JP2000292879A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material for a photomechanical process having ultrahigh contrast and excellent in dot quality even in the case of a short exposure time by carrying out exposure under specific conditions and using a specified processing agent in processing using an automatic processing machine. SOLUTION: A silver halide photographic sensitive material having at least one silver halide emulsion layer on the substrate and containing 1×10-5-1×10-3 mol/m2 at least one hydrazine derivative in the emulsion layer is exposed by using an image setter and processed by using an automatic processing machine to obtain an image having a density of >=4.5. In the exposure, 0.01-10 μJ/(sec/ cm2) exposure energy and 5×10-7-1×10-10 sec exposure time are adopted. In the processing using an automatic developer, a processing agent containing a compound of the formula as a developing agent but not substantially containing a hydroquinone derivative is used. In the formula, R11 and R12 are each alkyl or the like, (k) is 0 or 1, in the case of k=1, X is -CO- or the like and M1 and M2 are each H or an alkali metal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black-and-white silver halide photographic light-sensitive material for plate making (hereinafter simply referred to as a light-sensitive material).
And an image forming method.

[0002]

2. Description of the Related Art In recent years, in the silver halide photographic light-sensitive material for printing plate making, a screening method for forming an image with smaller halftone dots than before, such as high definition and FM screening, has begun to spread. For such a screening method, a super-hard contrast type photosensitive material in which the density of minute halftone dots is easy to be applied is preferable. As a photographic technique for obtaining such an ultra-high contrast image, a hydrazine derivative is contained in a silver halide photographic light-sensitive material.
No. 9,929 or Japanese Patent Application Laid-Open No.
No. 98239 and the like are disclosed.

In recent years, for reasons such as efficiency and cost reduction, it has been required to shorten the time from exposure to development to obtain a completed image. By shortening the exposure time, a more active photosensitive material is required, but in the hydrazine-containing photosensitive material as described above, high activation can be achieved by, for example, increasing the processing temperature or increasing the amount of hydrazine added. In this case, there is a problem that the deterioration of the black pot is remarkable and the deterioration of the dot material is large.

[0004] For the same reason, a reduction in processing time has been demanded. Conventionally, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine until it comes out of the drying zone usually required 90 seconds or more. The following rapid processing is required. However, in order to perform such rapid processing, in addition to the need for a photosensitive material having high activity, a material having a higher resistance to performance fluctuation of the processing solution due to running is required. However, the ultra-high contrast type photosensitive material has a problem that sensitivity and dot quality are deteriorated due to fluctuations in pH of a developing solution.

[0005] On the other hand, in recent years, interest in environmental issues has increased, and there has been a strong demand for reduction of waste liquids for photographic processing such as development, fixing and washing. Also, from the viewpoint of cost, reduction in waste of photographic processing has been strongly desired. In order to reduce the photographic processing waste liquid, there are known methods in which the replenishing amount of the processing liquid is reduced or the washing step is performed in a multi-stage countercurrent type of two or more stages.
In the low replenishment running process, there is a problem that the deterioration of the sensitivity fluctuation and the deterioration of the dot quality as described above are further increased.

Therefore, there has been a demand for solving the above-mentioned problems.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a halogenated material for printing plate making which is super-hard and excellent in dot quality even when the exposure time is shortened and also in the rapid processing in which the processing time is shortened. An object of the present invention is to provide a method for forming an image on a silver photographic light-sensitive material. In the above exposure and processing conditions,
An object of the present invention is to provide a method for exposing and processing a silver halide photographic light-sensitive material for printing plate making, which has a super-high contrast, is excellent in dot quality, and suppresses fluctuations in running performance even when replenished at a low level.

[0008]

The above objects of the present invention have been attained by the following items 1 to 5.

1. The support has at least one silver halide emulsion layer, and the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer contains at least one hydrazine derivative in an amount of 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol. / M ² containing silver halide photographic light-sensitive material is exposed with an imagesetter and then processed with an automatic processor to obtain an image having a density of 4.5 or more.
01 to 10 μJ / (sec · cm ² ), exposure time 5 ×
10 ^-7 to 1 × 10 ^-10 seconds, and contains a compound represented by the following general formula (B) as a developing agent during processing using the automatic developing machine, and is substantially a hydroquinone derivative. An image forming method, wherein the processing is performed using a processing agent containing no.

[0010]

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Wherein R ₁₁ and R ₁₂ are each an alkyl group,
Represents an amino group, an alkoxyl group or an alkylthio group, which may have a substituent and may be bonded to 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.

2. The replenishment amount of the developing solution during processing is 30 to 150 ml per m ^{2 of the} silver halide photographic material, and the replenishment amount of the fixing solution is 50 to 150 m ² per 1 m ^{2 of the} silver halide photographic material.
2. The image forming method according to the above item 1, wherein processing is performed with 300 ml.

3. 3. The image forming method according to 1 or 2, wherein the total processing time (Dry to Dry) of the silver halide photographic light-sensitive material is from 10 seconds to 60 seconds.

4. 4. The image forming method according to any one of the above items 1 to 3, wherein processing is performed using a processing solution prepared from a solid processing agent.

[0015] 5. Washing step a is 2 or more stages countercurrent, one of the 1 to 4, wherein the replenishing amount of washing water or rinsing solution is a silver halide photographic material 1 m ² per 50~400ml Item 2. The image forming method according to Item 1.

Hereinafter, the present invention will be described in detail.

The hydrazine derivative used in the present invention will be described.

As the hydrazine derivative, a compound represented by the following general formula [H] is preferably used.

[0019]

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In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group which may have a substituent, B ₀ represents a blocking group, and A ₁ , A ₂ represents a hydrogen atom or one of them represents a hydrogen atom and the other represents an acyl group, an alkylsulfonyl group, an arylsulfonyl group or an oxalyl group. Here, G ₀ is a —CO— group, —COCO
— Group, —CS— group, —C (＝ NG ₁ D ₁ ) — group, —SO—
A —SO ₂ — group or —P (O) (G ₁ D ₁ ) — group, wherein G ₁ is a mere bond, a —O— group, a —S— group, or a
Represents an N (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they are the same or different. You may. D
₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, a methyl group, an ethyl group, a t-butyl group,
Octyl group, cyclohexyl group, benzyl group, which are further substituted with suitable substituents (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, Ureido group).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group.
For example, a benzene ring or a naphthalene ring is mentioned, and A ₀
The heterocyclic group represented by is preferably a heterocyclic ring containing at least one hetero atom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring,
Imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring, and, in -G ₀ -D ₀ group represented by A _0, G ₀ represents a -CO- group, -COCO- group, -CS- group, -C (= N
G ₁ D ₁ ) —, —SO—, —SO ₂ —, or —P
(O) represents a (G ₁ D ₁ ) — group. G ₁ is just a bond,
O—, —S— or —N (D ₁ ) —, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom;
When multiple D ₁ are present in a molecule, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. Aromatic groups A _0, heterocyclic group or -G ₀ -D ₀ group may have a substituent.

Particularly preferred as A ₀ are an aryl group and a -G ₀ -D ₀ group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, a photographically inert alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, Examples thereof include a phenoxy group and an alkylphenoxy group, and the total number of carbon atoms in the substituent is preferably 8 or more.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P
(O) represents a (G ₁ D ₁ ) — group. Preferred G ₀ is-
A CO— group and a —COCO— group, and G ₁ represents a simple bond, a —O— group, a —S— group, or a —N (D ₁ ) — group, and D ₁ represents an aliphatic group or an aromatic group. , A heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the molecule, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. A ₁ , A ₂
Are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or an oxalyl group (ethoxalyl group, etc.) Represents

Of the compounds represented by the general formula [H], those more preferably used are the compounds represented by the following general formula [H-2].

Formula [H-2] R ₀ -SO ₂ NH-Ar-NHNH-G ₀ -D _{0 In the} formula, R ₀ represents an alkyl group, an aryl group or a heterocyclic group, and Ar represents an arylene group or Represents a heterocyclic group, G
₀ and D ₀ have the same meanings as in the general formula [H], respectively.

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

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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Other hydrazine derivatives that can be preferably used include US Pat. No. 5,545,505.
No., compounds H-1 to H-2 described in columns 11 to 20
9, Nos. 5,464,738 and compounds 9 to 12 described in columns 9 to 11.

These hydrazine derivatives can be synthesized by referring to a known method.

The content of the hydrazine derivative used in the present invention is from 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ² ,
It is preferably 1 × 10 ⁻⁵ to 4 × 10 ⁻⁴ mol / m ² ,
More preferably, it is 5 × 10 ⁻⁵ to 4 × 10 ⁻⁴ mol / m ² . The hydrazine derivative used in the present invention may be used alone, or two or more hydrazine compounds having different structures may be used in combination.

The silver halide photographic light-sensitive material used in the present invention includes hydroxylamine compounds, alkanolamine compounds and ammonium phthalate compounds described in US Pat. No. 5,545,505, and US Pat.
The hydroxamic acid compound described in US Pat. No. 5,507, the N-acyl-hydrazine compound described in US Pat. No. 5,558,983, the acrylonitrilo compound described in US Pat. No. 5,545,515, the US Pat. 937,449
It is preferable to add a high-contrast accelerator such as a benzhydrol, diphenylphosphine, a dialkylpiperidine, or a hydrogen atom donor compound such as an alkyl-β-ketoester described in (1).

Among them, 4 represented by the following general formula (P)
Grade onium compounds and amino compounds represented by the general formula [Na] are preferably used.

[0041]

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

[0043]

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In the general formula [Na], R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, a substituted aryl group or a saturated or unsaturated group. Represents a saturated heterocycle. R ₁₁ , R ₁₂ and R ₁₃ may form a ring. Particularly preferred are aliphatic tertiary amine compounds.
These compounds preferably have a diffusion-resistant group or a silver halide adsorbing group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable, and examples thereof include those having the same meaning as the diffusion-resistant group in A in the general formula [H].
Further, preferred adsorbing groups include a heterocyclic ring, a mercapto group,
Examples include a thioether group, a thione group, and a thiourea group.

More preferred nucleation accelerators than the nucleation accelerator represented by the general formula [Na] include compounds represented by the following general formula [Na2].

[0046]

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In the general formula [Na2], R ¹ , R ² , R
³ and R ⁴ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a saturated or unsaturated heterocyclic ring. These can be linked to each other to form a ring. Further, R ¹ and R ² and R ³ and R ⁴ are not hydrogen atoms at the same time. X represents an S, Se or Te atom. L ¹ and L ² each represent a divalent linking group. Specific examples include the following groups or combinations thereof, and groups having appropriate substituents (eg, an alkylene group, an alkenylene group, an arylene group, an acylamino group, a sulfonamide group, and the like).

[0048] _{-CH 2 -, - CH = CH} -, - C 2 H
₄ -, _{pyridinediyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an alkyl group or an aryl group), - O -, -
S -, - (CO) - , - (SO 2) -, - CH 2 N-.

The linking group represented by L ¹ or L ² preferably contains at least one or more of the following structures in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ )
_{HCH 2 O] -, - [} OC (CH 3) HCH 2 O] -, -
_{[OCH 2 C (OH) HCH} 2] -.

Specific examples of the nucleation accelerator represented by the general formula [Na] or [Na2] are shown below, but the present invention is not limited thereto.

[0052]

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[0053]

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[0054]

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[0055]

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In the general formula (P), substituents represented by R _{1 to} R ₄ include alkyl groups (methyl group, ethyl group,
Propyl group, butyl group, hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (Piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), amino group and the like.

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

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

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

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

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

[0062]

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

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

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

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

[0067] X _p ^- is a counter ion necessary to neutralize a charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like . n _p represents the number of counter ions required to neutralize the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0068]

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or an electron-donating substituent whose Hammett's substituent constant sigma value (σP) is negative.

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

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

Hereinafter, specific examples of the quaternary onium compound will be described, but the invention is not limited thereto.

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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

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

The quaternary onium compound and the amino compound are
They may be used alone or in combination of two or more.
It may be added to any of the constituent layers of the silver halide photographic light-sensitive material, but is preferably added to at least one of the constituent layers on the side having the photosensitive layer, and further to the photosensitive layer and / or an adjacent layer thereof. .

The emulsion used in the present invention preferably contains an iridium salt and a rhodium salt. Preferably, the silver halide grains are added in at least one of the steps of forming or growing the grains, and more preferably as a water-soluble salt. As a ligand of these complex salts, a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group, a pseudohalogen group, an alkoxyl group, an ammonium group, and any combination thereof can be used. Each of the addition amounts was 1 × 10 ⁻⁹ to 1 × 10 per mol of silver halide.
^-4 mol, preferably 1 × 10 ^-8 to 1 × 10 ^-4 mol.

Further, ruthenium salts, osnium salts, iron salts,
1 from group 3 of the periodic table such as copper salt, platinum salt, palladium salt
A complex salt containing a Group 3 element may be added together.

In the silver halide photographic light-sensitive material used in the present invention, it is advantageous to use gelatin as a binder or protective colloid in the hydrophilic colloid layer.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used. The addition amount on the side having the emulsion layer is 0.5 to 2.8 g / m ² , and more preferably 0.8 to 2.4 g / m ² .

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

These monomers include a hydroxyl group, a sulfo group,
It may have a water-soluble group such as a carboxyl group or an amide group, and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, -NR ₁ NR ₂ -R ₃ (R ₁ , R ₂ , R ₃ may be a hydrogen atom, an aliphatic group, an aromatic group,
Sulfinic acid residue, acyl group, oxalyl group, carbamoyl group, amino group, alkylsulfonyl group, arylsulfonyl group, sulfoxy group, iminomethylene group, alkenyl group, alkynyl group, aryl group, alkoxyl group,
(An arbitrary group bonded through an alkenyloxy group, an alkynyloxy group, an aryloxy group, or the like), a cationic group, or the like. As a synthesis method, in addition to a usual synthesis method, polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohols. After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

The silver halide photographic light-sensitive material used in the present invention is most effective when used as an output light-sensitive material. Light sources include an Ar laser, a He-Ne laser, a red laser diode, and an infrared semiconductor laser. , Red L
Although an ED laser is typical, an arbitrary laser such as a blue laser such as a He-Cd laser can be used. The output method may be performed by using a single laser or a plurality of lasers simultaneously.

The image setter used in the present invention is an exposure apparatus using a laser beam. Specifically, for example, FTR3050 (Dainippon Screen Co., Ltd.)
Manufactured).

The exposure time when the image setter used in the present invention is used refers to the time during which the photosensitive material is irradiated with the laser. In the case of multiple exposures, the exposure time refers to the total time of exposure. In order to obtain the effects of the present invention,
It is necessary that the exposure time is 5 × 10 ^-7 ~1 × 10 ^-10 seconds, ^{preferably, 1 × 10 -8 ~5 × 10} -10 seconds, more preferably, 1 × 10 ^{- 8} to 1 × 10 ^-9 seconds.

The exposure energy in the imagesetter used in the present invention refers to the energy applied to a silver halide photographic material. In the case of multiple exposures, the exposure energy refers to the total energy of the exposure. In order to obtain the effects of the present invention, the exposure energy must be 0.0
1 to 100 μJ / (sec · cm ² ) is required,
Preferably, it is 0.1 to 10 μJ / (sec · cm ² ).

The exposure system in the image setter used in the present invention is an outer cylindrical system in which a silver halide photographic material is wound around the outer surface of a drum for exposure, and the silver halide photographic material is mounted inside the drum for exposure. A generally known method such as an inner cylindrical method, a method of exposing a silver halide photographic light-sensitive material in a flat shape, and the like can be used.

The developing agent represented by formula (B) used in the present invention will be described.

In the processing method for a silver halide photographic light-sensitive material used in the present invention, the developing solution contains substantially no hydroquinone derivative (dihydroxybenzene compound), and the compound represented by the general formula (B) Is used as a developing agent.

As the developing agent represented by the general formula (B), a compound represented by the following general formula (Ba) in which R ₁ and R ₂ are bonded to each other to form a ring is preferably used. .

[0100]

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In the formula, R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxyl group, a sulfo group, a carboxyl group, an amide group or a sulfonamide group;
₁₁ represents O or S, and Y ₁₂ represents O, S or NR ₁₄ . R ₁₄ represents an alkyl group or an aryl group. M ₁ ,
M ₂ represents a hydrogen atom or an alkali metal atom, respectively.

Examples of the alkyl group represented by R ₁₃ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-pentyl group, a 2-ethyl-hexyl group, an octyl group and a decyl group. No.

The aryl group represented by R ₁₃ includes, for example, a phenyl group and a naphthyl group.

The amino group represented by R ₁₃ includes, for example, an amino group, an N, N-dimethylamino group, an N, N-diethylamino group and the like.

The alkoxyl group represented by R ₁₃ includes
For example, a methoxy group, an ethoxy group, a propoxy group and the like can be mentioned.

Examples of the sulfonamide group represented by R ₁₃ include a methanesulfonamide group and a butanesulfonamide group.

Each substituent described above may have a substituent.

The substituent of the alkyl group described above includes
Halogen atom (eg, Cl, Br, etc.), hydroxyl group, aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl group, etc.), heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group) , N, N'-diethylpyrazolidinyl group, pyridyl group, etc.)
20 alkoxyl groups (eg, methoxy group, ethoxy group, etc.), 6-20 carbon atom aryloxy groups (eg, phenoxy group, etc.), 1-20 carbon atom alkenyloxy groups (eg, allyloxy group, etc.), 1 carbon atom 20 alkynyloxy groups (such as propargyloxy group), heterocyclic oxy groups (such as pyridyloxy group), and having 1 to 26 carbon atoms
(E.g., acetylamino, heptylamino, propionylamino, etc.) and amino groups (e.g., amino, methylamino, dimethylamino, dibenzylamino, etc.).

Examples of the substituent of the amino group described above include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl group, a naphthyl group, etc.), To 20 alkyl groups (e.g., methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl group, etc.), heterocyclic groups (e.g., 2,2,2)
6,6-tetramethylpiperidyl group, quinolizinyl group,
An N, N′-diethylpyrazolidinyl group, a pyridyl group, etc.), an alkoxyl group having 1 to 20 carbon atoms (eg, methoxy, ethoxy group, etc.), an aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group, etc.), An alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group);
Examples thereof include 20 alkynyloxy groups (eg, propargyloxy group), heterocyclic oxy groups (eg, pyridyloxy group), and acyl groups having 1 to 20 carbon atoms (eg, acetyl group, heptyl group, propionyl group, etc.).

Examples of the substituent of the alkylthio group include a halogen atom (eg, Cl, Br and the like), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl group and a naphthyl group), a heterocyclic group (eg, a phenyl group and a naphthyl group). 2,2,6,6
-Tetramethylpiperidyl group, quinolizinyl group, N,
N'-diethylpyrazolidinyl group, pyridyl group, etc.), an alkoxyl group having 1 to 20 carbon atoms (eg, methoxy group, ethoxy group, etc.), an aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group, etc.), carbon An alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (such as a propargyloxy group),
Heterocyclic oxy group (eg, pyridyloxy group), carbon number 1
And 26 amino groups (for example, acetylamino group, heptylamino group, propionylamino group, etc.), amino group (for example, amino, methylamino, dimethylamino, dibenzylamino group, etc.).

Examples of the substituent of the aryl group described above include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group, and an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl). Group), a heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolidinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), having 1 to 20 carbon atoms
(E.g., a methoxy group, an ethoxy group, etc.), an aryloxy group having 6-20 carbon atoms (e.g., a phenoxy group), an alkenyloxy group having 1-20 carbon atoms (e.g., an allyloxy group), Alkynyloxy group (e.g., propargyloxy group), heterocyclic oxy group (e.g., pyridyloxy group), having 1 to 26 carbon atoms
(E.g., acetylamino, heptylamino, propionylamino, etc.) and amino groups (e.g., amino, methylamino, dimethylamino, dibenzylamino, etc.).

Examples of the substituent of the alkoxyl group described above include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl group, a naphthyl group, etc.), To 20 alkyl groups (eg, methyl group, ethyl group, butyl group, cyclohexyl group, isopropyl group, dodecyl group, etc.), heterocyclic groups (eg, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N′-diethylpyrazolidinyl group, pyridyl group, etc.), aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group), alkenyloxy group having 1 to 20 carbon atoms (eg, allyloxy group, etc.), carbon number of 1 -20 alkynyloxy groups (for example, propargyloxy group and the like);
Heterocyclic oxy group (eg, pyridyloxy group), carbon number 1
And 26 amino groups (for example, acetylamino group, heptylamino group, propionylamino group, etc.), amino group (for example, amino, methylamino, dimethylamino, dibenzylamino group, etc.).

Examples of the substituents of the above sulfo group, carboxyl group, amide group and sulfonamide group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group, an alkali metal group (eg, sodium, potassium, etc.), 6
To 20 aryl groups (eg, phenyl group, naphthyl group, etc.), alkyl groups having 1 to 20 carbon atoms (eg, methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl group, etc.), and heterocyclic groups (eg, 2, 2, 6) , 6-tetramethylpiperidyl group, quinolizinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), having 1 to 20 carbon atoms
(E.g., a methoxy group, an ethoxy group, etc.), an aryloxy group having 6-20 carbon atoms (e.g., a phenoxy group), an alkenyloxy group having 1-20 carbon atoms (e.g., an allyloxy group), Alkynyloxy group (eg, propargyloxy group, etc.), heterocyclic oxy group (eg, pyridyloxy group),
And an amino group (for example, amino, methylamino, dimethylamino, dibenzylamino group, etc.).

In the following, formula (B) or (B-
Specific examples of the compound represented by a) are shown below, but the present invention is not limited thereto.

[0115]

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[0116]

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[0117]

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[0118]

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

In the processing agent used in the image forming method of the present invention, compounds having substantially hydroquinone as a mother nucleus (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone,
Hydroquinone monosulfonate).

In the present invention, “contains substantially no hydroquinone derivative” means that the content of the hydroquinone derivative per liter of developer is less than 0.01 mol. In addition, the hydroquinone derivative described above has a content of 0.1%.
When it is contained in an amount of 01 mol or more, failures such as black spots are likely to occur.

In the present invention, the processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the silver halide photographic light-sensitive material in order to reduce the amount of waste liquid. The replenishing amount of the developing solution is 1 m ^{2 of the} silver halide photographic material to be processed.
30 to 150 ml is preferable, more preferably,
It is 50 to 130 ml. The replenishment amount of the fixing solution is 50 to 300 ml per 1 m ^{2 of the} silver halide photographic material to be processed.
And more preferably 100 to 250 ml.

The replenishing amount of the developing solution and the replenishing amount of the fixing solution as used herein indicate the amount of the replenishing solution, and more specifically, the replenishing amounts of the respective solutions when replenishing the same solution as the developing mother liquor and the fixing mother liquor. And the total amount of each of the concentrated solution and the water in the case where the developing concentrated solution and the fixing concentrated solution are replenished with a solution diluted with water. In the case of a solid developing agent and a solid fixing agent, the total volume of the solid processing agent and the volume of water when replenished with a solution dissolved in water, respectively. The total amount of the solid treating agent volume and the water volume when each of the agent and water is separately replenished. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately.

In the case of a solid processing agent, the amount of the processing agent to be charged at one time is preferably 0.1 to 50 g. The solid processing agent in this range is directly charged into a processing tank of an automatic developing machine and slowly dissolved. Processing does not affect the photographic state. This is because the solid processing agent does not dissolve rapidly but dissolves slowly, so even if the amount added at a time is large, the composition is balanced to the amount consumed during processing and shows stable photographic performance. . It was found that the photographic performance could be kept constant by injecting the replenishing water along with the dissolution. The processing liquid is always adjusted to the processing temperature,
It is maintained at a nearly constant temperature. That is, since the dissolution speed is substantially constant, the calculated addition of the solid processing agent and the balance of the components are achieved.

In the image forming method of the present invention, it is preferable that after development and fixing, the image is subjected to washing and / or stabilizing bath. As a stabilizing bath, for the purpose of stabilizing the image,
Inorganic and organic acids and salts or alkali agents thereof (for example, borate, metaborate, borax, phosphate, carbonate, hydroxide) for adjusting the membrane pH (to adjust the membrane surface pH after treatment to 3 to 8) Potassium, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid and the like are used in combination, and aldehydes (formalin, glyoxal, glutaraldehyde, etc.) Chelating agents (eg, ethylenediaminetetraacetic acid or an alkali metal salt thereof, nitrilotriacetate, polyphosphate, etc.), fungicides (eg, phenol, 4-
Chlorophenol, cresol, o-phenylphenol, chlorophen, dichlorophen, formaldehyde, p-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride , N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc., a color tone regulator and / or a residual color improver (for example, a nitrogen-containing hetero compound having a mercapto group as a substituent). Ring compounds, specifically 2-mercapto-
Sodium 5-sulfonate-benzimidazole, 1-
Phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-mercapto-5-propyl-
1,3,4-triazole, 2-mercaptohypoxanthine, etc.). Among them, the stabilizing bath preferably contains a fungicide. These may be replenished in liquid or solid form.

The amount of replenishment is 50 to 400 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material.

In the image forming method of the present invention, it is preferable to form a washing tank or a stabilizing tank with a large number of tanks of two or more layers in order to improve the washing efficiency in view of a demand for shortening the developing time. The amount of the silver halide photographic light-sensitive material, which preferably comprises 2 to 6, more preferably 2 to 4 tanks, and which processes the amount of the washing or stabilizing replenisher from the previous bath per unit area, is 2
It is good to replenish in an amount of up to 50 times, preferably 3 to 30 times by a multistage countercurrent method.

In this case, the replenishing amount is preferably 50 to 400 ml or less, more preferably 70 to 200 ml, per m ^{2 of the} silver halide photographic material.

In the present invention, processing is performed using an automatic developing machine in view of a demand for shortening the developing time. As for the processing time, it is preferable that the total processing time (Dry to Dry) from when the leading end of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 10 seconds to 60 seconds.

The term "total processing time" as used herein includes the total processing time required for processing a black-and-white photographic light-sensitive material, and specifically, for example, development, fixing, washing or rinsing necessary for processing.
The time including all steps such as drying, that is, Dry t
o Dry time.

If the total processing time is less than 10 seconds, desensitization and softening will occur.
Etc., and satisfactory photographic performance cannot be obtained. Preferably
The total processing time is 15 seconds to 44 seconds. Also one
0m ^TwoStable production of large amounts of silver halide photographic materials
For running processing, the development time is 2 seconds to 18 seconds
It is preferred that

The silver halide photographic light-sensitive material used in the present invention includes generally known sulfur sensitization, Se, Te.
Sensitization, reduction sensitization and noble metal sensitization may be appropriately selected and used together. Further, the chemical sensitization may not be performed. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanines, polysulfide compounds and the like can be used in addition to the sulfur compounds contained in gelatin.
An oxidizing agent for silver can also be used in the production process of the silver halide photographic material.

The silver halide photographic light-sensitive material used in the present invention contains pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or chloroiodobromide containing 60 mol% or more of silver chloride as a halogen composition. Preferably it is silver.

The average grain size of the silver halide is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. What is particle size?
In the case where the particles are spherical or particles that can be approximated to spheres, they mean particle diameter. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see C.I. E. FIG. K. Mees & T. H. J
ames: The theory of the p
photographic process, 3rd edition, 3
See pages 6 to 43 (1966, published by Mcmillan).

The shape of the silver halide grains is not particularly limited, and may be any of tabular, spherical, cubic, tetradecahedral, octahedral, and other shapes. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
So-called monodisperse emulsions containing 0%, preferably 95% are preferred.

The method of reacting the soluble silver salt with the soluble halide salt in preparing the silver halide emulsion may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The surface of the silver halide grains can be controlled in halogen composition using water-soluble halides or silver halide fine grains. This technique is known in the art as conversion and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen compositions, dopant species and amounts, distribution of lattice defects, and the like. In the present invention, as the silver halide grains, particle size, sensitivity, crystal habit, photosensitive wavelength, halogen composition, monodispersity, amount and type of doping agent, potential, pH, desalting method and other production conditions, surface A plurality of types of particles having different states, chemically sensitized states, and the like can be used in combination. In that case,
These silver halide grains may be contained in the same layer, or may be contained in a plurality of different layers.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (RD).
17643, pages 22 to 23 (December, 1978).

In the silver halide photographic light-sensitive material used in the present invention, the silver content of the silver halide emulsion layer is 2.0 g / g.
m ^{2 to} 3.5 g / m ² , more preferably 2.5 g
/ M ² or more and 3.5 g / m ² or less. When the silver content is high, the running stability is poor, and when the silver content is low, a sufficient density cannot be obtained.

In the silver halide photographic light-sensitive material used in the present invention, the silver halide emulsion can be spectrally sensitized to a desired wavelength by a sensitizing dye. Sensitizing dyes that can be used include cyanines, merocyanines, complex cyanines, complex merocyanines, holopolar cyanines, hemicyanines, styryl dyes and hemioxonol dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei 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, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and 2-thiooxazolidin-2,4-
A 5- to 6-membered heterocyclic ring such as a dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

Specifically, (RD) 17643 (1978)
December 2013) page 2, page 3, US Patent No. 4,425,42
No. 5, No. 4,425,426 can be used. The sensitizing dye is disclosed in U.S. Pat.
The dissolution may be carried out using ultrasonic vibration described in US Pat. No. 485,634.

The sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in RD17643 (published December 1978), page 23, IV, section J.

The silver halide photographic light-sensitive material used in the present invention may be variously prepared for the purpose of preventing fog during the production process, storage or photographic processing of the silver halide photographic light-sensitive material, or stabilizing photographic performance. Can be contained. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazain Benzenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes, etc .; Sulfonic acid, benzene sulfinic acid, benzenesulfonic acid amide, can be added to many compounds known as antifoggants or stabilizers such as potassium bromide. Particularly preferably,
A substituted or unsubstituted heterocyclic or fused heterocyclic ring containing any of N, O, S and Se, and a water-soluble halide.

The emulsion layer and the non-photosensitive hydrophilic colloid of the silver halide photographic material used in the present invention may contain an inorganic or organic hardener. 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), 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.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) ) Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, isocyanates, carboxyl group-activated hardeners and the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer may contain a coating aid, an antistatic agent, an improvement in slipperiness,
Various known surfactants may be used for various purposes such as emulsification and dispersion, prevention of adhesion and improvement of photographic properties.

In the silver halide photographic light-sensitive material used in the present invention, various other additives are used. For example, a desensitizer, a plasticizer, a development accelerator, oil, colloidal silica and the like can be mentioned.

These additives and the above-mentioned additives are specifically described in (RD) No. 17643 (supra),
What is described on page 31 etc. can be used.

The silver halide photographic light-sensitive material used in the present invention has a layer structure comprising at least two layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween. Further, it may have a non-photosensitive emulsion. As the non-emulsion layer, any number of layers may be provided as necessary between the support and the emulsion layer closest to the support, between a plurality of emulsion layers, and outside the emulsion layer farthest from the support. Can be. These layers include:
Disperse water-soluble or water-insoluble dyes, image-wise or non-image-wise development control (suppression or acceleration) agents, contrast agents, physical property modifiers, etc. in aqueous solution or organic solvent, or in the form of solid fine particles In protected form (whether or not protected by oil).

The emulsion layer may be on one side or both sides of the support. Even on one side, an arbitrary number of hydrophilic or non-hydrophilic layers can be provided in combination on the opposite side. In particular, when a layer of a hydrophobic polymer is provided outside the hydrophilic colloid layer with respect to the support, the drying property can be improved.

In the silver halide photographic light-sensitive material used in the present invention, a photographic emulsion layer and other layers are coated on one or both sides of a flexible support usually used for a silver halide photographic light-sensitive material. Useful as flexible supports are
Films composed of synthetic polymers of cellulose acetate, cellulose butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate (which may contain colored pigments), or paper supports coated with polymers such as polyethylene and polyethylene terephthalate And so on. These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

In the processing method for a silver halide photographic light-sensitive material used in the present invention, the developing waste liquid can be regenerated by energizing. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The silver halide photographic light-sensitive material used in the present invention can be processed while current is applied. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. Further, there is a method of processing a silver halide photographic light-sensitive material while energizing the developing solution. In this case, an additive which can be added to the developing solution as described above can be added.

The sulfite and metabisulfite used as a preservative in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

In the developing solution, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) , Dissolution aids (eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (Eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (eg, US Pat. No. 2,30)
No. 4,025, compounds described in JP-B-47-45541, etc.), hardeners (for example, glutaraldehyde or
Bisulfite adduct) or an antifoaming agent. The pH of the developer is 8.5 or more to 10.5
It is preferably adjusted to less than 9.0, and particularly preferably adjusted to 9.0 to 10.4.

The inhibitor used in the image forming method of the present invention refers to a compound having a mercapto group or a monocyclic or condensed heterocyclic compound. A monocyclic or fused heterocyclic compound having a mercapto group is also an inhibitor in the present invention.

Specific examples are shown below, but the compounds used in the present invention are not limited to the following.

As specific examples, for example, oxazole compounds, benzoxazole compounds, thiazole compounds,
Benzothiazole compounds, imidazole compounds, benzimidazole compounds, pyrazole compounds, indazole compounds, triazole compounds, benzotriazole compounds, tetrazole compounds, pyrimidine compounds, triazine compounds, quinoline compounds, quinarizone compounds, purine compounds, etc. It may have a substituent or a mercapto group. Examples of the substituent include a methyl group, a sulfo group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a phenyl group, a halogen atom, and the like, but are not limited thereto. Also,
The inhibitor is usually 0.3 to 1.5 g, more preferably 0.3 to 0.75 g per liter.

As a special type of development processing of the light-sensitive material used in the present invention, an activator processing solution in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution for development. May be used. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions. In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of 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 that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum and the like. The fixing solution optionally contains compounds such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent having a water softening ability. be able to. In the development processing, washing is performed after fixing, and the washing layer may be a method in which fresh water is supplied at a rate of several liters per minute depending on the processing, or the washing water is circulated.
A method of reusing after treating with a chemical, a filter, ozone, light, or the like, or a method of replenishing a small amount of a stabilizing solution in accordance with a treatment amount by using a washing bath as a stabilizing bath with a stabilizer added is used. This step is usually at room temperature, but it may be heated to 30 ° C to 50 ° C. In addition, when a stabilizing bath is used, it is possible to perform a pipeless treatment that does not need to be directly connected to the water supply. A rinsing bath can be provided before and after each treatment layer.

The mother liquor or replenisher of the developing solution, the fixing solution or the stabilizing solution is usually supplied by diluting the working solution or the concentrated solution immediately before it is used. It may be in the form of a concentrated liquid, a viscous liquid in a semi-kneaded state having a high viscosity, or may be a method in which a simple substance or a mixture of solid components is dissolved at the time of use. When a mixture is used, a method in which components that are difficult to react with each other are adjacently packed in layers and then vacuum-packaged, and then opened and dissolved at the time of use, or a method of tableting can be used. In particular, the method of adding a tablet formed product to the dissolution layer or the directly treated layer is a method which is extremely excellent in workability, space saving and preservation, and is particularly preferably used.

In the drying zone of the automatic developing machine, a method of drying using hot air is usually used. However, a heat transfer material of 90 ° C. or more (for example, a heat roller of 90 ° C. to 130 ° C.) or 150 ° C. or more is used. (For example, tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, and silicon carbide, etc.) by direct current generation and radiation, and heat energy from a resistance heating element to copper, stainless steel, nickel, various ceramics, etc. That emits infrared rays by transmitting heat to the radiator or emitting infrared rays), or those provided with a known drying means such as a dehumidifier, a microwave generator, or a water-absorbing resin. . Further, a control mechanism for a dry state may be provided.

[0163]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of silver halide emulsion A1) Using a double jet method, silver chloride had an average diameter of 70 mol%, and the remainder was silver bromide.
9 μm silver chlorobromide core particles were prepared. At the time of mixing the core particles, K ₃ Rh (NO) ₄ (H ₂ O) ₂ was added in an amount of 40 μg per 1 mol of silver to 1 mol of silver at the end of grain formation in the presence of 60 μg.
An aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining the same at ℃, pH 3.0, and silver potential (EAg) 165 mV.

EAg was added to the core particles with a salt solution of 125 m
V and shelled using a double jet method. At that time, K ₃ RhCl ₆ was added to the halide solution in an amount of 20 μg per mole of silver.
And K ₂ IrCl ₆ were added in an amount of 100 μg per mole of silver. Further, KI conversion was performed using silver iodide fine particles, and the resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (70 mol% of silver chloride, iodine having an average diameter of 0.17 μm). (A silver bromide of 0.2 mol%, the balance being silver bromide). Then, JP-A-2-280
No. 139, which is a modified gelatin wherein the amino group in the gelatin is substituted by phenylcarbamyl.
-280139, Exemplified compound G-8 on page 287 (3))
It was desalted using. EAg after desalting is 190 mV at 50 ° C.
Met.

To the obtained emulsion, potassium bromide was added in an amount of 100 mg per 1 mol of silver and citric acid to give a pH of 5.6.
EAg was adjusted to 123 mV, and sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added to silver 1
The reaction was performed by adding 170 mg to the mole. And
Inorganic sulfur (S8) compound dispersed in a solid (Seisin Enterprise Co., Ltd .; saponin added using PM-1200 and dispersed to an average of 0.5 μm) is 0.6 m / mol silver.
g, and 6 mg of chloroauric acid were added thereto, and the mixture was chemically ripened at a temperature of 52 ° C. until the maximum sensitivity was obtained. Then, at 40 ° C., 120 mg of sensitizing dye d-1 and 150 mg of sensitizing dye d-10 were added.
4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene (TAI) at 60
After 0 mg, 20 mg of 1-phenyl-5-mercaptotetrazole and 300 mg of potassium iodide were added, the pH was adjusted to 5.1 with citric acid.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for He-Ne laser light source) On a support, a gelatin subbing layer of the following formula 1 was coated with a gelatin amount of 0.2 g / g.
such that m ^2, and more amount of silver 3.3 g / m ² of silver halide emulsion layers of the formulation 2 as an upper layer, the amount of gelatin is 1.2
g / m ^2, and a protective layer coating solution of the following Formulation 3 was simultaneously and multi-layer coated so that the gelatin amount was 0.6 g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 4 was provided with a gelatin amount of 1.9 g / m ^2, and a backing protective layer of the following formulation 5 was provided thereon with a gelatin amount of 0.6 g / m 2. ^The emulsion layer side and the emulsion layer side were simultaneously layer-coated at a speed of 150 m / min by a curtain coating method so as to obtain a layer 2 and cooled and set. Then, the backing layer side was simultaneously layer-coated and cooled and set at -1 ° C. A sample was obtained by simultaneously drying both sides.

Formulation 1 (Gelatin undercoat layer) Gelatin 0.2 g / m ² 1-phenyl-5-mercaptotetrazole 2.0 mg / m ² Fungicide Z 0.5 mg / m ² Solid disperse dye 1-25 12 mg / m ² Prescription 2 (composition of silver halide emulsion layer) Silver halide emulsion A1 (in terms of silver amount) 3.3 g / m ² hydrazine derivative H-25 Addition amount shown in Table 1 / m ² hydrazine derivative H-8 Table 1 the amount / m ² active agent S-1 (Sodium - iso - amyl -n- decyl sulfosuccinate) 2 mg / m ² 2-mercapto hypoxanthine 2 mg / m ² nicotinamide 1 mg / m ² gallate n- propyl ester 50 mg / m ² mercaptopyrimidine ^{1mg / m 2 EDTA 25mg / m} 2 polymer latex L4 0.65 g / m ² composite latex PL-10 1.4g / m ² Charge k 10 mg / m ² (gelatin coating solution pH using phthalated gelatin was 4.8.) Formulation 3 (Emulsion protective layer composition) Gelatin ^{0.6g / m 2 S-1 27mg} / m 2 Fluorine-based Surfactant F-16 30 mg / m ² Fluorosurfactant F-17 0.5 mg / m ² Matting agent: spherical polymethyl methacrylate having an average particle size of 3.5 μm 15 mg / m ² Matting agent: average particle size 8 μm 13 mg / m ² amine compound Na-21 12.5 mg / m ² Hydroquinone 200 mg / m ² Colloidal silica (mean particle size 0.05 μm) 250 mg / m ² Sliding agent R-21 75 mg / m ² Compound S 80 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h2 180 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ² 2-mercaptohypoxanthine 30 mg / m ² Prescription 4 (backing layer composition) Gelatin 1.9 g / m ² S-1 5 mg / m ² Polymer latex L3 0.3 g / m ² colloidal silica (average 500 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² Hard film Formulation h3 50 mg / m ² Zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² Formulation 5 (backing protective layer) Gelatin 0.6 g / m ² Matting agent: Monodisperse polymethyl methacrylate 50 mg / m ² mat having an average particle size of 5 μm agent, average particle size: 3μm indefinite based silica 12.5 mg / m ² Sodium - di - (2-ethylhexyl) Sulfosuccinate ^{10mg / m 2 S-1 1mg} / m 2 Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² Fluorine-containing surfactant F-17 0.5mg / m ² hardener h1 64 mg / m ² sodium polystyrenesulfonate 10 mg / ^{m 2}

[0169]

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[0173]

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The sample thus obtained was exposed with a laser sensitometer using a 633 nm He-Ne laser as a light source at an exposure energy and exposure time as shown in Table 1. Next, an automatic processor GR-27 manufactured by Konica Corporation
And treated under the following conditions and under the following conditions.

[0182] The PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).

(Composition of developer A) DTPA / 5Na (diethylenetriaminepentaacetic acid / 5 sodium salt) per liter of working solution 1 g Sodium sulfite 31.5 g Potassium carbonate 41.4 g Sodium carbonate 72.4 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g Potassium bromide 4.72 g 5-Methylbenzotriazole 0.27 g 1-Phenyl-5-mercaptotetrazole 0.03 g Dimezone S 1.1 g Sodium erythorbate (B-1) 50 g Diethylaminopropanediol 25 g Isoelite P (Salt water refined sugar) 20 g) KOH was added so that the pH of the working solution was 10.4.

Developer B In the composition of developer A, sodium erythorbate (B
-1) A developer B was prepared in the same manner except that 30 g of hydroquinone was used instead of 50 g.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per liter of working 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 Sulfuric acid Aluminum (27% aqueous solution) 25 ml of sulfuric acid was used to adjust the pH of the working solution to 4.9.

The following were evaluated for the obtained samples.

(Processing conditions) (Process) (Temperature) (Time) Current image 35 ° C. 30 seconds Fixed 35 ° C. 20 seconds Water washing Normal temperature 20 seconds Squeeze / dry 50 ° C. 30 seconds Total 100 seconds Running condition is one day 250 sheets of samples Encyclopedia size 24x7 / day, the photosensitive material 1 m ² per developer 200
The processing was performed while replenishing 250 ml of the fixing solution and 250 ml of the fixing solution.

The samples were evaluated at the start of running and after 7 days of running processing (blackening rate: 50%), and the new solution and after running in the table represent before and after running, respectively.

<Evaluation of Sensitivity and Gamma> The sensitivities in the following table indicate the values of Sample No. The relative sensitivity was expressed assuming that the sensitivity at a density of 1 was 2.5 at 100. Gamma is represented by a tangent between densities of 0.1 and 3.0, and it is shown that a super-high contrast image can be obtained only when the gamma value in the table is 10 or more.

<Evaluation of Black Pots> The developed samples thus obtained were visually evaluated using a 100-fold loupe, and ranked in 5 stages from 5 to 1 in ascending order of occurrence of black pots.
Ranks 1 and 2 are unfavorable levels for practical use.

<Evaluation of Point Material> H of 633 nm was used as a light source.
2400 dpi with laser sensitometer using e-Ne laser
The developed sample obtained by outputting a 50% halftone dot of 175 Lpi was visually evaluated using a 100-fold loupe, and was ranked in 5 ranks of 5 to 1 in the order of excellent dot quality. Ranks 1 and 2 are unfavorable levels for practical use.

Table 1 shows the obtained results.

[0193]

[Table 1]

As is clear from Table 1, the sample used in the present invention has no deterioration in dot quality and no black spot even when the exposure time is short. Further, it can be seen that the sensitivity fluctuation and the deterioration of the dot quality when running are small.

Example 2 The sample prepared in Example 1 was similarly exposed, and low replenishment rapid processing was performed using the same processing solution by an automatic developing machine GR-26SR (manufactured by Konica Corporation) under the following conditions.

The obtained developed sample was evaluated in the same manner as in Example 1.

Processing conditions Rapid processing (Process (temperature) (time) Development 35 ° C. 12 seconds Fixing 35 ° C. 10 seconds Rinse at room temperature 10 seconds Drying 50 ° C. 15 seconds Total 47 seconds Running conditions are 24 hours a day and a large-sized sample 250 sheets / day, developer 120 / m ^{2 of} photosensitive material
and 150 ml of fixer.

The samples at the start of the running and after 7 days of the running process (blackening rate: 50%) were evaluated. The terms “new solution” and “after running” in the table mean before and after running, respectively.

Table 2 shows the results.

[0200]

[Table 2]

As is clear from Table 2, the sample of the present invention has a small deterioration in dot quality and a small deterioration in running performance even when subjected to rapid processing with low replenishment.

Example 3 (Preparation of Silver Halide Emulsion B1) Chlorobromide having a silver chloride content of 70 mol% and a balance of silver bromide having an average thickness of 0.05 μm and an average diameter of 0.15 μm using a double jet method. Silver core particles were prepared. At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At this time, K ₂ IrCl ₆ was added in an amount of 20 × 10 ⁻⁸ mol per mol of silver. The resulting emulsion had a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (silver chloride content: 90 mol%, silver iodide content: 0,0 μm, average diameter: 0.25 μm) .2 mol%, the balance being silver bromide).

Next, modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted by phenylcarbamyl, for example, JP-A-2-280139).
No. 287 (3), Exemplified compound G-8). The EAg after desalting was 190 mV at 50 ° C.

The obtained emulsion was mixed with TAI at a ratio of 1 to 1 mol of silver.
× 10 ^-3 mol, potassium bromide and citric acid were further added to adjust the pH to 5.6 and the EAg to 123 mV, and 5 mg of chloroauric acid and 0.5 mg of sulfur white per mol of silver were added. Chemical ripening was performed at 60 ° C. until the maximum sensitivity was obtained. After ripening, TAI was added at 2 × 10 ^-3 per mole of silver.
Mole, 1-phenyl-5-mercaptotetrazole
× 10 ^-4 mol and gelatin were added.

(Preparation of Silver Halide Emulsion B2) The silver chloride content was 60 mol% and the silver iodide content was 1.
5 mol%, the balance is made of silver bromide.
Silver chloroiodobromide core grains having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, 2 × 10 ⁻⁸ mol of K ₃ Rh (H _{2 O} ) Br ₅ was added per mol of silver. The core particles were shelled using a double jet method. The resulting emulsion had a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (silver chloride content: 90 mol%, silver iodide content: 0,10 μm, average diameter: 0.42 μm). .2 mol%, the balance being silver bromide). Next, JP-A-2-
Denatured gelatin described in JP-A-280139 (the amino group in gelatin is substituted with phenylcarbamyl; for example, Exemplified Compound G on page 287 (3) of JP-A-2-280139)
Desalting was performed using -8). The EAg after desalting is 18 at 50 ° C.
It was 0 mV.

The obtained emulsion was mixed with TAI per mole of silver.
10 ^-3 mol was added, and further, potassium bromide and citric acid were added to adjust the pH to 5.6 and the EAg to 123 mV.
7 mg of chloroauric acid and 0.7 mg of sulfur flower were added per mole, and the mixture was chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. After ripening, TAI was added in an amount of 2 × 10 ⁻³ mol per mol of silver and 1-phenyl-5-mercaptotetrazole in 3 ×
10 ^-4 mol and gelatin were added.

(Preparation of a silver halide photographic light-sensitive material for a printing plate making scanner for a red semiconductor laser light source) A gelatin undercoat layer having the following formula 10 was formed on a polyethylene terephthalate support so that the gelatin amount was 0.2 g / m ^2. Further, a silver halide emulsion layer 1 having a formulation of 11 was added thereon with a silver amount of 0.3 g / m 2.
^2, the gelatin amount 0.3 g / m ^2, further thereon, so the amount of gelatin coating solution having the following formulation 12 as gelatin intermediate layer is 0.3 g / m ^2, further halogen prescription 13 thereon The silver halide emulsion layer 2 was coated simultaneously so that the amount of silver was 2.9 g / m ² and the amount of gelatin was 0.8 g / m ² , and the protective layer of the following formula 14 was 0.8 g / m ² . . On the other side of the undercoat layer, a backing layer of the following formulation 15 was further provided with a polymer layer of the following formulation 16 so that the amount of gelatin became 0.6 g / m ² , and further a further polymer layer of the following formulation 17 was further provided thereon. A sample was obtained by simultaneously coating the backing protective layer with the emulsion layer so that the amount of gelatin was 0.4 g / m ² .

Formulation 10 (Gelatin undercoat layer composition) Gelatin 0.3 g / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 0.4 mg / m ² 2-mercaptobenzthiazole 5 mg / m ² Formulation 11 (halogenated) Silver emulsion layer 1 composition) Silver halide emulsion B2 (in terms of silver amount) 0.3 g / m ² Compound t-5 10 mg / m ² S-1 1.7 mg / m ² Formulation 12 (gelatin intermediate layer composition) Gelatin 0. 6 g / m ² S-1 2 mg / m ² Hydroquinone 50 mg / m ² Prescription 13 (composition of silver halide emulsion layer 2) Silver halide emulsion B1 Silver amount 2.9 g / m ² equivalent amount Sensitizing dye d-5 6 mg / amount / m ² amine compound according to the addition amount / m ² hydrazine derivative H-8 table 3 according to m ² sensitizing dye d-2 3 mg / m ² hydrazine derivative H-25 table 3 Na-9 5mg / m ^Two Compound e 100 mg / m ² Gallic acid n-propyl ester 50 mg / m ² Polymer latex L4 0.5 g / m ² Composite latex PL-10 1.2 g / m ² S-1 0.7 mg / m ² 2-mercaptohypoxanthine 1 mg / m ² Ethylenediaminetetraacetic acid 50 mg / m ² Formulation 14 (Emulsion protective layer composition) Gelatin 0.6 g / m ² Sodium-di-n-hexylsulfosuccinate 20 mg / m ² Quaternary onium compound (P-26) 15 mg / m ² slip agent R-5 100 mg / m ² Hydroquinone 100 mg / m ² Compound S 0.2 g / m ² Compound P 5 mg / m ² KBr 50 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 25 mg / m ² composite latex PL-10 0.4g / m ² fluorine-containing surfactant F-17 2mg / m ² fluorine-containing surfactant F- 6 20 mg / m ² hardener h1 70 mg / m ² formulation 15 (backing layer composition) Gelatin 0.6 g / m ² polymer latex L3 0.3 g / m ² composite latex PL-10 0.5g / m ² formulation 16 ( Hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² hardener h3 50 mg / m ² Formulation 17 (backing protective layer) Gelatin 0.4 g / m ² matting agent: average Monodisperse polymethyl methacrylate having a particle size of 5 μm 50 mg / m ² sodium-di-n-hexylsulfosuccinate 20 mg / m ² fluorinated surfactant F-17 2 mg / m ² dye k 40 mg / m ² hardener h4 50 mg / m ² Further, the amount of light changes the sample obtained in this way, a laser sensitometer using infrared semiconductor laser as a light source in an exposure time shown in Table 3 While step exposure, the definition of the 8 cm ² / L (specific surface area of the specific surface area of the automatic processor GR-26 developing tank using a developer and fixer having the following composition: Numbering of JP-A-7-77782 0085 And modified under the following conditions. After dissolving the tablets with a dissolving mixer, the developing and fixing were finished to make 1 L for 25 tablets.

The obtained developed sample was subjected to PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).

<Processing liquid formulation> (1) Pure water 224 ml DTPA · 5Na 1.00 g sodium sulfite 31.5 g potassium carbonate 41.4 g sodium carbonate 72.4 g 8-liter per 1 L of starting developer A (DS) used solution Mercaptoadenine 0.06 g Diethylene glycol 50 g Potassium bromide 4.72 g 5-Methylbenzotriazole 0.27 g 1-Phenyl-5-mercaptotetrazole 0.03 g Dimezone S 1.1 g Sodium erythorbate (B-1) 50 g Diethylaminopropanediol 25 g Isoelite P (Saltwater Mineral Sugar Co., Ltd.) 20 g KOH (55% aqueous solution) and pure water 500 ml (p
H10.0). When using pure water 500
and 500 ml of the above concentrated solution. (Na
Ratio: 81.4%) Developer B In the composition of Developer A, sodium erythorbate (B
-1) A developer B was prepared in the same manner except that 30 g of hydroquinone was used instead of 50 g.

(2) Replenished Developing Tablet (D-SR) Preparation of Granulated Part A (per liter of liquid used) Diethylenetriaminepentaacetic acid / 5 sodium salt 1.00 g Sulfite 0.25 mol 8-mercaptoadenine 0.06 g 5-methylbenzotriazole 0.27 g Potassium bromide 4.72 g 1-phenyl-5-mercaptotetrazole 0.03 g Dimezone S 1.1 g Sodium erythorbate (B-1) 35.6 g Isoelite P (Shiomizu Port Refining Co., Ltd. )) 20 g D-mannitol (Kao Corporation) 4 g The above ingredients were mixed in a commercially available bantam mill for 30 minutes, and further granulated for 10 minutes at room temperature with a commercially available stirring granulator.
The granulated product was dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain a granulated product A part.

When developer B was used, a replenishment developing tablet to which 20 g of hydroquinone was added instead of 35.6 g of sodium erythorbic acid (B-1) was used.

Preparation of granulated B part (per liter of liquid used) Carbonate 1.0 mol D-mannitol (Kao Corporation) 5 g Lithium hydroxide 3.4 g The above materials were mixed in a commercially available bantam mill for 30 minutes. After granulating at room temperature for 10 minutes with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed dryer, and the granulated product B
Got the parts.

The mixture obtained by thoroughly mixing the above-mentioned parts A and B for 10 minutes is mixed with the machine UDINA DFE30.4.
9. Using a 0 tableting machine (manufactured by Masina Co., Ltd.)
Filling with 83 g, 25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² .

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

(4) Supplementary Fixing Tablet Preparation of Granulated Part A (for 1 L of Working Solution) Ammonium Thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium bisulfite 10 g Sodium acetate 40 g Isoelite P (brine water refined sugar ( 5 g Pine Flow (trade name: Matsutani Chemical) 8 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then the granulated material was flown. Granulated material A dried at 40 ° C for 2 hours in a bath dryer
Got the parts.

Preparation of granulated B parts (per liter of liquid used) 10 g of boric acid 3 g of tartaric acid 18 g of sodium hydrogen sulfate 37 g of aluminum sulfate / 18 hydrate 37 g of pine flow (trade name: Matsutani Chemical) 4 g 30 g of the above material in a commercially available bantam mill After mixing for 10 minutes at room temperature with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed drier to obtain granulated product B.
Got the parts.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the resulting mixture was used in a Masina UD DFE 30
25 tablets with a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² using a 40 tableting machine at a filling amount of 11.0 g per tablet.

The developers DS and D-SR were sealed in a polyethylene container, stored at 50 ° C. and 80% RH for 7 days, and then opened and used. The oxygen permeability of the container was 30 ml / atm · m ² · day · 25 ° C.

<Automatic developing machine> An automatic developing machine GR-26 was used.

Processing Conditions (Step) (Temperature) (Time) Developing 35 ° C. for 15 seconds Fixing 34 ° C. for 10 seconds Washing 35 ° C. to room temperature for 15 seconds Drying 45 ° C. for 15 seconds 250 sheets / day, 180 developer / m ^{2 of} photosensitive material
The processing was performed while replenishing 250 ml of the fixing solution and 250 ml of the fixing solution.

The samples at the start of the running and after 7 days of the running process (blackening rate: 50%) were evaluated. The terms “new solution” and “after running” in the table mean before and after running, respectively.

Table 3 shows the results.

[0224]

[Table 3]

As is clear from Table 3, even when the solid processing agent is used, the sample of the present invention has a small deterioration of the dot substance and a small performance deterioration in running.

Example 4 An automatic developing machine GR-2 was prepared using the developing solution and the fixing solution of Example 3.
The film was rapidly processed using 6SR (manufactured by Konica Corporation) under the conditions of Example 2 using the film of Example 1. At that time, the washing unit was modified so that a washing tank was provided in three stages with a capacity of 4 L, and the washing tank could be replenished with the washing tank in the downstream tank closest to the drying unit. Further, the temperature of the washing tank was controlled so that the temperature of the washing water on the most upstream side of the fixing tank was adjusted to 35 ° C., and development processing was performed. The tablets were replenished after dissolution with a dissolution mixer (finished to 1 L for 25 for both development and fixing).

<Automatic developing machine> The automatic developing machine GR-26SR was modified so that a washing section was provided with three tanks each having a capacity of 4 liters and the downstream tank closest to the drying section could be filled with washing water.

The temperature of the rinsing tank was controlled so that the temperature of the rinsing water on the most upstream side of the fixing tank was adjusted to 35 ° C. to carry out development processing. The tablets were replenished after dissolution with a dissolution mixer (finished to 1 liter per 25 for both development and fixing).

The running conditions were as follows: the sample was operated 24 hours a day, and 250 samples of all sizes were processed per day, while replenishing 120 ml of the developing solution and 150 ml of the fixing solution per 1 m ^{2 of} the photosensitive material.

The samples at the start of the running and after 7 days of the running process (blackening rate: 50%) were evaluated. The terms “new solution” and “after running” in the table mean before and after running, respectively.

The results are shown in Table 4.

[0232]

[Table 4]

As is clear from Table 4, even if the sample of the present invention is treated by a low replenishing method using a solid processing agent and a method in which the washing step is performed in a multi-stage countercurrent method of two or more stages, the sample of the present invention does not deteriorate in dot quality. It can be seen that the performance degradation during running is small.

[0234]

According to the present invention, a silver halide photographic image for printing plate making having an ultra-high contrast and excellent in quality can be obtained even when the exposure time is shortened, and even in the rapid processing in which the processing time is shortened.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/30 G03C 5/30 11/00 11/00

Claims (5)

[Claims] 1. A support having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer contains at least one hydrazine derivative in an amount of 1 × 10 ^-5 to 1 × 10 ^-5. A silver halide photographic light-sensitive material containing × 10 ⁻³ mol / m ² was exposed with an imagesetter, and then exposed.
In an image forming method for obtaining an image having a density of 4.5 or more by processing with an automatic developing machine, the exposure energy at the time of exposure is 0.01
-10 μJ / (sec · cm ² ), exposure time 5 × 10
^-7 to 1 × 10 ^-10 seconds, and contains a compound represented by the following general formula (B) as a developing agent during processing using the automatic developing machine, and substantially contains a hydroquinone derivative. An image forming method, wherein the processing is carried out using a processing agent not containing. Embedded image Wherein R ₁₁ and R ₁₂ are each an alkyl group, an amino group,
Represents an alkoxyl group or an alkylthio group, which may have a substituent and may combine with each other to form a ring; k represents 0 or 1, and when k = 1, X is -CO
-Or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ] 2. A replenishing amount of a developing solution during processing is 30 to 150 ml per m ^{2 of a} silver halide photographic light-sensitive material, and a replenishing amount of a fixing solution is 50 to ³ per m ^{2 of a} silver halide photographic light-sensitive material.
2. The image forming method according to claim 1, wherein the processing is performed with 00 ml. 3. The image forming method according to claim 1, wherein the total processing time (Dry to Dry) of the silver halide photographic light-sensitive material is from 10 seconds to 60 seconds. 4. The image forming method according to claim 1, wherein the processing is performed using a processing solution prepared from a solid processing agent. 5. The method according to claim 1, wherein the washing step is a multi-stage countercurrent type having two or more steps, and the replenishment amount of the washing water or the rinsing liquid is 50 to 400 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. The image forming method according to any one of claims 1 to 4.