JPH08314076A - Method for processing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To secure satisfactory dot quality even when a large amount of running processing is carried out in a state of reducing a replenishing amt. of developer, to enhance sensitivity, and to enable processing good in initial developability by incorporating a specified compound in a developer at the time of development processing with the developer containing a specified developing agent and controlling the pH of the developer in the specified range. CONSTITUTION: The negative silver halide photographic sensitive material is developed with the developer containing no hydroquinone but the developing agent represented by formula I and further a compound of formula II and controlled within a pH of 9.5-10.6. In formulae I and II, each of R1 and R2 is an optionally substituted alkyl or optionally substituted amino group or the like; (k) is 0 or 1 and, when k=1, X is -CO- or -CS-; each of M1 and M2 is an H or alkali metal atom; R is at least one group selected from among a group of -SO3 M or -COOM or the like; M is an H or alkali metal atom; (n) is 1 or 2; and (m) is 2 or 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a black-and-white silver halide photographic light-sensitive material, and more particularly to a method for processing a negative type black-and-white silver halide photographic light-sensitive material for printing plate making.

[0002]

BACKGROUND OF THE INVENTION Black-and-white silver halide photographic light-sensitive materials, particularly negative-working black-and-white silver halide light-sensitive materials for printing plates, are generally automatic after exposure and have a developing section, a fixing section, a washing section or a stabilizing bath section, and a drying section. It is processed in the developing machine.

In recent years, interest in the environment has risen, and attention has been paid to the safety of processing solutions. In the developing solution, US Pat.
A method using ascorbic acids as described in 6,816 is known.

Further, there is also an interest in reducing the amount of photographic processing waste liquid. Photographic effluents usually cannot be released to public sewers, and waste liquors are collected and destroyed by cumbersome and costly incineration methods. From these points, it has been strongly desired to reduce the photographic processing waste liquid. As a means for solving such a reduction of the photographic processing waste liquid, it is considered to reduce the replenishing amount of the developing solution, which is usually 250 ml / m ² or more, when the processing is performed by using an automatic processor.

Further, the printing plate making operation includes a step of faithfully reproducing the halftone dot image. In order to produce excellent printed matter, it is necessary to faithfully reproduce the target halftone dots on the photosensitive material for plate making. In recent years, in the field of printing plate making, it has been required to improve the halftone dot quality. For example, a method called high-definition printing of 600 lines / inch or more and FM screening composed of a uniform random pattern of extremely small dots is 25 μm or less. It is necessary to reproduce the minute points of. These are an image output machine equipped with a laser light source such as an Ar laser, a HeNe laser, and a semiconductor laser, exposure by a so-called plate-making scanner, and when performing a returning operation of exposing a transparent halftone image original with a printer, It is necessary that the target minute halftone dots be faithfully reproduced.

On the other hand, since a halftone image is used, there is known a photographic technique which can reproduce an image in super-high contrast due to its photographic characteristics. Among them, a photographic light-sensitive material containing a hydrazine derivative as disclosed in, for example, US Pat. No. 4,269,929 is known.

[0007]

However, in the developers using these ascorbic acid type developing agents, the activity is low, and particularly in the case of the light-sensitive material containing the hydrazine derivative as described above, the replenishing amount is simply reduced. After running a large amount of light-sensitive material of 100 m ² or more, if you try to reproduce minute spots of 25 μm or less, halftone quality will deteriorate, desensitization, initial developability deterioration and sandiness will occur. There was a problem that so-called black spots were likely to occur.

Therefore, an object of the present invention is to perform a large-scale running process of 100 m ² or more with a developer of an ascorbic acid developing agent which is environmentally friendly and highly safe and with a reduced developer replenishing amount. Another object of the present invention is to provide a method for processing a black-and-white silver halide photographic light-sensitive material, which has good halftone dot quality, high sensitivity, good initial developability, and hardly causes black spots. Another object of the present invention is a method for processing a black-and-white silver halide photographic light-sensitive material having good halftone dot quality and good initial developability when reproducing minute points of 25 microns or less in a printing plate-making light-sensitive material. To provide.

[0009]

The above object of the present invention has been achieved by the following constitution.

(1) A negative-type silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one surface of a support is prepared by the following general formula (1) without substantially containing hydroquinone. When developing with a developer containing a developing agent represented by the formula, the developer contains a compound represented by the following general formula (2), and the pH of the developer is 9.5 or more 1
A processing method for a negative-type black-and-white silver halide photographic light-sensitive material, which is less than 0.6.

[0011]

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[Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
A substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ and R ₂ may combine with each other to form a ring. 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. ]

[0013]

[Chemical 4]

[Wherein R represents a —SO ₃ M group, a —COOM group (where M represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group. Represents at least one selected from the group consisting of a substituted or unsubstituted ammonio group. n is 1
Alternatively, it represents an integer of 2, and m represents an integer of 1, 2 or 3. (2) The method for processing a negative-working black-and-white silver halide photographic light-sensitive material according to (1), wherein at least one hydrazine derivative is contained in at least one layer on the side of the silver halide photographic emulsion layer.

(3) The negative-working black-and-white silver halide photographic light-sensitive material according to (2), wherein at least one layer on the side of the silver halide photographic emulsion layer contains at least one nucleation accelerator. Processing method.

(4) The developer contains a compound represented by the following general formula (S) (1),
(2) or the processing method for a negative-working black-and-white silver halide photographic light-sensitive material according to (3).

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, -SO ₃ M ¹ group, -COOM ¹ group (here Wherein M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, at least one selected from the group consisting of a substituted or unsubstituted ammonio group, or It represents those substituted with a substituent having at least one selected from the group. M ¹ is a hydrogen atom,
It represents an alkali metal atom or a substituted or unsubstituted amidino group (which may form a hydrohalide or sulfonate). (5) The negative-working black-and-white silver halide photographic light-sensitive material is processed in an automatic processor having at least a developing tank, a fixing tank, a washing tank or a stabilizing bath, and a drying section while supplementing at least a developing replenisher, The negative-type black-and-white silver halide photograph described in (1), (2), (3) or (4), wherein the replenishing amount of the developing replenisher is 220 ml or less per 1 m ^{2 of the} light-sensitive material to be processed. Method of processing photosensitive material.

The present invention will be specifically described below.

In the present invention, the hydrazine derivative is preferably a compound represented by the following general formula [H].

[0020]

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In the formula, A represents an aryl group or a heterocycle containing at least one sulfur atom or oxygen atom, and G represents a-(CO) _n- group, a sulfonyl group, a sulfoxy group, -P (= O). R
Represents a ₂ -group or an iminomethylene group, n represents an integer of 1 or 2, and A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or Represents an unsubstituted acyl group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group,
It represents an amino group, a carbamoyl group, or an oxycarbonyl group. R ₂ is a substituted or unsubstituted alkyl group,
An alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an amino group and the like.

Of the compounds represented by the general formula [H], the compounds represented by the following general formula [Ha] are more preferred.

[0023]

[Chemical 6]

In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg, pyridyl group, cenyl group, Represents a furyl group),
Those groups which are further substituted with an appropriate substituent are preferably used. Further, R ¹ preferably contains at least one diffusion resistant group or silver halide adsorption promoting group.

As the anti-diffusion group, a ballast group commonly used in a non-moving photographic additive such as a coupler is preferable, and as the ballast group, an alkyl group having 8 or more carbon atoms which is relatively inactive to photographic properties is preferable. , Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

In the general formula [Ha], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different. .

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and a —CON (R ⁴ ) (R ⁵ ) group (R ³ represents an alkynyl group or a saturated heterocyclic group,
R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0032]

[Chemical 7]

[0033]

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[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

Specific examples of other preferable hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, column 4 to column 60.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by the method as described in No. 248, columns 59 to 80.

The amount of addition may be any amount as long as it gives a high contrast (amount of high contrast), and the optimum amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc. Generally, it is in the range of 10 ^-6 to 10 ^-1 mol, and preferably in the range of 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

The hydrazine derivative used in the present invention is
It is added to the silver halide emulsion layer or its adjacent layer.

In order to effectively promote the contrast increase by the hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb].

[0042]

[Chemical 12]

In the general formula [Na], R ₁₁ , R ₁₂ , and R ₁₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. A ring can be formed by R ₁₁ , R ₁₂ , and R ₁₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is more preferable. Further, as preferable adsorption groups, heterocycle, mercapto group, thioether group,
Examples thereof include thione group and thiourea group. General formula (N
As a], a compound having at least one silver halide adsorption group in the molecule is preferable, and a compound having at least one thioether group as a silver halide adsorption group in the molecule is particularly preferable.

Specific examples of these nucleation accelerators [Na] will be given below.

[0045]

[Chemical 13]

[0046]

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[0047]

[Chemical 15]

[0048]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group, and Ar and R ₁₄
May be linked by a linking group to form a ring. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Further, as a preferable silver halide adsorbing group, a group having the same meaning as the silver halide adsorbing group of the compound represented by the general formula [H] can be mentioned.

Specific examples of the compound of the general formula [Nb] include those shown below.

[0051]

[Chemical 17]

[0052]

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Specific examples of other preferable nucleation promoting compounds are described in JP-A-6-258751 (13), page [0062] to (15), page [006].
(2-1) to (2-20) described in "5" and 3-1 described in No. 6-258751 (15), page "0067" to (16), "0068" ~ 3-6.

These nucleation accelerating compounds can be used in any layer as long as they are on the silver halide emulsion layer side, but are preferably used in the silver halide emulsion layer or its adjacent layer.

In the present invention, the black-and-white silver halide photographic light-sensitive material is preferably subjected to photographic processing after exposure by an automatic processor having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

The developer used in the present invention contains substantially no hydroquinone, contains the compound represented by the following general formula (1), and contains the compound represented by the general formula (2). .

[0057]

[Chemical 19]

In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ and R ₂ may combine with each other to form a ring. 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.

[0059]

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In the formula, R represents a —SO ₃ M group, a —COOM group (where M represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, It represents at least one selected from the group consisting of a substituted or unsubstituted ammonio group. n represents an integer of 1 or 2 and m represents an integer of 1, 2 or 3.

The compound represented by the general formula (1) will be described.

In the compound represented by the general formula (1), a compound represented by the following general formula [1-a] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0063]

[Chemical 21]

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

The alkyl group in formula (1) or [1-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula (1) or the general formula [1-a] according to the present invention are shown below.
The present invention is not limited to these.

[0067]

[Chemical formula 22]

[0068]

[Chemical formula 23]

These compounds are typically ascorbic acid, erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

The compound represented by the general formula (2) will be described.

In the general formula (2), R is --SO ₃ M
Group, a -COOM group (wherein M 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 ammonio group. At least one is represented, and R is more preferably a —SO ₃ M group. n represents an integer of 1 or 2 and m represents 1, 2 or 3
Represents the integer.

Specific examples of the compound represented by the general formula (2) are shown below, but the invention is not limited thereto.

[0073]

[Chemical formula 24]

The compound represented by the general formula (2) can be easily synthesized by a known synthesis method.

The amount of the compound represented by the general formula (2) of the present invention to be used is 0.02 mol to 0.
It is preferably 5 mol, more preferably 0.025 mol to 0.
It is preferably 3 mol.

In the present invention, substantially no hydroquinone is contained. The term "substantially free" means an amount of less than 0.01 mol per liter of the developing solution.

In the present invention, the developing agent of the general formula (1) according to the present invention and 3-pyrazolidones (eg 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-methyl-o-
Aminophenol, N-methyl-p-aminophenol, 2,4
-A developing agent such as diaminophenol) can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are usually preferably used in an amount of 0.01 to 1.4 mol per liter of the developing solution.

The developer of the present invention may contain a compound represented by the following general formula (S).

General 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 ¹ group, a —COOM ¹ group (here, M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, at least one selected from the group consisting of a substituted or unsubstituted ammonio group, or this group Represented by being substituted with a substituent having at least one selected from the group consisting of: M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide salt or a sulfonate salt).

Further, in the general formula (S), the alkyl group represented by Z ¹ is preferably one having 1 to 30 carbon atoms, particularly straight chain, branched or cyclic alkyl having 2 to 20 carbon atoms. The group may have a substituent in addition to the above substituents. The aromatic group represented by Z ¹ preferably has 6 to 3 carbon atoms.
It is a monocyclic or condensed ring of 2 and 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 1 to 6 heteroatoms independently selected from nitrogen, oxygen and sulfur in one ring. It has a 5- or 6-membered ring and may have a substituent in addition to the above. Among the compounds represented by the general formula (S), Z ¹ is preferably a heterocyclic group having one or more nitrogen atoms.

In the formula, Z ¹ is a hydroxyl group, a —SO ₃ M ¹ group,
-COOM ¹ group (where M ¹ is a hydrogen atom, an alkali metal atom,
Or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, at least one selected from the group consisting of substituted or unsubstituted ammonio groups, or a substituent having at least one selected from this group Has been replaced by M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide salt or a sulfonate salt). The ammonio group preferably has 20 or less carbon atoms, and the substituent is a substituted or unsubstituted linear, branched, or cyclic alkyl group (for example, methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group). Etc.), a substituted or unsubstituted phenyl group or a naphthyl group.

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

[0083]

[Chemical 25]

In the formula, Z is a group necessary for forming an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (eg, pyrrole, imidazole, pyrazole, pyrimidine, pyridazine, pyrazine, etc.). is there. Where:
R ¹¹ and R ¹² are hydrogen atom, —SM ¹ group, halogen atom, alkyl group (including those having a substituent), alkoxy group (including those having a substituent), hydroxyl group, —CO
OM ¹ group, —SO ₃ M ¹ group, alkenyl group (including those having a substituent), amino group (including those having a substituent), carbamoyl group (including those having a substituent), phenyl group ( At least one group selected from (including those having a substituent), and R ¹¹ and R ¹² may form a ring.
The ring that can be formed is a ring having at least one 5- or 6-membered ring, and is preferably a nitrogen-containing heterocycle. M ¹ is the same as M ¹ defined in the compound represented by the general formula (S). In the formula, the compound represented by the general formula (Sa) is a compound having at least one -SM ¹ group or a thione group, and is a hydroxyl group, -CO
It has at least one substituent selected from the group consisting of an OM ¹ group, a —SO ₃ M ¹ group, a substituted or unsubstituted amino group, and a substituted or unsubstituted ammonio group. It may have a substituent other than the above-SM ¹ group or thione group, and the substituent includes a halogen atom (eg, fluorine, chlorine, bromine) and a lower alkyl group (having a substituent). A methyl group, an ethyl group or the like having a carbon number of 5 or less is preferable), a lower alkoxy group (including a group having a substituent, methoxy, ethoxy, butoxy or the like having a carbon number of 5 or less is preferable), a lower alkenyl Examples thereof include groups (including those having a substituent, those having 5 or less carbon atoms are preferable), carbamoyl groups, phenyl groups and the like. Furthermore, in the general formula (Sa), the compounds represented by the following general formulas A to F are particularly preferable.

[0085]

[Chemical formula 26]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a —SM ₁ group, a halogen atom, a lower alkyl group (including those having a substituent. Carbon number 5
The following are preferred. ), Lower alkoxy groups (including those having a substituent, those having 5 or less carbon atoms are preferable), hydroxy group, —COOM ₂ , —SO ₃ M ₃ group, lower alkenyl group (including those having a substituent) A group having 5 or less carbon atoms), an amino group, a carbamoyl group or a phenyl group, at least one of which is a -SM ₁ group. 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,
It is preferable to have a water-soluble group such as —SO ₃ M ₃ group and amino group. The amino group represented by R ₁ , R ₂ and R ₃ 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 an unsubstituted ammonium group.

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

[0088]

[Chemical 27]

[0089]

[Chemical 28]

[0090]

[Chemical 29]

[0091]

Embedded image

[0092]

[Chemical 31]

[0093]

Embedded image

The amount of the general formula (S) compound used in the present invention is
The amount is preferably from 10 ^-6 to 10 ^-1 mol, and more preferably from 10 ^-5 to 10 ^-2 mol, in 1 liter of the developing solution.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

In the present invention, the developer contains an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine). Etc.) are preferably added. As the pH buffer, carbonate is preferable, and the addition amount thereof is preferably 0.5 mol or more and 2.5 mol or less, and more preferably 0.75 mol or more and 1.5 mol or less, per liter. If necessary, a solubilizing agent (for example, polyethylene glycols, their esters, alkanolamines, etc.), a sensitizer (for example, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example ethylenediamine tetrachloride). Acetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphates, etc., development accelerators (eg US Pat. No. 2,304,025)
Nos. 5,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg glutaraldehyde or its bisulfite adduct), an antifoaming agent and the like can be added. The pH of the developer is preferably adjusted to 9.5 or more and less than 10.6. More preferably, it is pH 9.8 or more and less than 10.5.

The developing waste liquid can be regenerated by energizing it. Specifically, an anion exchange is performed by putting a cathode (for example, an electric conductor or semiconductor such as stainless steel wool) in the developing waste solution and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) in the electrolyte solution. The waste developer tank and the electrolyte solution tank are in contact with each other through the film, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention while energizing. At that time, various additives added to the developer,
For example, preservatives, alkaline agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developing solution, can be additionally added. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added.

Further, a light-sensitive material containing a developing agent in a light-sensitive material, for example, an emulsion layer or a layer adjacent to the light-sensitive material may be processed with a developer. Such a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8 to 5.8.
Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

The fixing solution contains a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates capable of softening water. Compounds such as agents may be included.

In the present invention, a developing solution and a fixing solution obtained by dissolving a developing agent and a fixing agent which are solid processing agents in water can be used.

The solid processing agent as used herein is a powder processing agent, a solid processing agent such as tablets, pills, granules, etc., and is subjected to a moisture-proofing treatment if necessary. Also, paste and slurry are included.

The powder used in the present invention refers to an aggregate of fine crystal grains. The granules referred to in the present invention are obtained by subjecting a powder to a granulation step, and mean granules having a particle diameter of 50 to 5000 μm. The tablet in the present invention refers to a powder or granules compression-molded into a certain shape.

The solid processing agent can be used as a photographic processing agent such as a developing agent, a fixing agent and a rinsing agent.

Further, depending on the amount of silver halide photographic light-sensitive material to be processed, the solid development replenisher may be directly replenished into the processing tank of the automatic processor for processing.

In the present invention, the fixing treatment is followed by washing with water and / or treatment with a stabilizing bath. As a stabilizing bath, adjust the film pH for the purpose of stabilizing the image (pH of the film surface after processing)
3 to 8) and inorganic and organic acids and salts thereof,
Or an alkaline agent and its salt (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide,
Used in combination with sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc.), aldehydes (eg formalin, glyoxal, glutaraldehyde, etc.), chelating agent ( For example, ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphates, etc., antifungal agents (eg phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, P- Hydroxybenzoate, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-
2'-hydroxy diphenyl ether, etc.), color tone adjusting agent and / or residual color improving agent (eg nitrogen-containing heterocyclic compound having mercapto group as a substituent; specifically, 2-mercapto-5-sodium sulfonate-benzimidazole) , 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,
4-triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an antifungal agent. These may be replenished in liquid or solid form. In the case of replenishing in solid form, the above-mentioned production method and use method of the solid treatment agent can be used.

In order to reduce the amount of waste liquid, the present invention is processed while supplementing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The developer replenishment rate is 22 per 1 m ^2.
It is 0 ml or less. It is preferably 30 to 200 ml per 1 m ² . Also, the replenisher of the fixing solution is 10 to 330 ml per 1 m ² .
The following is preferred. The developer replenishing amount and the fixer replenishing amount herein refer to the amount of replenishing liquid. Specifically, it is the replenishing amount of each liquid when replenishing the same liquid as the developing mother liquid and the fixing mother liquid, and each concentrating liquid when replenishing with the liquid obtained by diluting the developing concentrated liquid and the fixing concentrated liquid with water. And the total amount of water, the total amount of each solid processing agent and the volume of water when the solid development processing agent and the solid fixing processing agent are replenished with a liquid dissolved in water, and the solid development processing agent. And the total amount of each solid processing agent volume and water volume when the solid fixing processing agent and water are separately replenished. When the solid processing agent is replenished, it is preferable to represent the total amount of the volume of the solid processing agent directly added to the processing tank of the automatic processor and the volume of replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as or different from the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine. Especially the developer replenishment amount is 1
When the amount is 120 ml or less per m ² , the developing replenisher is preferably a liquid different from the developing mother liquor in the tank of the automatic processor or a solid processing agent, and is represented by the general formula (S) contained in the developing replenisher. The amount of the compound contained in the developing mother liquor is preferably larger than that contained in the developing mother liquor, and the amount of the compound represented by the general formula (1) contained in the developing replenisher is smaller than that contained in the developing mother liquor.
The amount is preferably 1.2 to 4 times. Further, particularly when the replenishing amount of the fixing solution is 150 ml or less per 1 m ² , it is preferable that the fixing developing replenishing solution is a liquid or a solid processing agent different from the fixing mother liquor in the tank of the automatic developing machine, and is contained in the fixing replenishing solution. The amount of thiosulfate is preferably larger than the amount contained in the fixing mother liquor.

In the present invention, the developer and the fixing agent which are solid processing agents may be dissolved in water.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

In the present invention, the total processing time (Dry to Dry) from the insertion of the leading edge of the film into the automatic developing machine until the film comes out from the drying zone when the processing is performed by using the automatic developing machine is demanded from the desire of shortening the developing processing time. It is preferably 50 seconds or less and 10 seconds or more. The total processing time referred to here includes the total process time required for processing the black-and-white light-sensitive material, and specifically, necessary for processing, for example, developing, fixing, bleaching, washing with water, stabilizing treatment,
Time that includes all the process time such as drying, that is, Dry to D
It's ry time. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 15 to 44 seconds. Also, 10m ²
The development time is preferably 20 seconds or less and 5 seconds or more in order to stably perform a large amount of the light-sensitive material.

In order to bring out the effect of the present invention remarkably, a heat transfer member at 60 ° C. or higher (for example, 60 ° C. to 13 ° C.) is used in an automatic processor.
A heat roller at 0 ° C or a radiant object at 150 ° C or higher (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc., can be used to generate heat and radiate heat from a resistance heating element. Energy of copper, stainless steel, nickel,
It is preferable to use one having a drying zone by emitting infrared rays by transmitting it to a radiator such as various ceramics to generate heat.

A heat roller may be used as an example of the heat transfer material having a temperature of 60 ° C. or higher. As for the heat roller, it is preferable that the outer circumference of the hollow roller made of aluminum is covered with silicone rubber, polyurethane, or Teflon. It is preferable that both ends of the heat roller are disposed inside the vicinity of the conveying port of the drying section by bearings of a heat-resistant resin (for example, product name: Rulon) and rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller, and the gear is rotated in the carrying direction by the drive means and the drive transmission means. A halogen heater is inserted in the roller of the heat roller, and this halogen heater is preferably connected to a temperature controller arranged in the automatic developing machine.

Further, the temperature controller is connected with a thermistor arranged in contact with the outer peripheral surface of the heat roller, and the temperature controller detects the temperature from the thermistor at 60 ° C to 150 ° C, preferably 70 ° C to 130 ° C. Therefore, it is preferable to control the halogen heater on and off.

The following examples can be given as examples of the radiation object that emits a radiation temperature of 150 ° C. or higher. (Preferably 250 ° C or higher) Tungsten, carbon, tantalum, nichrome, zirconium oxide / yttrium oxide / thorium oxide mixture, silicon carbide, molybdenum disilicide, lanthanum chromate There is a method of controlling or transferring the heat energy from the resistance heating element to the radiator to control, and examples of the radiator include copper, stainless steel, nickel and various ceramics.

In the present invention, a heat conductor having a temperature of 60 ° C. or higher and a radiant body having a reflection temperature of 150 ° C. or higher may be combined. Further, warm air of 60 ° C. or lower as in the past may be combined.

Further, in the present invention, an automatic developing machine having the method and mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560, 544 (2) page upper left column to 545 (3) page upper left column (2) Rinse water regeneration purifying agent and device: JP-A-6-250352 (3 ) Page “0011” to (8) Page “0058” (3) Waste liquid treatment method: JP-A-2-64638, 388 (2) Page, lower left column to 39
Page 1 (5) Page, lower left column (4) Rinse bath between developing bath and fixing bath: JP-A-4-313749
(18) Page “0054” to (21) Page “0065” (5) Water replenishment method: JP-A 1-281446 250 (2) Page left lower column to right lower column (6) Outside temperature and humidity detection and automatic development Method for controlling dry air of machine: JP-A-1-315745, page 496 (2), lower right column to 501 (7), page lower right column, and JP-A-2-108051, 588 (2) page, lower left column to 589 (3 ) Page lower left column (7) Silver recovery method of fixing waste liquid: JP-A-6-27623 (4) page 001
2 "-(7) page" 0071 ".

The halogen composition of silver halide in the silver halide emulsion used in the present invention is not particularly limited, but when the processing is carried out with a small replenishing amount or when the rapid processing is carried out,
It is preferable to use a silver halide emulsion having a composition of silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is preferably 0.6 μm or less, and particularly preferably 0.4 to 0.1 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles which can be approximated to a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size. For more information on how to determine the average particle size, see: The Theory of the Photographic Process (CEMees & T.H.Ja).
mes: The theory of the photographic process),
3rd edition, pp. 36-43 (1966 (published by McMillan "Mcmillan")).

The shape of silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any one-side mixing method, simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Gives a silver halide emulsion having a substantially uniform grain size.

In order to bring out the effect of the present invention remarkably, the silver halide emulsion of at least one silver halide emulsion layer contains tabular grains, and all of the emulsion layers in which tabular grains are used. It is preferred that 50% or more of the total projected area of the grains be tabular grains having an aspect ratio of 2 or more.
The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of tabular grains and the distance between two parallel planes. In the present invention, the tabular grains can be represented by the aspect ratio rather than the scale of the aspect ratio because the grain consisting of 50 mol% or more of silver chloride has the (100) plane as the main plane.
To 8 are preferred. In addition, iodide is added to the internal nucleation site.
It can be contained in the range of 0.001 to 1 mol%.
For the tabular grains rich in silver chloride component, the method described in US Pat. No. 5,320,938 can be referred to.
The larger the aspect ratio or the aspect ratio, the flatter the plate. The thickness of the tabular grains is preferably 0.01 to 0.5 µ, but can be arbitrarily selected by setting the aspect ratio and average volume grain size. The distribution of tabular grain diameters is often used as a coefficient of variation (standard deviation S when the projected area is approximated by a circle
Value divided by diameter D 100 times S / D) is 40% or less, especially 3
It is preferably a monodisperse emulsion having a content of 0% or less. Further, two or more kinds of tabular grains and normal crystal grains can be mixed.

Of these tabular grains, tabular grains having a (100) plane having a silver chloride content of 50 mol% or more as a main plane are preferably used. These are described in US Pat. Nos. 5,264,337, 5,314,798, and US Pat. No. 5,320,958 and the like, the target tabular grain can be easily obtained. The tabular grains can be formed by epitaxially growing silver halide having a different composition on a specific surface site or by shelling. Further, in order to control the photosensitizing nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions. For the preparation of particles, an acidic method, a neutral method, an ammonia method, or the like can be appropriately selected. When doping the metal,
Particularly, it is preferable to form particles under acidic conditions of pH 1 to 5. Ammonia, thioethers, thiourea compounds, thione compounds and the like can be used as a silver halide solvent in order to control grain growth during formation of tabular grains. As a thioether compound, 3,6,9,15,18,21-hexoxa-12-thiatricosane, 3,9,15-trioxa-6,12- described in German Patent 1,147,845
Dithiaheptadecane; 1,17-Dioxy-3,9-15-trioxa-6,12-dithiaheptadecane-4,14-dione; 1,20-
Dioxy-3,9,12,18-tetroxa-6,15, -dithiaeicosane-4,17-dione; 7,10-dioxa-4,13-dithiahexadecane-2,15-dicarboxamide, JP-A-56 -94347 and JP-A-1-121847, and oxathioether compounds described in JP-A-63-259653 and 63-301939. Especially as thiourea, those described in JP-A-53-82408 are useful. Specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea; 1,3-dimethylimidazole-2-thione; 1,3-dimethylimidazole-4-phenyl-2-thione;
Tetrapropyl thiourea etc. are mentioned.

During physical aging or chemical aging, metal circles such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. Iridium 10 ^-9 to obtain high illuminance characteristics
Doping in the range from 1 to 10 ^-3 is often customary in silver halide emulsions. In the present invention, rhodium, ruthenium, osmium and / or rhenium is used in an amount of 10 10 per mol of silver halide in order to obtain a high contrast emulsion.
It is preferable to dope in the range of ^-9 mol to 10 ^-3 mol.

When the metal compound is added to the particles,
Halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl, metal
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the maximum oxidation level to the minimum oxidation level. Preferable ligands include JP-A 2-2082,
The hexadentate ligands described in No. 2-20853, No. 2-20854, No. 2-20855 and common sodium salts, potassium salts, cesium salts or the first, second and second salts as alkali complex salts. There are tertiary amine salts. It is also possible to form a transition metal complex salt in the form of an aco complex. As an example of these,
For example, K ₂ [RuC _l6 ], (NH ₄ ) ₂ [RuC _l6 ], K ₂ [Ru (NO) C
_{l4 (SCN)], K 2} [ can be expressed as such _{RuC l5 (H 2 O)]} . The Ru part can be represented by replacing it with Rh, Os, Re, Ir, Pd and Pt.

Rhodium, ruthenium, osmium and /
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there are a method of uniformly distributing in the particles, and a method of forming a core-shell structure and localizing a large amount in the core part or the shell part.

The better results are often obtained when a large amount is present in the shell part. In addition, a method of increasing the existing amount may be used as it is continuously outside the particles, in addition to localizing in a discontinuous layer structure. The addition amount can be appropriately selected within the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Resear
ch Disclosure) No. 176, 17643, pages 22-23 (December 1978)
It is described in the literature described or cited.

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used, but as the preferable sulfur sensitizer, other than the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfates, thioureas, Rhodanines, polysulfide compounds and the like can be used. A known selenium sensitizer can be used as the selenium sensitizer. For example, U.S. Pat.No. 1,623,499, JP-A-50-71325, JP-A-60-15
The compounds described in JP-A No. 1994-154, etc. can be preferably used.

As the tellurium sensitizer, known tellurium sensitizers can be used. For example U.S. Patent 1,623,499
Nos. 3,772,031 and 3,320,069 can be preferably used.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained.

Examples of the reduction sensitizer include stannous salt, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used.

The sensitizing effect can be further enhanced by adding these sensitizers in the form of fine particles dispersed therein. Also, AgI
When particles are finely dispersed and added during chemical sensitization, AgI is formed on the surface of the particles and the effect of dye sensitization can be enhanced. When forming AgI of tabular grains, the contribution of the transition line portion ranging from 0 to 1000 lines is often utilized.

The selenium sensitizers that can be used in the present invention include a wide variety of selenium compounds. For example, in this regard, U.S. Patents 1,574,944, 1,602,592, 1,623,
499, JP 60-150046, JP 4-25832, 4-109
No. 240, No. 4-147250, etc. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenoate). Urea, N, N, N'-trimethyl
-N'-heptafluoroselenourea, N, N, N'-trimethyl-N '
-Heptafluoropropylcarbonyl selenourea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonyl selenoureas, etc.), selenoketones (eg, selenoacetone,
Selenoacetophenone, etc.), selenoamides (eg,
Selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, tri-p
-Triselenophosphate, diphenyltetrafluorophenylselenophosphate, etc.) and selenides (diethylselenide, diethyldiselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

Specific examples of the technique for using these selenium sensitizers are described in US Pat. Nos. 1,574,944, 1,602,592 and 1,623,49.
No. 9, No. 3,297,446, No. 3,297,447, No. 3,320,069,
3,408,196, 3,408,197, 3,442,653, 3,4
No. 20,670, and No. 3,591,385.

The amount of the selenium sensitizer used varies depending on the selenium compound used, the silver halide grains, the chemical ripening conditions and the like, but is generally about 10 ^-8 to 10 ^-3 mol per mol of silver halide. In addition, the addition method may be a method of adding it by dissolving it in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent depending on the properties of the selenium compound used, or by adding it in advance with a gelatin solution. Also in the method, the method disclosed in JP-A-4-140739,
That is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used. In addition, particle size 0.01 ~
It can be used as a solid dispersion of 500μ. The solid dispersion method can be produced according to the solid dispersion method of the dye or pigment. The temperature of chemical ripening using the selenium sensitizer in the present invention is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. The pH is 4
-9, pAg is preferably in the range of 5-10 adjusted with a water-soluble halide such as potassium bromide or sodium chloride or silver nitrate.

Tellurium compounds can be used in addition to the selenium compounds. Tellurium compounds are selenium compounds Se
It can be represented by substituting a Te atom. For example, N, N-dimethyl tellurourea, N, N, N'-triethyl tellurourea, N, N, N'-trimethyl-N'-heptafluoro tellurourea, N, N, N'-trimethyl-N'- 4-nitrophenyl carbonyl tellurourea, diphenyl tetrafluorophenyl tellurophosphate, diphenyl pentafluorophenyl tellurophosphate, triphenylphosphine selenide and the like.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with 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. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, 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, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon ring fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole , Quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. As a nucleus having a ketomethylene structure in the merocyanine dye or the composite merocyanine dye,
5-6 such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus
A member ring can be applied. Specifically, those described in Research Disclosure Vol. 176, RD-17643 (December, 1978), pages 2-3, US Pat. Nos. 4,425,425 and 4,425,426 can be used. The sensitizing dye may be dissolved using ultrasonic vibration described in US Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention in an emulsion, U.S. Patent Nos. 3,482,981, 3,585,195 and 3,469,98 are cited.
7, 3,425,835, 3,342,605, British Patent 1,271,3
No. 29, No. 1,038,029, No. 1,121,174, U.S. Pat.
The methods described in No. 101 and No. 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Research Disclosure is a combination of dyes that exhibit useful supersensitization and substances that exhibit supersensitization.
Volume 176, 17643 (issued December 1978), page 23, IV, section J.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3, 3a, 7-Tetrazaindenes), pentazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. may be added. it can.

As the binder or protective colloid of the photographic emulsion according to the present invention, it is advantageous to use gelatin, 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (eg vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

In order to bring out the effect of the present invention more remarkably, at least one hydrophilic colloid layer is provided on the opposite side of the silver halide photographic emulsion layer, and at least one hydrophobic polymer layer is provided on the outer side thereof. It is preferable. Here, the hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer includes a so-called back layer. In the present invention,
A structure having at least one hydrophobic polymer layer outside the back layer is preferable. In the present invention, the hydrophobic polymer layer is a layer containing a hydrophobic polymer as a binder.
Specific examples of the binder for the polymer layer include polyethylene, polypropylene, polystyrene, polyvinyl chloride,
Polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene,
Fluorine-based resins such as polyvinylidene fluoride, butadiene rubber, chloroprene rubber, rubbers such as natural rubber, acrylic acid or methacrylic acid esters such as polymethyl methacrylate and polyethyl acrylate, polyester resins such as polyethylene phthalate, nylon 6, nylon Examples thereof include polyamide resins such as 66, cellulose resins such as cellulose triacetate, water-insoluble polymers such as silicone resins, and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. Particularly preferable binders are copolymers of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymer, styrene-butadiene-acrylic acid copolymer (acrylic acid is 5 mol% or less is preferable),
Styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrile-methyl methacrylate-ethyl acrylate -
Acrylic acid copolymers (acrylic acid 5 mol% or less), ethyl acrylate-glycidyl methacrylate-acrylic acid copolymers and the like. These may be used alone or in combination of two or more.

The hydrophobic polymer layer in the present invention may include a matting agent, a surfactant, a dye, a slip agent, a cross-linking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica for photographic use, if necessary. Additives may be added. About these additives, Research Disclosure Vol. 176 1
You can refer to the description in paragraph 7646 (December 1978).

The hydrophobic polymer layer in the invention may be one layer or two or more layers. The thickness of the polymer layer of the present invention is not particularly limited. However, if the thickness of the hydrophobic polymer layer is too small, the water resistance of the hydrophobic polymer layer will be insufficient and the back layer will swell in the treatment liquid, which is inappropriate. On the contrary, when the thickness of the hydrophobic polymer layer is too large, the water vapor permeability of the polymer layer becomes insufficient, and the moisture absorption / desorption of the hydrophilic colloid layer of the back layer is hindered, resulting in poor curling. Of course, the thickness of the hydrophobic polymer layer also depends on the physical properties of the binder used. Therefore, it is necessary to determine the thickness of the polymer layer in consideration of both of them. The preferred thickness of the hydrophobic polymer layer depends on the binder species of the hydrophobic polymer layer, but is in the range of 0.05 to 10 μm, more preferably 0.1 to 5 μm. When the hydrophobic polymer layer of the present invention comprises two or more layers, the sum of the thicknesses of all the hydrophobic polymer layers is the thickness of the hydrophobic polymer layer of the silver halide photographic light-sensitive material of the present invention.

The method for applying the hydrophobic polymer layer in the invention is not particularly limited. After coating and drying the back layer, a polymer layer may be coated on the back layer and then dried, or the back layer and the hydrophobic polymer layer may be simultaneously coated,
You may dry after that. The hydrophobic polymer layer may be dissolved in a solvent for the binder of the polymer layer and applied in a solvent system, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

On the surface opposite to the emulsion layer of the black and white silver halide photographic light-sensitive material of the present invention, an adhesive layer / antistatic layer / hydrophilic colloid-containing back layer / hydrophobic polymer layer is provided on a support. It is preferable. Furthermore, you may provide a protective layer on it. After coating a vinylidene chloride copolymer or styrene-glycidyl acrylate copolymer with a thickness of 0.1 to 1 μm on a corona-discharged support as an adhesive layer, an average particle size of 0.
It can be provided by applying a gelatin layer or a polymer layer containing fine particles of tin oxide and vanadium pentoxide having a size of 01 μ to 1 μ. Further, as the antistatic layer, a styrene sulfonic acid / maleic acid copolymer can be formed by forming a film with the aforementioned aziridine or carbonyl active type cross-linking agent. A dye back layer may be provided on these antistatic layers. These layers should contain an inorganic filler such as colloidal silica for dimensional stability, silica for preventing adhesion, a methyl methacrylate matting agent, a silicon-based slipping agent or a release agent for controlling transportability, etc. You can The back layer may contain a backing dye, and as the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can be fixed in the form of fine particles. The concentration for preventing halation is preferably 0.1 to 2.0 at each photosensitive wavelength.

An inorganic or organic hardener is added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention as a crosslinking agent for hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,
3-dihydroxydioxane, etc., active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide]
Etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazoles,
Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activating type hardener and the like can be used alone or in combination. These hardeners are available from Research Disclosure.
Volume 176, 17643 (issued in December 1978) Page 26, A ~
It is described in section C.

The light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

In each layer, in addition to gelatin, dextrins,
The degree of swelling can be controlled by introducing a hydrophilic polymer such as starch or glucose or a hydrophobic latex. The swelling degree is generally 120 to 200. The drying of each layer is
The temperature and time are adjusted according to the evaporation rate of water. Generally, a temperature of 25 ° C. to 200 ° C. and a time of 0.1 second to 200 seconds are generally applied. The degree of swelling can be measured by immersing in water and measuring with a microscope, or by a swelling degree meter. As the degree of swelling, the ratio (Lw / Ld) of the dry film thickness = Ld (film thickness after humidity conditioning at 23 ° C and 50% relative humidity for 24 hours) to the swollen thickness Lw in water at 23 ° C is 100. The value multiplied by can be used as an index.

The surface tension and the wetting index can be determined by referring to JIS.

The film surface pH on the silver halide photographic emulsion layer side used in the present invention is preferably pH 4.5 or more and pH 5.8 or less. The film surface pH is a pH measured after coating and drying, and the measurement is carried out by dropping 1 cc of pure water per cm ^{2 of the} measured portion with a pH measuring meter. To lower the pH, use citric acid,
Acids such as oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid,
Further, when raising the pH, an alkaline agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium acetate or the like can be used. Similar methods can be applied when adjusting the pH when using photographic additives.

Various other additives are used in the light-sensitive material used in the present invention. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and the like.

The support used in the present invention may be either permeable or impermeable, but for the purpose of the present invention, a permeable plastic support is preferable. For the plastic support, a polyethylene compound (for example, polyethylene terephthalate, polyethylene naphthalate, etc.),
A support made of a triacetate compound (eg, triacetate cellulose) or a polystyrene compound is used. Among them, in the present invention, in order to improve the drying property and dimensional stability in an automatic processor, a support comprising a styrene-based polymer having a syndiotactic structure or a stretched film made of a composition containing the same. (Hereinafter abbreviated as SPS) is particularly preferable. SPS refers to a homopolymer whose constituent unit is composed of SPS units having syndiotactic stereoregularity, but a small amount, for example, 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol%. % SPS modified with less than the second 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 methacrylate,
Examples thereof include those containing polar vinyl monomers such as maleic anhydride and acrylonitrile. It is generally produced by polymerizing styrene or a derivative thereof under suitable reaction conditions using an organometallic catalyst. The syndiotactic polystyrene is a racemic diad having a stereoregularity of 75% or more, preferably 80% or more, or a racemic pentad, 30% or more, preferably 50% or more. In that case, a general plastic plasticizer can be added as the second component in a range that does not deteriorate the flexural modulus, and such a thing is performed to obtain an appropriate flexural modulus.

SPS can be synthesized by polymerizing styrene or a derivative thereof in the presence of a catalyst of a condensation product of a titanium compound and a trialkylaluminum at a suitable reaction temperature. These are disclosed in JP-A-62-187708 and JP-A-1-4.
The methods described in Japanese Patent Nos. 6912 and 1-178505 can be referred to. The degree of polymerization of SPS is not particularly limited, but those of 10,000 or more and 5 million or less can be preferably used. In order to increase the flexural modulus of SPS, it is necessary to select the optimum stretching conditions. At a point 30 ° C ± 25 ° C from the glass transition point of the unstretched film, that is, at 120 ° C ± 25 ° C, first set 3.3
Stretch to ± 0.3 times. Next, it is laterally stretched by 3.6 ± 0.6 times under the same temperature condition. The heat treatment after stretching is performed at 230 ± 18 ° C. Good results are obtained when the heat treatment is performed not only in the first stage but also in the second stage. Thus, an SPS film having a flexural modulus of 350 kg / mm ² or more is manufactured.

A film having such a high flexural modulus is
It is difficult to apply the photographic layer as it is and firmly bond it. The fact that there are many patents and documents about the method
Reference is made to pages 3 to 4 of JP-A-3-54551, which can be referred to.

For example, regarding the surface treatment, it is described that a corona discharge treatment or an undercoat layer is further applied. Examples of the undercoat layer include vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and the like.

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

In order to further improve the curl and curl of the support, it is preferable to perform heat treatment after film formation. Most preferred is after film formation and after emulsion coating, but it may be after emulsion coating. The heat treatment condition is preferably 45 ° C. or higher and the glass transition temperature or lower, and 1 second to 10 days. From the viewpoint of productivity, it is preferably within 1 hour.

In the present invention, the compounds described below are preferably contained in the silver halide photographic light-sensitive material.

(1) Solid Dispersed Fine Particles of Dye Compounds described in JP-A-7-5629, page (3), page [0017] to page (16), [0042] (2) compound having an acid group JP-A-62- JP 237445 gazette 292 (8) page lower left column 11th line ~ 309 (2
5) Compound described in the lower right column, line 3 on page 3 (3) Acidic polymer JP-A-6-186659, page (10), page [0036] to page (17), [0062]
Compounds described (4) Sensitizing dyes JP-A-5-224330, page (3), page [0017] to page (13), [0040]
Compounds described in JP-A-6-194771 (11) page [0042] to (22) page [0094]
Compounds described in JP-A-6-242533, page (2), page [0015] to page (8), [0034], Compounds described in JP, JP-A-6-337492, page (3), [0012] to (34), [0056]
Compounds described in JP-A-6-337494, page (4), page [0013] to page (14), [0039]
Compounds described (5) Supersensitizer JP-A-6-347938, page (3), page [0011] to page (16), [0066]
Compounds described (6) Redox compounds JP-A-4-245243 JP 235 (7) -250 (22) Compounds described above For the above-mentioned additives and other known additives,
For example, Research Disclosure No.17643 (1978
December), No.18716 (November 1979) and No.308119 (19)
The compound described in December 1989). The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII The various photographic additives used in the present invention may be dissolved in an aqueous solution or an organic solvent, but when they are poorly soluble in water, they are made into a fine-grain crystal state to give water, gelatin, hydrophilicity. Alternatively, it can be used by dispersing it in a hydrophobic polymer. In order to disperse the dye, dye, desensitizing dye, hydrazine, redox compound, antifoggant, ultraviolet absorber, etc. of the present invention, they can be dispersed by a known disperser. Specific examples include a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, and a high speed impeller disperser. These photographic additives dispersed in the present invention are fine particles having an average particle size of 100 μm or less, and are usually used in an average particle size of 0.02 to 10 μm. As a dispersion method, a method of mechanically stirring at high speed (Japanese Patent Laid-Open No. 58-105141), gelatin dissolved in an organic solvent by heating and containing the surfactant or antifoaming agent described above,
A method in which a hydrophilic polymer is added and dispersed to remove the organic solvent (JP-A-44-22948). A solution prepared by dissolving in an acid such as citric acid, acetic acid, sulfuric acid, hydrochloric acid or malic acid has a pH of 4.
A method in which crystals are precipitated and dispersed in a polymer of 5 to 7.5 (JP-A-50-80119), and the pH is adjusted to 4 by dissolving in an alkali such as sodium hydroxide, sodium hydrogencarbonate or sodium carbonate.
A method in which crystals are precipitated and dispersed in a polymer such as gelatin of 5 to 7.5 (JP-A-2-15252) and the like can be applied. For example, hydrazine, which is difficult to dissolve in water, is disclosed in JP-A-2-
No. 3033 can be referred to for melting, and this method can be applied to other additives. Further, a dye having a carboxyl, a sensitizing dye, an inhibitor and the like can increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxyl group. That is, it is preferable to add a calcium ion, a magnesium ion, or the like to the hydrophilic colloid layer from 200 to 4000 ppm to form a sparingly soluble salt. The use of another salt is not limited as long as it is possible to form a poorly soluble salt. The method for dispersing fine particles of a photographic additive can be arbitrarily applied to a sensitizer, a dye, an inhibitor, an accelerator, a contrast-increasing agent, a contrast-increasing aid, etc., depending on its chemical and physical properties.

A plurality of constituent layers of the present invention from 2 to 10 layers
For simultaneous coating at high speeds of 30 to 1000 meters per minute, the known slide hopper or curtain coatings described in US Pat. Nos. 3,636,374 and 3,508,947 can be used. In order to reduce unevenness during coating, it is preferable to use the hydrophilic polymer which can reduce the surface tension of the coating liquid and can impart thixotropic property in which viscosity is reduced by shearing force.

The light-sensitive material of the present invention may be provided with a crossover cut layer, an antistatic layer, an antihalation layer and a back coat layer.

A known method is used for packaging the photographic light-sensitive material comprising the photographic element of the present invention.

Since the silver halide photographic light-sensitive material is weak against heat and humidity, it is preferable to avoid storing it under severe conditions. Generally, it is better to store at 5 ° C to 30 ° C. Humidity should be between 35% and 60% relative humidity. In order to protect it from humidity, it is generally packaged in polyethylene of 1 to 2000 µ. Polyethylene can suppress the permeation of water by improving the regularity of crystals by using a metallocene catalyst. Also,
Moisture permeation can be suppressed by coating the surface of polyethylene by vapor deposition with a thickness of 0.1 to 1000 μm.

[0169]

The present invention will be specifically described with reference to the following examples. Of course, the present invention is not limited to the examples described below.

(Preparation of support) (SPS synthesis) Using 200 parts by weight of toluene, 100 parts by weight of styrene, 56 g of triisobutylaluminum, and 234 g of pentamethylcyclopentadienyl titanium trimethoxide were reacted at 96 ° C. for 8 hours. I went. The catalyst was decomposed and removed with a solution of sodium hydroxide in methanol, and then 3 times with methanol.
It was washed twice to obtain 34 parts by weight of the target compound (SPS).

(Preparation of SPS Film) The obtained SPS is 330
Melt extrusion into film form from T die at ℃,
It was rapidly solidified on a cooling drum to obtain an uncentrifuged film. At this time, the take-up speed of the cooling drum is set in two steps, and the unstretched films having thicknesses of 1370μ, 1265μ and 1054μ are preheated at 135 ° C, longitudinally stretched (3.1 times), and then horizontally stretched at 130 ° C (3.4 times). Then, heat fixation was further performed at 250 ° C. As a result, a biaxially stretched film having a flexural modulus of 450 kg / mm ² and a thickness of 100 μm was obtained as a support.

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

(Preparation of silver halide emulsion A) A silver chlorobromide core particle having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which is composed of 70 mol% of silver chloride and the rest is silver bromide, is prepared by the simultaneous mixing method. did. When the core particles were mixed, K ₃ RuCl ₆ was added in an amount of 8 × 10 ^-8 mol per mol of silver. The core particles were shelled using the double jet method. At this time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ^-7 mol per mol of silver. The obtained emulsion has a thickness of 0.10 μm and a mean diameter of 0.25 μm, which is a core / shell type monodisperse (coefficient of variation 10%) (100) plane as the principal plane of silver chloroiodobromide (silver chloride 90 mol%, iodine This was a tabular grain emulsion consisting of 0.2 mol% of silver bromide and the rest consisting of silver bromide. Then, the modified gelatin described in JP-A-2-280139 (wherein the amino group in gelatin is substituted with phenylcarbamyl, for example, Exemplified Compound G-8 on page 287 (3) of JP-A-2-280139) is used for desalting. did. The EAg after desalting was 190 mv at 50 ° C.

The resulting emulsion was treated with 4-hydroxy-6-methyl-1,
A pH of 5.3 was obtained by adding 3,3a7-tetrazaindene at 1 × 10 ^-3 mol per mol of silver and further adding potassium bromide and citric acid.
6. Adjust the EAg to 123mv, add 2 × 10 ^-5 mol of chloroauric acid, and then add 3 × 10 ^-6 mol of inorganic sulfur to a temperature of 60 ° C.
Chemical aging was performed until the maximum sensitivity was obtained at. After aging 4-
Hydroxy-6-methyl-1,3,3a7-tetrazaindene silver 1
2 × 10 ⁻³ mol, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added per mol.

(Preparation of silver halide emulsion B) 60 mol% of silver chloride, 2.5 mol% of silver iodide, the rest of which is silver bromide and has an average thickness of 0.05 μm and an average diameter of 0.15 μm. A silver bromide core grain was prepared. K ₃ Rh when mixing core particles
(H ₂ O) Br ₅ was added in an amount of 2 × 10 ^-8 mol per mol of silver. The core particles were shelled using the double jet method. At this time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ^-7 mol per mol of silver. The obtained emulsion has an average thickness of 0.10 μm and an average diameter of 0.4.
It was a 2 μm core / shell type monodisperse (variation coefficient 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol% silver iodobromide, the balance being silver bromide) tabular grain emulsion. . Then, Japanese Patent Laid-Open
Modified gelatin described in 2-280139 (a gelatin in which the amino group is replaced with phenylcarbamyl, for example
Desalination was performed using 2-280139, Exemplified Compound G-8) on page 287 (3). The EAg after desalting was 180 mv at 50 ° C.

The resulting emulsion was treated with 4-hydroxy-6-methyl-1,
A pH of 5.3 was obtained by adding 3,3a7-tetrazaindene at 1 × 10 ^-3 mol per mol of silver and further adding potassium bromide and citric acid.
6. Adjust to EAg123mv, add 2 × 10 ^-5 mol of chloroauric acid, add 3 × 10 ^-5 mol of N, N, N'-trimethyl-N'-heptafluoroselenourea, and add 60 ° C. Chemical aging was performed until the maximum sensitivity was obtained at. 4-hydroxy after aging
2 × 10 ⁻³ mol of −6-methyl-1,3,3a7-tetrazaindene, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added per mol of silver.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for HeNe laser light source) On one undercoat layer of the above-mentioned support, a gelatin undercoat layer of the following Formulation 1 was added at a gelatin amount of 0.5 g / such that m ^2, formulated on the 2
Silver amount 1.5 g / m ² of the silver halide emulsion layer 1, so that the amount of gelatin is 0.5 g / m ^2, further amount of gelatin coating solution having the following formulation 3 as an intermediate protective layer on the upper layer 0.3 g / m ²
In addition, a silver halide emulsion layer 2 of Formulation 4 was further added thereon to obtain a silver amount of 1.4 g / m ² and a gelatin amount of 0.4 g / m ^2, and a coating solution of the following Formulation 5 was further added to the gelatin amount. Is 0.
Simultaneous multi-layer coating was applied so as to obtain 6 g / m ² . On the other side of the undercoat layer, a backing layer having the following formulation 6 with a gelatin content of 0.
As will become 6 g / m ^2, the hydrophobic polymer layer of the following formulation 7 thereon, further the amount of gelatin backing protective layer having the following composition 8 thereon the emulsion layer side so as to 0.4 g / m ² A sample was obtained by simultaneous multilayer coating.

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Solid dispersion 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 Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Solid of dye AD-8 so that the silver amount becomes 1.5 g / m ^2. Dispersed 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 Hydrazine derivative H-7 20 mg / m ² redox compound: RE-1 20 mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6- hydroxy purine ^{5mg / m 2 EDTA 30mg / m} 2 colloidal silica (average particle size 0.05 .mu.m) 10 mg / m ² formulation 3 (intermediate layer composition) gelatin 0.3 g / m ² S 1 2 mg / m ² Formulation 4 (silver halide emulsion layer 2 composition) Silver halide emulsion B silver amount 1.4 g / sensitizing dyes as m becomes ² d-1 3 mg / m ² Sensitizing dye d-2 3 mg / m ² hydrazine derivative H-20 20 mg / m ² Nucleation accelerator: Exemplified compound Nb-12 40 mg / m ² Redox compound: RE-2 20 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 Dye AD-5 solid dispersion (average particle size 0.1 μm) 40 mg / m
² S-1 12 mg / m ² Matting agent: Monodisperse silica 25 mg / m ^{2 with an} average particle size of 3.5 μm Nucleation accelerator: Exemplified compound Na-3 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) 1.0g / m ² Hardener g 6mg / m ² Formulation 8 (backing protective layer) Gelatin 0.4g / m ² Matting agent: Monodisperse polymethylmethacrylate 50mg with average particle size 5μm / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² Dye k 20 mg / m ² H _{- (OCH 2 CH 2) 68} -OH 50mg / m 2 Hardener: K-1
20 mg / m ²

[0179]

[Chemical 33]

[0180]

Embedded image

[0181]

Embedded image

The surface resistivity of the backing side after coating and drying is 23 ° C.
In 6 × 10 ¹¹ in 20% RH, the film surface pH of the surface of the emulsion side is 5.5, the degree of swelling was 175. After exposing the obtained sample to the following exposure, at the start, put the use solution of the developer, the use solution of the fixer having the following composition and the rinse solution into the tank of the automatic developing machine. Then, the dry processing part of the automatic processor for rapid processing (GR-26SR Konica Co., Ltd.) was modified to a heat roller system heated to 60 ° C, and the one that was improved to enable rapid processing by changing the transport speed was used. It processed on the following processing conditions. In addition, 150 ml of the developing solution used and 1 ml of the fixing solution per 1 m ^{2 of} the light-sensitive material were previously prepared.
While replenishing each with 180 ml and a rinse solution of 250 ml, 100 sheets of large-size film in which 80% of the area was blackened were processed per day, and this was run for 8 days to process 800 sheets in total. The evaluation is the performance after running 800 sheets. The surface resistivity of the backing side after the treatment was 3 × 10 ¹¹ at 23 ° C. and 20% RH.

[0183]

[0184]

[Table 1]

[0185]

[Table 2]

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) 25 ml used The pH of the liquid was 4.9.

Water and sulfuric acid were added to make up to 500 ml, and the pH was adjusted to pH 4.9 at the time of use. At the time of use, 500 ml of water was added to make a 1 liter developer.

(Rinse Solution) EDTA.2Na 40 g KOH 23 g K ₂ CO ₃ 12 g Potassium Sulfite 110 g Sunbag-P (San-ai Petroleum) 20 g (Relative Sensitivity Evaluation Method) Using a 633 nm interference filter as a substitute evaluation for HeNe laser exposure. The above treatment was carried out after exposure through an optical wedge for 10 ⁻⁷ seconds. Konica Digital Densitometer PDA-
The relative sensitivity is shown in FIG.

(Evaluation of halftone dot quality) Made by Dainippon Screen
SG-747RU with 16 micron random pattern halftone dots (FM
After exposure with a screen), the above treatment was performed. The midpoint of the halftone dot pattern (target 50%) was visually evaluated for the halftone dot quality using a loupe of 100 times. The highest rank was 5 and the rank was lowered to 4, 3, 2, 1 according to the halftone dot quality, and the evaluation was performed.

(Evaluation of initial developability) After the same exposure as that used in the evaluation of the halftone dot quality, the development time was set to 7
The halftone development as described above was performed for the development processing in seconds.

(Evaluation of black spots) Black spots (sandy defects) in the unexposed portion of the obtained developed sample were visually evaluated using a magnifying glass of 40 times. The case where black spots did not occur was ranked as 5, and as the occurrence of black spots increased, the evaluation was lowered to 4, 3, 2, 1. Ranks 2 and 1 are practically unfavorable levels.

Table 3 shows the evaluation results.

[0193]

[Table 3]

[0194] Except for processing while replenishing the working solution of Example 2 photosensitive material 1 m ² per developer by 270ml was evaluated in the same manner as in Example 1. The developer used is developer 4.

As a result, the maximum density decreased by 0.5 in the case of 270 ml as compared with the case where the development replenishment amount was 150 ml.

As is clear from this result, it is understood that the maximum concentration decreases when the replenishment amount is increased.

[0197]

INDUSTRIAL APPLICABILITY According to the present invention, even when a large amount of 100 m ² or more running processing is carried out in a state where the developer replenishment amount is reduced using a developer of an ascorbic acid developing agent which is environmentally friendly and highly safe, It was possible to provide a processing method for a black-and-white silver halide photographic light-sensitive material, which has good halftone quality, high sensitivity, good initial developability, and hardly causes black spots. Further, it was possible to provide a method of processing a black-and-white silver halide photographic light-sensitive material having good halftone quality and good initial developability when reproducing minute points of 25 microns or less in a printing plate-making light-sensitive material. .

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 5/31 G03C 5/31

Claims (5)

[Claims] 1. A negative type silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one surface of a support is represented by the following general formula (1) without substantially containing hydroquinone. When developing with a developer containing a developing agent, the developer contains a compound represented by the following general formula (2), and the pH of the developer is 9.5 or more and 10.6 or more.
A method for processing a negative-working black-and-white silver halide photographic light-sensitive material, characterized in that Embedded image [Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ and R _{2 s} may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X is -CO-
Or represents -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ] [Chemical 2] [In the formula, R represents a -SO ₃ M group, a -COOM group (wherein M represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, a substituted or It represents at least one selected from the group consisting of unsubstituted ammonio groups. n represents an integer of 1 or 2 and m represents an integer of 1, 2 or 3. ] 2. The method for processing a negative-working black-and-white silver halide photographic light-sensitive material according to claim 1, wherein at least one hydrazine derivative is contained in at least one layer on the side of the silver halide photographic emulsion layer. 3. The processing of the negative-working black-and-white silver halide photographic light-sensitive material according to claim 2, wherein at least one layer on the side of the silver halide photographic emulsion layer contains at least one nucleation accelerator. Method. 4. The processing of a negative-working black-and-white silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the developer contains a compound represented by the following general formula (S). Method. Formula (S) Z ¹ -SM ¹ [wherein Z ¹ is an alkyl group, an aromatic group or a heterocyclic group, a hydroxyl group, -SO ₃ M ¹ group, -COOM ¹ group (wherein M ¹ Represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, at least one selected from the group consisting of a substituted or unsubstituted ammonio group, or selected from this group Represented by a substituent having at least one of the following: M ¹ is a hydrogen atom,
It represents an alkali metal atom or a substituted or unsubstituted amidino group (which may form a hydrohalide or sulfonate). ] 5. The negative-working black-and-white silver halide photographic light-sensitive material is processed in an automatic processor having at least a developing tank, a fixing tank, a washing tank or a stabilizing tank, and a drying section while supplementing at least a developing replenisher. 5. The method for processing a negative-type black-and-white silver halide photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein the replenishing amount of the developing replenisher is 220 ml or less per 1 m ^{2 of the} light-sensitive material to be processed. .