JP2000147701A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material for forming a printing plate superior in scratch resistance and good in reproducibility of microdots and the method for processing it, and further, to provide the photosensitive material high in gamma and superior in dots reproducibility even in the case of mass processing and low replenishing, and its processing method. SOLUTION: The silver halide photographic sensitive material is provided with hydrophilic colloidal layers including a photosensitive silver halide emulsion layer and it is characterized by containing at least one kind of urethane latex in the hydrophilic colloidal layers and containing a gelatin in the total gelatin amount of 1.1-3.6 g/m2 on the side of the emulsion layer. The constituent layers of this photosensitive material contain a hydrazine derivative and an amine compound and/or a quarternary onium compound. This photosensitive material is processed in the total processing time of 10-60 sec by using a multistage countercurrent system in a replenishing rate of a rinsing water or a stabilizing water of 50-400 ml per 1 m2 of the photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for plate-making printing having excellent abrasion resistance and a processing method therefor.

[0002]

2. Description of the Related Art In recent years, in the silver halide photographic light-sensitive material for printing plate making (hereinafter, also simply referred to as "light-sensitive material"), a screening method for forming an image with a smaller halftone dot than before, such as high definition and FM screening, has been adopted. It is beginning 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 a super-high contrast image, for example, US Pat. No. 4,269,929 in which a hydrazine derivative is contained in a photosensitive material or JP-A-4-98239 in which a nucleation accelerator is contained. No. are disclosed.

On the other hand, in recent years, there has been a strong demand for reduction of photographic processing waste liquids such as development, fixing, and washing and replenishment of the processing liquids due to increased interest in environmental issues or cost. Further, a reduction in processing time is required for reasons such as efficiency and cost reduction. For example, 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 is as follows: Usually, it took 90 seconds or more, but recently, ultra-rapid processing of 60 seconds or less has been required.

[0005] However, when such ultra-rapid processing is performed, problems such as abrasion failure easily occurring during film transport during development processing and insufficient film drying properties arise. Furthermore, if the above-mentioned low replenishment of the processing solution is added to this, it becomes difficult to obtain faithful reproducibility of fine halftone dots required for a photographic material for plate making printing.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photograph having excellent scratch resistance and gamma and excellent reproducibility of fine halftone dots even when a low replenishment and a large amount of running are rapidly processed. An object of the present invention is to provide a photosensitive material and a processing method therefor.

[0007]

The object of the present invention has been attained by the following.

(1) In a silver halide photographic material having a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer on a support, at least one urethane latex is contained in the hydrophilic colloid layer. And the total amount of gelatin on the silver halide emulsion layer side is from 1.1 to 1.1.
A silver halide photographic light-sensitive material characterized by being 3.6 g / m ² .

(2) The halogen according to (1), wherein the amount of urethane latex in the hydrophilic colloid layer is 0.01 to 1.5 times the total amount of gelatin on the silver halide emulsion layer side. Silver halide photographic material.

(3) The silver halide according to (1) or (2), wherein the photosensitive silver halide emulsion layer and / or the hydrophilic colloid layer contains at least one hydrazine derivative. Photosensitive material.

(4) The photosensitive silver halide emulsion layer and / or hydrophilic colloid layer contains at least one kind of amine compound and / or quaternary onium compound. The silver halide photographic light-sensitive material according to any one of the above-mentioned items.

(5) Any one of the above (1) to (4)
The silver halide photographic light-sensitive material according to item 1 was adjusted to a pH of 9.0 to 9.0.
By processing with a developer of 11.0, a gamma of 10
A method for processing a silver halide photographic light-sensitive material, characterized by forming the above-mentioned high contrast image.

(6) The processing is carried out with a replenishing amount of the developing solution of 30 to 150 ml per m ^{2 of the} photosensitive material and a replenishing amount of the fixing solution of 50 to 300 ml per m ^{2 of the} photosensitive material.
The method for processing a silver halide photographic light-sensitive material described in the above.

(7) Total processing time of the photosensitive material (Dry t
o Dry) is 10 to 60 seconds, wherein the method for processing a silver halide photographic light-sensitive material according to the above (5) or (6),

(8) The washing step is a multi-stage countercurrent type having two or more steps, and the replenishing amount of the washing water or the stabilizing replenisher is 50 to 400 ml per 1 m ^{2 of the} light-sensitive material. A method for processing a silver halide photographic light-sensitive material according to any one of the above (7) to (7).

Hereinafter, the present invention will be described in detail.

The urethane latex used in the present invention is selected from the group consisting of polyisocyanates, polyols and reaction products of various organic acids.

Preferred polyisocyanates are adducts made from monomers or organic diisocyanates, which can contain biuret, allophanate or urethane groups or isocyanate rings.

As the isocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2
4,4-trimethyl 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane-
1,3- and 1,4-diisocyanate isocyanatomethylcyclopentene, 1-isocyanate-3,3
Includes 5-trimethyl-5-isocyanatomethylcyclohexane, 2,4-hexahydrotoluene diisocyanate, 5,6-hexahydrotoluene diisocyanate and mixtures of isomers thereof. Also, 2,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate , 2,6
-Tolylene diisocyanate, diphenylmethane-2,
4'- and / or 4,4'-diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenylpolymethylene polyisocyanate, etc. Can be included.

Preferred polyols include ethylene glycol, 1,2-propylene glycol,
3-propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
Includes 2,2-dimethyl-1,3-propylene glycol, glycerin, trimethylolpropane, and the like.

In order to make these urethane polymers water-dispersible, it is necessary to incorporate organic acids into the polymers via chemical bonds. Preferred organic acids are at least one isocyanate-reactive hydrogen and at least one hydrophilic group, for example an aliphatic hydroxycarboxylic acid, an aminocarboxylic acid having an aliphatic or aromatic primary or secondary amino group. And aliphatic hydroxysulfonic acids, and aminosulfonic acids having an aliphatic or aromatic primary or secondary amino group, but the present invention is not limited to these.

The above-mentioned polyisocyanates and polyols may be used in various combinations from the viewpoints of solubility of the polyadduct, hydrophilicity or hydrophobicity, compatibility with the hydrophilic colloid, and easy production of the polyadduct. Choice is possible.

These urethane latexes are described in "Polyurethane Handbook" by Gunter Otel (G
unter Oertel: Polyurethane
Handbook) p. 21 (1985), edited by Shunsuke Murahashi et al., “Synthetic Polymers” V p. The compounds can be synthesized under various conditions with reference to the methods described in 309 to 359 and the like.

The urethane latex according to the present invention has a weight average molecular weight of 5 × 10 ³ or more, preferably 1 × 10 ^{4 to} 5 × 10 ⁶ .

In the present invention, the urethane latex can be added in any amount of 0.01 to 1.5 times the total gelatin amount on the silver halide emulsion layer side. If the amount of the urethane latex is at least 1.5 times the amount of the gelatin, the ultra-high contrast photographic characteristics using the hydrazine derivative in the present invention will not be obtained, and will cause coating failure. or,
If it is less than 0.01 times, the effect of the present invention cannot be obtained. The amount of the urethane latex that provides the effect of the present invention satisfactorily is 0.1 to the total amount of gelatin on the silver halide emulsion layer side.
It may be 1 to 1.2 times, more preferably 0.2 to 1 times.
It is 0 times.

In the light-sensitive material of the present invention, the total amount of gelatin on the silver halide emulsion layer side is from 1.1 to 3.6 g / m ² , preferably from 1.1 to 3.0 g / m ² , more preferably from 1.1 to 3.0 g / m ^2. Is from 1.5 to 2.8 g / m ² . The term "emulsion layer side" as used herein means, for example, a photosensitive emulsion layer, a non-light-sensitive emulsion layer, a protective layer of the same emulsion layer, an intermediate layer, an undercoat layer, a dye layer, an antistatic layer and the like, which are necessary layers for a usual photosensitive material. .

Next, specific examples of the compound of the urethane latex used in the present invention are shown, but the present invention is not limited thereto.

Preferred examples of the water-soluble polyadduct of the present invention are exemplified by non-dissociated carboxylic acids, but the present invention is not limited thereto. (The numbers in parentheses indicate the molar ratio of each component).

P-1: 2,2-bis (hydroxymethyl) propionic acid / 4,4'-diphenylmethane diisocyanate (50/50) polyadduct P-2: 2,2-bis (hydroxymethyl) propion Acid / tolylene diisocyanate (50/50) polyadduct P-3: 2,2-bis (hydroxymethyl) propionic acid / hexamethylene diisocyanate (50/50) polyadduct P-4: 2,2 -Bis (hydroxymethyl) propionic acid / 1,5-naphthylene diisocyanate (50/5
0) Polyadduct P-5: 2,2-bis (hydroxymethyl) propionic acid / isophorone diisocyanate (50/50) polyadduct P-6: 2,2-bis (hydroxymethyl) propionic acid / m -Tetramethylxylylene diisocyanate (5
0/50) polyadduct P-7: 2,2-bis (hydroxymethyl) propionic acid / 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol (32.5 / 40 / 10 / 17.5) Polyadduct P-8: 2,2-bis (hydroxymethyl) propionic acid / 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate (50/45/5) polyadduct P-9: 2,2-bis (hydroxymethyl) propionic acid / 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / 1,4-butanediol (42.5 / 35/15 / 7.5 ) Polyadduct P-10: 2,2-bis (hydroxymethyl) propionic acid / 4,4'-diphenylmethane diisocyanate /
Hexamethylene diisocyanate / triethylene glycol (35/40/10/15) polyadduct P-11: 2,2-bis (hydroxymethyl) propionic acid / 4,4'-diphenylmethane diisocyanate (50 / 50) Polyadduct P-12: 2,2-bis (hydroxymethyl) butanoic acid / tolylene diisocyanate (50/50) polyadduct P-13: 2,2-bis (hydroxymethyl) butanoic acid / Hexamethylene diisocyanate (50/50) polyadduct P-14: 2,2-bis (hydroxymethyl) butanoic acid / 1,5-naphthylene diisocyanate (50/50)
Polyadduct P-15: 2,2-bis (hydroxymethyl) butanoic acid / isophorone diisocyanate (50/50) polyadduct P-16: 2,2-bis (hydroxymethyl) butanoic acid / m-tetra Methyl xylylene diisocyanate (50
/ 50) polyadduct P-17: 2,2-bis (hydroxymethyl) butanoic acid / 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol (32.5 / 40/10 / 17.5) Polyadduct P-18: 2,2-bis (hydroxymethyl) butanoic acid / 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / (50/45/5) polyadduct P -19: 2,2-bis (hydroxymethyl) butanoic acid / 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / 1.4-butanediol (42,5 / 35/15 / 7.5) Polyadduct P-20: 2,2-bis (hydroxymethyl) butanoic acid / 4,4'-diphenylmethane diisocyanate / hexamethylene Diisocyanate / triethylene glycol (35/40/10/15) polyadduct In the light-sensitive silver halide emulsion layer and / or hydrophilic colloid layer of the light-sensitive material of the present invention, at least one hydrazine derivative is contained. It is preferable to be contained.

The hydrazine derivative preferably used in the present invention includes a compound represented by the following general formula (H).

[0031]

Embedded image

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

Of the compounds represented by the general formula (H), more preferred are the compounds represented by the following general formula (Ha).

[0034]

Embedded image

In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, chenyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

The ballast group is preferably a ballast group commonly used in immobile photographic additives such as couplers, and is relatively inert to photographic properties having 8 or more carbon atoms, such as an alkyl group, an alkenyl group, and an alkynyl. Groups, alkoxy groups, phenyl groups, phenoxy groups, alkylphenoxy groups and the like.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, Xs may be the same or different.

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

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

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

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

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

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

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization, the type of the inhibitor, etc., it is generally 10 ^-6 to 10 ^-1 per mol of silver halide.
Molar range, preferably from 10 ^-5 to 10 ^-2 mol.

In the present invention, the hydrazine derivative is preferably added to at least one of the light-sensitive silver halide emulsion layer and / or the hydrophilic colloid layer, and more preferably, the light-sensitive silver halide emulsion layer and / or the same. Adjacent layer,
More preferably, it is added to the photosensitive silver halide emulsion layer.

In order to effectively promote the contrast enhancement by the hydrazine derivative, a quaternary onium compound having a quaternary nitrogen compound and / or a quaternary phosphorus compound in the structure, an amine compound, or an alcohol compound having a molecular weight of 120 or more is selected. It is preferable to use at least one nucleation accelerator used.

In the present invention, in order to effectively promote the contrast enhancement by the hydrazine derivative, the following general formula [Na]
Alternatively, it is preferable to use a compound represented by [Nb].

[0061]

Embedded image

In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group. R ₁ , R ₂ and R ₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable.

Preferred examples of the silver halide-adsorbing group include a heterocyclic group-containing compound, a mercapto group, a thioether group, a thione group and a thiourea group. General formula [Na]
Particularly preferred are compounds having at least one thioether group as a silver halide adsorptive group in the molecule.

Hereinafter, these compounds represented by the general formula [Na]
The following is a specific example.

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
And R ₄ may be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Specific compounds of the general formula [Nb] include the following.

[0070]

Embedded image

[0071]

Embedded image

Specific examples of other preferable compounds are described in JP-A-6-258755, page (13), “0062” to (1).
5) (2-1) to (2) described on page “0065”
-20) and the compound of JP-A-6-258755 (15)
3-1 to 3-6 described on page “0067” to (16) page “0068”.

The above-mentioned compound preferably used in the present invention may be used in any layer as long as it is a photographic constituent layer on the side of the silver halide emulsion layer, and can be used in the same manner as in the above-mentioned hydrazine derivative. Also, two or more kinds may be used in combination.

The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like, but is generally 10 ^-6 per mol of silver halide.
The range is preferably 10 to 10 ^-1 mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

Next, the quaternary onium salt compound used in the silver halide photographic light-sensitive material of the present invention will be described. The quaternary onium salt compound used in the present invention is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in a molecule, and is preferably a compound represented by the following formula (P).

[0076]

Embedded image

In the formula, Q represents a nitrogen atom or a phosphorus atom;
₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Further, R _{1 to} R ₄ may be linked to each other to form a ring.

As the substituent represented by R _{21 to} R ₂₄ , an alkyl group (for example, methyl, ethyl, propyl, butyl,
Hexyl, cyclohexyl group, etc.), alkenyl group (eg, allyl, butenyl group, etc.), alkynyl group (eg, propargyl, butynyl group, etc.), aryl group (phenyl, naphthyl group, etc.), heterocyclic group (eg, piperidinyl, piperazinyl, morpholinyl, Pyridyl, furyl, thienyl,
Tetrahydrofuryl, tetrahydrothienyl, sulfolanyl group and the like), amino group and the like. Examples of the ring that can be formed by connecting R _{21 to} R ₂₄ to each other include a piperidine ring, a morpholine ring, a piperazine ring, a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, and the like. Groups represented by R ₂₁ to R ₂₄ is a hydroxyl group, an alkoxy group, an aryloxy group,
It may have a substituent such as a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ , 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.

The quaternary onium salt compounds used in the present invention include the following general formulas (Pa), (Pb) and (Pc)
Or a compound represented by the following general formula [T].

[0082]

Embedded image

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 carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. A ¹ , A ² ,
Preferred examples of A ³ , A ⁴ and A ⁵ include 5- to 6-membered rings (rings such as pyridine, imidazole, thiazole, oxazole, pyrazine and pyrimidine), and a more preferred example is a pyridine ring. .

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

R ¹ , R ² and R ⁵ each represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. As the substituent,
The substituents are the same as those 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 are each an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0086] X _p ^- is a counter ion necessary to balance the charge of the whole molecule, for example chloride, bromide,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. n _p represents the number of counter ions required to balance the charge of the entire molecule, and n _p is 0 in the case of an internal salt.

[0087]

Embedded image

The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value for the phenyl group is described in many literatures, for example, Journal of Medical C
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 salt compounds will be shown below, but the present invention is not limited thereto.

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

The above quaternary onium salt compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews. 55. p.
335-483 can be referred to.

The addition amount of these quaternary onium salt compounds is as follows:
The amount is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol, per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating. The amount added to the hydrophilic colloid layer may be an amount according to the above silver halide emulsion layer.

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

The light-sensitive material of the present invention has a pH of 9.0 to 11.1.
By processing with a developing solution of 0, a high-contrast image having a gamma of 10 or more can be formed.

The pH of the developer is preferably in the range of 9.0 to 11.0, more preferably in the range of 9.5 to 10.6. The effect of the present invention is not exhibited in a pH range other than this.

In the present invention, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material in response to a demand for reducing the amount of waste liquid. The replenishing amount of the developing solution is 30 to 150 ml per 1 m ^{2 of} the photosensitive material to be processed, and more preferably 50 to 150 ml.
１３０130 ml. The replenishing amount of the fixing solution is 50 to 300 ml per 1 m ^{2 of} the photosensitive material to be processed, and more preferably 1 to ² ml.
It is 00 to 250 ml.

The replenishing amount of the developing solution and the replenishing amount of the fixing solution as referred to herein indicate the amount of the replenishing solution. Specifically, the replenishing amounts of the respective solutions when the same solution as the developing mother liquor and the fixing mother liquor are replenished. And the total amount of each concentrated solution and water when the concentrated solution for development and the concentrated solution for fixing are replenished with a solution diluted with water.

In the case of a solid developing agent and a solid fixing agent, the total amount of the volume of each solid processing agent and the volume of water when replenished with a solution dissolved in water is used. This is the total amount of the respective solid processing agent volumes and water volumes when the fixing processing agent and water are 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 almost constant, the calculated addition of the solid processing agent and the balance of the components are achieved.

According to the processing method of the present invention, after the development and the fixing,
Preferably, it is treated in a washing and / or stabilizing bath.
As a stabilizing bath, the film pH is used to stabilize the image.
(For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, etc.) Sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid,
Malic acid, acetic acid, etc. used in combination), aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetic acid salt, polyphosphate, etc.), Fungicides (for example, phenol, 4-chlorophenol, cresol, o-phenylphenol, chlorophen, dichlorophen, formaldehyde, p-hydroxybenzoate, 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 adjuster and / or Or a residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent, specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzol Thiazole, 2-mercapto-5-propyl-1,3,3
4-triazole, 2-mercaptohypoxanthine, etc.)
Is contained. Among them, the stabilizing bath preferably contains a fungicide. These may be replenished in liquid or solid form. The replenishment amount is 5 per m ^{2 of} photosensitive material.
It is 0 to 400 ml.

In the processing method of the present invention, the washing tank or the stabilizing tank is preferably constituted by a large number of two or more tanks in order to improve the washing efficiency in view of the demand for shortening the developing time. Preferably composed of 2 to 6 tanks, more preferably 2 to 4 tanks,
And a carry-in amount of 2 to 50 volumes per unit area of the photosensitive material for processing the amount of washing water or stabilizing replenisher per unit area,
It is preferable to replenish it in a multistage countercurrent system in an amount of 3 to 30 times.

In this case, the replenishment amounts of the washing water and the stabilizing replenisher are preferably 50 to 400 ml, and more preferably 70 to 200 ml, per m ² of the photographic material.

In the present invention, processing is carried out using an automatic developing machine because 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, the steps required for processing, such as development, fixing, washing or rinsing, and drying. Time including all of the above, that is, Dry to
It is the time of Dry.

If the total processing time is less than 10 seconds, desensitization, softening, etc. occur, and satisfactory photographic performance cannot be obtained. Preferably, the total processing time is 15 seconds to 44 seconds. Also one
In order to stably process a large amount of photosensitive material of 0 m ² or more, the development time is preferably 2 seconds to 18 seconds.

The light-sensitive material of the present invention is most effective when used as an output light-sensitive material.
An r laser, a He-Ne laser, a red laser diode, an infrared semiconductor laser, and a red LED laser are typical, but other arbitrary lasers such as a blue laser such as a He-Cd laser can be used. The effects of the present invention are not limited to laser output photosensitive materials, but are also effective in applications such as photographic photosensitive materials and return photosensitive materials.

In the silver halide photographic light-sensitive material of the present invention, sulfur sensitization, Se, Te sensitization, reduction sensitization and noble metal sensitization, which are generally known for a photosensitive silver halide emulsion, are appropriately selected. May be 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. Further, an oxidizing agent for silver can be used in the production process of the photosensitive material.

The light-sensitive material of the present invention is preferably pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or silver chloroiodobromide containing 60 mol% or more of silver chloride as a halogen composition. .

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, this means particle diameter. If the particle is a cube, convert it to a sphere,
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. Jam
by es: The theory of the photo
ographic process, 3rd edition, 36-4
See page 3 (1966, published by Mcmillan).

The shape of the silver halide grains is not limited, and may be any of a flat plate shape, a spherical shape, a cubic shape, a tetrahedral shape, a regular octahedral shape, and any 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.

In at least one of the steps of forming or growing the silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, rhodium salts, ruthenium salts, osnium salts, iron salts, It is preferable to add a complex salt containing an element of Groups 3 to 13 of the periodic table, such as a copper salt, a platinum salt, and a palladium 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 alkoxy group, an ammonium group, and any combination thereof can be used. The surface of the silver halide grains can be controlled in halogen composition by 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 light-sensitive material of the present invention, the silver content of the silver halide emulsion layer is preferably from 2.0 to 3.5 g / m ² , more preferably from 2.5 to 3.5 g / m ² . When the silver content is high, the running stability is poor, and when the silver content is low, a sufficient density cannot be obtained.

The silver halide emulsion can be spectrally sensitized to a desired wavelength by using 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, and the like are mentioned, and an alicyclic hydrocarbon ring is fused to these nuclei. Nucleus, nucleus fused with aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-2,4-dione nucleus, thiazolidine-2,4-nucleus are used as nuclei having a ketomethylene structure.
A 5- to 6-membered heterocyclic ring such as a 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 4,425,425
And Nos. 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. 5,634.

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 (RD) 17643 (published December 1978), page 23.
It is described in section J of IV.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7). -Tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, potassium bromide and the like. Can be. Particularly preferred are substituted or unsubstituted heterocyclic or fused heterocyclic rings containing any of N, O, S, and Se, and water-soluble halides.

The emulsion layer and the non-photosensitive hydrophilic colloid of the light-sensitive material of 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 (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.),
Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β-
(Vinylsulfonyl) propionamide]), an active halogen compound (2,4-dichloro-6-hydroxy-s)
-Triazines, etc.), mucohalic acids (mucochloric acid,
Phenoxime cochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, isocyanates, carboxyl group-active hardeners and the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer may be coated with various known additives for various purposes such as coating aid, antistatic, improvement of slipperiness, emulsification dispersion, prevention of adhesion and improvement of photographic properties. Surfactants may be used.

In the light-sensitive material of 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.

Gelatin is advantageously used 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, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group, an amide group, etc., and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, ₁ NR ₂ -R ₃ (R ₁ , R ₂ and R ₃ may be different from each other, a hydrogen atom, an aliphatic group, an aromatic group, a sulfinic acid residue, a carbonyl group, an oxalyl group,
Carbamoyl group, amino group, sulfonyl group, sulfoxy group, iminomethylene group, alkenyl group, alkynyl group,
An arbitrary group bonded through an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, etc.), a cation 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 photosensitive material of the present invention contains various other additives. For example, desensitizers, plasticizers, development accelerators, oils, sliding agents, 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 of 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. In these layers, a state in which a water-soluble or water-insoluble dye, an imagewise or non-imagewise development adjusting (suppression or acceleration) agent, a contrasting agent, a physical property adjusting agent, etc. are dissolved in an aqueous solution or an organic solvent, Alternatively, it can be contained in a form dispersed in solid fine particles (which may or may not be 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 light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one or both sides of a flexible support usually used for the light-sensitive material. Useful as flexible supports are films of synthetic polymers of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate (which may contain colored content), or polyethylene or polyethylene. Paper supports coated with polymers such as terephthalate. These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

The developing agents which can be used in the processing method of the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5
-Dimethylhydroquinone, etc.), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N
-Methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1- (p-hydroxyphenyl)- 3
-Aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-
Methylphenyl) -3-aminopyrazoline, etc.), transition metal complexes (Ti, V, Cr, Mn, Fe, Co, Ni,
It is a complex salt of a transition metal such as Cu. These may have a reducing power to be used as a developer.
It is in the form of a complex salt such as i ³⁺ , V ²⁺ , Cr ²⁺ , Fe ²⁺ , and the ligand is an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) and the like. Salts, phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid, and salts thereof, and the like. And the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid; It is preferable to use a combination of an aminophenol and ascorbic acid, a combination of a 3-pyrazolidone and a transition metal complex, or a combination of an aminophenol and a transition metal complex. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

In the processing method of the present invention, a silver sludge inhibitor is disclosed in JP-B-62-4702 and JP-A-3-51.
No. 844, No. 4-26838, No. 4-362942
And compounds described in JP-A No. 1-319031 and the like can be used.

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 light-sensitive material of the present invention can be processed while energizing. 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. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

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 alkaline 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 (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. The pH of the developer is preferably adjusted to 8.5 to 12.0, and particularly preferably adjusted to 9.0 to 10.9.

The developing solution used in the processing method of the present invention may not substantially contain a dihydroxybenzene compound. In this case, it is preferable that a compound represented by the following general formula (B) is contained.

[0149]

Embedded image

[0150] Each R _11, R ₁₂ in the general formula (B), expressed independently substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, R _11, R ₁₂ may combine with each other to form a ring.
k represents 0 or 1, and when k is 1, X is -CO- or-
Represents a CS- group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Among the compounds represented by the general formula (B), a compound represented by the following general formula (Ba) in which R ₁₁ and R ₁₂ are bonded to each other to form a ring is preferred.

[0152]

Embedded image

In the above formula (Ba), R ₁₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group. , A sulfo group, a carboxy group, an amide group, represents a sulfonamide group, Y ₁₁ represents O or S,
Y ₁₂ represents O, S or NR ₁₄ . R ₁₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M
₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Examples of the substituent of the alkyl group include a halogen atom (for example, Cl, Br and the like), a hydroxy group, an aryl group having 6 to 20 carbon atoms (for example, phenyl and naphthyl group), and a heterocyclic group (for example, 2 , 2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc., C1-C20 alkoxy group (for example, methoxy group, ethoxy group, etc.), An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), 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 (for example, pyridyloxy group), acylamino group having 1 to 26 carbon atoms (for example, acetylamino, heptylamino, propionylamino group) ), Amino group (e.g. amino, methylamino, dimethylamino, dibenzylamino group, etc.)
And the like.

Examples of the substituent of the amino group include a halogen atom (for example, Cl, Br and the like), a hydroxy group, an aryl group having 6 to 20 carbon atoms (for example, a phenyl group and a naphthyl group), a C1 to C20 group and the like. An alkyl group such as methyl,
Ethyl, butyl, cyclohexyl, isopropyl, dodecyl group, etc., heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.) , Carbon number 1-2
0 alkoxy groups (for example, methoxy, ethoxy group, etc.),
An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), 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), Examples include a heterocyclic oxy group (for example, a pyridyloxy group) and an acyl group having 1 to 20 carbon atoms (for example, an acetyl group, a heptyl group, a propionyl group, and the like).

Examples of the substituent of the alkylthio group include a halogen atom (eg, Cl, Br, etc.), a hydroxy group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl group,
A naphthyl group, etc., a heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N'-
Diethylpyrazolidinyl group, pyridyl group, etc.), carbon number 1
An alkoxy group (e.g., methoxy group, ethoxy group, etc.), an aryloxy group having 6-20 carbon atoms (e.g., phenoxy group), an alkenyloxy group having 1-20 carbon atoms (e.g., allyloxy group, etc.), 1 carbon atom Alkynyloxy group (for example, propargyloxy group), heterocyclic oxy group (for example, pyridyloxy group), carbon number of 1-26
(E.g., acetylamino, heptylamino, propionylamino, etc.) and amino (e.g., amino, methylamino, dimethylamino, dibenzylamino, etc.).

Examples of the substituent of the aryl group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group,
An alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl,
Butyl, cyclohexyl, isopropyl, dodecyl group, etc.), heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolidinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), carbon An alkoxy group having 1 to 20 carbon atoms (such as a methoxy group or an ethoxy group), an aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), An alkynyloxy group having 1 to 20 atoms (eg, propargyloxy group), a heterocyclic oxy group (eg, pyridyloxy group), an acylamino group having 1 to 26 carbon atoms (eg, acetylamino, heptylamino, propionylamino group, etc.); An amino group (eg, an amino group,
Methylamino group, dimethylamino group, dibenzylamino group, etc.).

Examples of the substituent of the alkoxy group include:
A halogen atom (eg, Cl, Br, etc.), a hydroxy group,
An aryl group having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group, etc.), an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, butyl group, cyclohexyl group, isopropyl group, dodecyl group, etc.), heterocyclic ring 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), carbon atom An alkynyloxy group having the number of 1 to 20 (eg, propargyloxy group), a heterocyclic oxy group (eg, a pyridyloxy group), and a carbon number of 1 to 26;
(E.g., acetylamino, heptylamino, propionylamino, etc.) and amino (e.g., amino, methylamino, dimethylamino, dibenzylamino, etc.).

Examples of the substituents of the 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
Alkoxy group (for example, methoxy group, ethoxy group, etc.),
An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), 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 (for example, pyridyloxy group), acylamino group having 1 to 26 carbon atoms (for example, acetylamino, heptylamino, propionylamino group, etc.), amino group (for example, amino, methylamino, dimethylamino, dibenzylamino group, etc.) )
And the like.

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

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

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 image forming method of the silver halide photographic light-sensitive material of the present invention, development substantially free of hydroquinones (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate) is performed. Liquid can be used. The term "substantially not contained" means an amount of less than 0.01 mol per liter of the developer.

In the present invention, a developing agent comprising the transition metal complex salt according to the present invention and 3-pyrazolidones (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are usually used in an amount of 0.01 to 1.4 per liter of developer.
It is preferably used in molar amounts.

The inhibitor which can be used in the image forming method for a silver halide photographic light-sensitive material of the present invention is 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 of the present invention are not limited to the following. Specifically, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, an imidazole compound,
Benzimidazole compounds, pyrazole compounds, indazole compounds, triazole compounds, benzotriazole compounds, tetrazole compounds, pyrimidine compounds, triazine compounds, quinoline compounds, quinarizone compounds,
Examples include a purine compound and the like, and any compound may have a substituent and a mercapto group. Examples of the substituent include, but are not limited to, a methyl group, a sulfo group, a nitro group, an amino group, a carboxy group, a hydroxy group, a phenyl group, and a halogen atom. The amount of 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 of the present invention, a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is used in an activator processing solution for processing in an aqueous alkali solution to perform development. You may. 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 capable of softening water. 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 containing a stabilizer 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.

As the mother liquor or replenisher of the developing solution, the fixing solution, or the stabilizing solution, it is common to supply the working solution or the concentrated solution diluted immediately before, but the stock of the mother liquor or the replenisher 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 the tablet-formed product to the dissolution layer or the direct treatment layer is a workability,
This method is extremely excellent in terms of space saving and preservation, and can be particularly preferably used.

In the drying zone of the automatic developing machine, a method of drying with 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. (Such as 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 of the present invention), or those having known drying means such as a dehumidifier, a microwave generator, and a water-absorbing resin. . Further, a control mechanism for a dry state may be provided.

[0175]

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

Example 1 (Preparation of Silver Halide Emulsion A1) Using a double jet method, 70 mol% of silver chloride, the balance consisting of silver bromide having an average diameter of 0.0
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 mol of silver to 1 mol of silver at the end of grain formation in the presence of 80 μg.
An aqueous silver nitrate solution and a water-soluble halide solution were mixed at the same temperature while maintaining the same at 165 mV and a pH of 3.0 silver potential (EAg).

The 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.
Was added. 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% silver chloride, iodine iodine) having an average diameter of 0.15 μm. (A silver bromide of 0.2 mol%, the balance being silver bromide). Then, Japanese Patent Laid-Open No. 2-2
No. 80139, denatured gelatin (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-
Desalting was performed using 8). EAg after desalting is 190 at 50 ° C.
mV.

The resulting emulsion was added with 100 mg of potassium bromide per mole of silver and citric acid to adjust the pH to 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 Corporation; saponin added using PM-1200 and dispersed to an average of 0.5 μm) was 0.6 m / mol of silver.
g and 6 mg of chloroauric acid, and then chemically ripened at a temperature of 55 ° C. until the maximum sensitivity was obtained. At 40 ° C., 200 mg of sensitizing dye d-1 was added, and 4-hydroxy-6-methyl- 600 mg of 1,3,3a, 7-tetrazaindene (TAI) per mole of silver, 20 mg of 1-phenyl-5-mercaptotetrazole and 300 mg of potassium iodide
After adding mg, 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 prepared with a gelatin content of 0.1%.
Such that 55 g / m ^2, further amount of silver 3.4 g / m ² of silver halide emulsion layers of the formulation 2 as an upper layer, so that the amount of gelatin is 1.32 g / m ^2, further having the following formulation 3 The coating solution for the protective layer was simultaneously and multi-layer coated so that the amount of gelatin became 1.5 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 100 m / min by a curtain coating method so as to obtain a layer 2 and then 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 0.55 g / m ² 1-phenyl-5-mercaptotetrazole 2.0 mg / m ² Fungicide Z 0.5 mg / m ² Dye 1-25 (solid dispersion) 12 mg / M ² prescription 2 (composition of silver halide emulsion layer) Silver halide emulsion A-1 3.4 g / m ² equivalent of silver amount Hydrazine compound shown in Table 1 Amount shown in Table 1 Activator (S-1) sodium -Iso-amyl-n-decylsulfosuccinate 2 mg / m ² 2-mercaptohypoxanthine 2 mg / m ² nicotinamide 1 mg / m ² gallic acid n-propyl ester 50 mg / m ² mercaptopyrimidine 1 mg / m ² EDTA 25 mg / m ² polymer latex L4 0.65 g / m ² polymer latex L6 0.9 g / m ² dye k 23 mg / m ² (gelatin phthalated gelatin Formulation 3 (Emulsion protective layer composition) Gelatin 1.5 g / m ² activator (S-1) 27 mg / m ² Activator b 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 amorphous silica 13 mg / m ² amine exemplified compound Na-21 12.5 mg / m ² hydroquinone 100 mg / m ² colloidal Silica (average particle size 0.05 μm) 250 mg / m ² Slip agent (silicone oil) 25 mg / m ² Compound a 50 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 Urethane latte of the present invention Amount shown in Table 1 Formulation 4 (composition of backing layer) Gelatin 1.9 g / m ² Activator (S-1) 5 mg / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (mean particle size 0.05 μm) 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 hardener h3 50 mg / m ² Zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² Prescription 5 (backing protective layer) Gelatin 0.6 g / m ² Matting agent: Monodispersed polymethyl methacrylate 50 mg / m ^{2 having an} average particle size of 5 μm Matting agent: Average particle size 3 μm Variable silica 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² active agent (S-1) 1mg / m 2 Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² Compound a 50 mg / m ² hardener h1 64 mg / m ² sodium polystyrenesulfonate 10mg / m ² The thus obtained sample was used as a light source at 633 nm.
1.5 with a laser sensitometer using a He-Ne laser
Step exposure was performed while changing the amount of light at × 10 ⁻⁷ seconds, and processing was carried out using a processing agent having the following formulation under the following conditions using an automatic developing machine GR-27 manufactured by Konica Corporation.

[0181] The PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).

Further, in order to evaluate the reproducibility of minute halftone dots of the sample thus obtained, 3000 dpi / 300 l using an FTR3050Q manufactured by Dainippon Screen Co., Ltd.
Pi is set to output a small point (5% halftone dot), a middle point (50% halftone dot), a large point (95% halftone dot), and a solid (100% halftone dot). Exposure was performed while changing, and the same processing was performed. X-R for the obtained developed sample
The net% was measured with item 361T.

Further, in order to evaluate the scratch resistance, 2400 using FTR3050Q manufactured by Dainippon Screen Co., Ltd.
The medial point (50% halftone dot) was set to be output to a large size at dpi / 200 lpi, and one roll sample of 558 mm × 61 m was continuously processed, and the occurrence of scratches was visually evaluated.

(Developer composition) Diethylene-triamine pentaacetic acid / pentasodium salt 1 g per liter of working solution 1 g Sodium sulfite 42.5 g Potassium sulfite 17.5 g Potassium carbonate 55 g Hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl -3-pyrazolidone 0.85 g potassium bromide 4 g 5-methylbenzotriazole 0.2 g boric acid 8 g diethylene glycol 40 g 8-mercaptoadenine 0.3 g KOH was added so that the pH of the working solution became 10.4.

(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.

[0187] (Evaluation of gamma) Gamma is represented by a tangent between densities of 0.1 and 3.0, and indicates that a super-high contrast image can be obtained only when the gamma value in the table is 10 or more.

(Evaluation method of dot reproducibility of small dot) Small dot (target dot% 5%) at an exposure amount giving a solid density of 5.0
Shows the% of dots actually reproduced on the sample. The value in the table is 5
The closer to%, the better.

(Evaluation of Scratch Resistance) As described above, 55
One roll sample of 8 mm x 61 m was processed (approximately 10
0), and the total number of blackening flaws generated was counted. Naturally, the smaller the number, the better. If it exceeds 8, it is a practically problematic level. Table 1 shows the obtained results.

[0190]

[Table 1]

As is clear from Table 1, the sample of the present invention has excellent scratch resistance and gamma and excellent reproducibility of fine halftone dots.

Example 2 (Preparation of Silver Halide Emulsion B1) Using a double jet method, 70 mol% of silver chloride, the balance consisting of silver bromide having an average diameter of 0.1 was used.
2 μm silver chlorobromide core particles were prepared. At the time of mixing the core particles, K ₃ Rh (N0) ₄ (H ₂ O) ₂ was added in an amount of 50 μg per mole of silver to 1 mole of silver at the end of grain formation in the presence of 80 μg.
An aqueous silver nitrate solution and a water-soluble halide solution were mixed at the same temperature while maintaining the same at 165 mV and a pH of 3.0 silver potential (EAg).

EAg was added to the core particles with a salt solution for 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.
Was added. 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 (silver chloride: 70 mol%, iodine: 0.19 μm). (A silver bromide of 0.2 mol%, the balance being silver bromide). Then, Japanese Patent Laid-Open No. 2-2
No. 80139, denatured gelatin (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-
Desalting was performed using 8). EAg after desalting is 190 at 40 ° C.
mV.

1 g of potassium bromide and 1 g of citric acid were added to 1 mol of silver to the obtained emulsion to give a pH of 5.6 and EAg.
The reaction was adjusted to 123 mV by adding 170 mg of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) to 1 mol of silver. Then, an inorganic sulfur (S8) compound dispersed in a solid (Seisin Corporation; saponin added using PM-1200 and dispersed to an average of 0.5 μm) was added in an amount of 0.6 m per mol of silver.
g and 6 mg of chloroauric acid, and then chemically ripened at a temperature of 52 ° C. until the maximum sensitivity was obtained. At 40 ° C., 180 mg of sensitizing dye d-1 and 90 mg of d-10 were added, and TA was added.
I, 600 mg per mole of silver, 20 mg of 1-phenyl-5-mercaptotetrazole and 3 mg of potassium iodide
After adding 00 mg, 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 6 having a gelatin content of 0.
The silver halide emulsion layer of Formula 7 was further added thereon so as to have a silver amount of 3.4 g / m ² and a gelatin amount of 1.07 g / m ² so as to have a silver content of 3 g / m ² and 3 g / m ² . The coating solution for the protective layer was simultaneously and multi-layer coated so that the amount of gelatin became 1.05 g / m ² . On the other side of the undercoat layer, the following formulation 9
The backing layer of No. 1 was made to have a gelatin amount of 1.3 g / m ^2, and the backing protective layer of the following formula 10 was coated with the emulsion layer side so as to have a gelatin amount of 0.5 g / m ² by curtain coating. After the simultaneous coating of the emulsion layer side at a speed of 200 m / min and cooling setting, the backing layer side was simultaneously coated with the multilayer coating, and then cooled and set at -1 ° C., and both sides were simultaneously dried to obtain a sample.

Formulation 6 (Gelatin undercoat layer) Gelatin 0.3 g / m ² 1-phenyl-5-mercaptotetrazole 2.0 mg / m ² Fungicide Z 0.5 mg / m ² Dye 1-25 (solid dispersion) 5 mg / M ² prescription 7 (composition of silver halide emulsion layer) Silver halide emulsion B-1 silver amount 3.4 g / m ² equivalent hydrazine compound H-30 10 mg / m ² activator (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 polymer latex L6 0.85 g / m ² dye k 10mg / m ² (gelatin phthalated gelatin PH of the coating solution used was 4.8) Formulation 8 (Emulsion protective layer composition) Gelatin 1.05 g / m ² active agent b 0.5 mg / m ² Matting agent:. An average particle size 3.5μm spherical polymethyl Methacrylate 15 mg / m ² Average particle size 8 μm Irregular silica 13 mg / m ² Amine compound shown in Table 2 Amount shown in Table 2 Quaternary onium compound P-27 5 mg / m ² Sliding agent (silicone oil) 25 mg / m ² KBr 50 mg / m ² Compound P 10 mg / m ² Compound S 200 mg / m ² Hydroquinone 100 mg / m ² Colloidal silica (mean particle size 0.05 μm) 200 mg / m ² Hardener h4 40 mg / m ² Hardener h2 90 mg / m the amount formulations shown in ² activator G 20 mg / m ² fungicide Z 0.5 mg / m ² 2-mercapto urethane latex table 2 hypoxanthine 30 mg / m ² the invention (Backing layer composition) Gelatin 1.3 g / m ² (activator) S-1 5mg / m ² Polymer latex L6 0.8 g / m ² of sodium polystyrenesulfonate 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 hardener h3 50 mg / m ² zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² formulation 10 (backing protective layer) gelatin 0. 5 g / m ² matting agent: monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² average particle size 3 μm amorphous silica 12.5 mg / m ² activator G 20 mg / m ² fluorine-based surfactant F-16 20 mg / M ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² Compound a 50 mg / m ² Hard film Agent h4 50 mg / m ² The sample thus obtained was exposed in the same manner as in Example 1, and 120 ml of developing solution and 1 fixing solution per 1 m ^{2 of} the light-sensitive material were used.
The treatment was carried out under the same conditions as in Example 1 while replenishing 50 ml.

At the start of running and when the photosensitive material is 200 m ²
The same evaluation as in Example 1 was performed on the sample after running (the blackening ratio was 50%). In the table, before and after the run means before and after the running, respectively. Table 2 shows the obtained results.

[0198]

[Table 2]

As is clear from Table 2, the sample of the present invention has a low occurrence of scratches, and has excellent gamma and excellent reproducibility of minute halftone dots even after running a large number of sheets with low replenishment. I understand.

Example 3 The sample prepared in Example 2 was exposed in the same manner as in Examples 1 and 2, and an automatic developing machine GR using a developing solution and a fixing solution having the following compositions was used.
Rapid treatment was carried out using -26SR (manufactured by Konica Corporation) under the following conditions.

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

(Developer formulation) DTPA.5Na 3.6 g per liter sodium sulfite 25.0 g potassium sulfite 38.7 g potassium bromide 2.5 g potassium carbonate 40 g 8-mercaptoadenine 0.07 g diethylene glycol 50 g 5-methyl-benzo Triazole 0.15 g Hydroquinone 23 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (dimesone S) 0.8 g 1-phenyl-5-mercaptotetrazole 0.02 g Add water and potassium hydroxide to 1 liter / PH 10.4.

(Fixing solution formulation) Ammonium thiosulfate (72.5% W / V aqueous solution) per liter 262 g Water 79 g Sodium sulfite (anhydrous) 22 g Boric acid 9.8 g Sodium acetate trihydrate 38.5 g Tartaric acid 7.3 g Water Sodium oxide 0.25 g Aluminum sulfate (aqueous solution whose content in terms of Al ₂ O ₃ is 8.1% W / V) 32.9 g Adjust to pH 4.85 by adding glacial acetic acid or sulfuric acid, and add water to finish to 1 liter I got it.

Processing Conditions Rapid Processing (Step (Temperature) (Time) Development 35 ° C. for 12 seconds Fixing 35 ° C. for 10 seconds Rinse at room temperature for 10 seconds Drying at 50 ° C. for 15 seconds Total of 47 seconds The results obtained are shown in Table 3.

[0205]

[Table 3]

As is clear from Table 3, the sample of the present invention has excellent scratch resistance and gamma even when processed rapidly, and
It can be seen that the reproducibility of minute dots is excellent.

[0207]

Embedded image

[0208]

Embedded image

[0209]

Embedded image

[0210]

Embedded image

[0211]

Embedded image

[0212]

Embedded image

[0213]

As demonstrated in the examples, according to the present invention, silver halide having excellent scratch resistance and excellent gamma and excellent reproducibility of fine halftone dots even when subjected to low replenishment and rapid running of large amounts. A photographic material and a processing method thereof can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (for reference) G03C 5/31 G03C 5/31 11/00 11/00

Claims (8)

[Claims] 1. A silver halide photographic material comprising a support having at least one hydrophilic colloid layer containing at least one photosensitive silver halide emulsion layer, wherein at least one urethane latex is contained in the hydrophilic colloid layer. Contains, and
When the total amount of gelatin on the silver halide emulsion layer side is 1.1 to 3.
A silver halide photographic light-sensitive material, characterized in that the light-sensitive material has a weight of 6 g / m ² . 2. The amount of urethane latex in the hydrophilic colloid layer is 0.04 of the total amount of gelatin on the silver halide emulsion layer side.
2. The silver halide photographic light-sensitive material according to claim 1, wherein the ratio is 1 to 1.5 times. 3. The silver halide photographic material according to claim 1, wherein at least one hydrazine derivative is contained in the photosensitive silver halide emulsion layer and / or the hydrophilic colloid layer. . 4. The method according to claim 1, wherein the photosensitive silver halide emulsion layer and / or the hydrophilic colloid layer contains at least one kind of an amine compound and / or a quaternary onium compound. 4. The silver halide photographic light-sensitive material according to item 1. 5. A high contrast image having a gamma of 10 or more by processing the silver halide photographic light-sensitive material according to claim 1 with a developer having a pH of 9.0 to 11.0. A method for processing a silver halide photographic light-sensitive material, characterized by forming: 6. A replenishing amount of the developing solution is 30 per 1 m ^{2 of the} photosensitive material.
In ~ 150 mL, fixer replenishment rate is the light-sensitive material 1 m ² per 5
6. The method for processing a silver halide photographic light-sensitive material according to claim 5, wherein the processing is performed with 0 to 300 ml. 7. The processing time of the photosensitive material (Dry to
7. The method according to claim 5, wherein (Dry) is from 10 to 60 seconds. 8. The washing step is a multi-stage countercurrent type having two or more steps, and the replenishing amount of the washing water or the stabilizing replenisher is 1 m for the photosensitive material.
^The method for processing a silver halide photographic light-sensitive material according to any one of claims 5 to 7, wherein the amount per ² is 50 to 400 ml.