing.
Using a developing solution of H10 or less, the amount of replenishment can be reduced, and fluctuations in photographic performance can be suppressed even when running with rapid processing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location G03C 5/30 G03C 5/30 5/305 5/305 5/31 5/31

Claims (5)

[Claims] When a black-and-white silver halide photographic material having an emulsion layer containing a silver halide emulsion having a silver chloride content of 60 mol% or more on a support is treated with a developer having a pH of 8.5 to 10, At least one layer of the black-and-white silver halide photographic material contains a quaternary onium compound, and contains at least one of ascorbic acid or a derivative thereof and a compound represented by the following general formula (1) or (2). A method for processing a black-and-white silver halide photographic material, characterized by processing with a developing solution. Embedded image [In the formula, B represents a hydrogen atom, a hydroxyl group or CH ₂ COOM, and M represents a hydrogen atom, a cation or an alkali metal atom. When B is a hydrogen atom, A _{1 to} A ₉ each represent a hydrogen atom, a hydroxyl group, C _n H _{2n + 1} or (CH ₂ ) _m X; n is an integer of 1 to 3; X represents COO
Represents M, NH ₂ or a hydroxyl group, and n ₁ = 1, n ₂ = 1, n ₃ +
n ₄ is an integer of 1 to 4, all A ₁ to A ₅ are not a hydrogen atom. When B is a hydroxyl group or CH ₂ COOM, n ₁ + n ₂ = 2, n ₃ = 0, n ₄ = 1, A ₁ , A ₈ and A ₉ are hydrogen atoms, A _{2 to} A ₅ are each hydrogen atoms, Hydroxyl group, COOM, PO ₃ (M) ₂ , CH ₂ COOM, CH ₂ O
H or lower alkyl group, and at least one of A _{2 to} A ₅
One represents COOM, PO ₃ (M) ₂ or CH ₂ COOM, where M is as defined above. [Chemical formula 2] [In the formula, A _{11 to} A ₁₄ each represent a COOM or a hydroxyl group, R _{1 to} R ₄ each represent a hydrogen atom, a hydroxyl group or a lower alkyl group, and n _{11 to} n _{14 each} represent an integer of 0 to 2. X '
Alkylene or 2 to 6 carbon atoms atoms - (B ₁ O) _m -
Represents B ₂ —, B ₁ and B ₂ represent an alkylene group having 1 to 5 carbon atoms, and m represents 1 or 2. ] 2. The method for processing a black-and-white silver halide photographic material according to claim 1, wherein the developer contains a compound represented by the following general formula (S). General formula (S) Z ₁ -SM ₁ [wherein Z ₁ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ₂ group, a —CO ₂
An OM ₂ group (where M ₂ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonium group; It represents one substituted by one or a substituent having at least one selected from this group. M ₁ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate). ] 3. Processing is performed while replenishing a developing replenisher prepared from a solid processing agent using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing bath, and a drying unit. A method for processing a black-and-white silver halide photographic material according to claim 1 or 2. 4. Processing using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing bath, and a drying section while replenishing a developing replenisher at 30 ml or more and 250 ml or less per 1 m ^{2 of the} photosensitive material. Claim 1, characterized in that:
4. The method for processing a black-and-white silver halide photographic material according to 2 or 3. 5. The processing time (Dry) from the start of development of the photosensitive material to the exit of the drying zone using an automatic developing machine having a developing tank, a fixing tank, a washing tank or a stabilizing bath, and a drying section. 5. The method for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the processing is performed for 10 to 80 seconds.