JP2000019694A - Image forming method of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method by which development and fixing are simultaneously carried out with one treating liquid, high sensitivity is obtd. even in a low replenishing treatment and silver sludge can be significantly decreased. SOLUTION: In this image forming method, the development and fixing of a silver halide photographic sensitive material containing a hydrazine deriv. in silver halide emulsion layers and/or nonphotosensitive hydrophilic colloid layers are simultaneously carried out with a single treating liquid to obtain an image. The treating liquid contains a kind of a compd. expressed by formula. In the formula, Z is a group of nonmetal atoms necessary to form a heteroring containing a nitrogen atom, M is a hydrogen atom. alkali metal atom, alkaline earth metal atom or ammonium ion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image on a 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 Photosensitive materials are developed after exposure, fixed, washed,
It is processed by a process such as stabilization. Processing is usually performed using an automatic developing machine, and a method of replenishing a replenisher is generally widely used in order to keep the activity of the processing solution constant. The replenishment of the replenisher is intended to dilute the eluate from the light-sensitive material, correct the amount of evaporation, and replenish the consumed components.

In addition to such processing, there is a so-called one-bath processing in which development and fixing are performed with one processing solution.

[0004] The one-bath treatment has the advantages of reducing the number of processing tanks by one in comparison with the ordinary two-bath treatment, making it possible to reduce the size of the automatic developing machine and reducing the preparation of the solution. There is a serious problem that silver stains or silver sludge, in which silver adheres and accumulates on rollers and the like, and the sensitivity is greatly reduced, and a solution has been strongly desired.

[0005] On the other hand, in recent years, interest in environmental issues has increased, and there has been a strong demand for reduction of photographic processing waste liquid.

Therefore, the conventional replenishing amount of the processing solution is usually 350 ml or more per 1 m ^{2 of the} photosensitive material to be processed, but in recent years, it has become necessary to process at less than 250 ml per 1 m ² .

However, when such low replenishment is performed, the above-mentioned problems of silver contamination and sensitivity reduction become more remarkable.

[0008] In addition, even in the form of one-liquid treatment, since there is still a troublesome liquid preparation operation with a liquid treatment agent, there is a strong demand for a one-bath treatment using a solid treatment agent.

Further, when a single bath treatment is carried out with a conventional treatment solution using only hydroquinone, there is a problem that fog tends to increase, and improvement has been strongly desired.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for forming an image on a photosensitive material which uses development and fixing simultaneously with a single processing solution, has high sensitivity even in low replenishment processing, and has significantly reduced silver sludge. To provide.

[0011]

The above object of the present invention is attained by the following constitutions.

1. Image formation by simultaneously developing and fixing a silver halide photographic material containing at least one hydrazine derivative in a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer with one processing solution to obtain an image A method for forming an image of a silver halide photographic light-sensitive material, wherein the processing solution contains at least one compound represented by the following general formula (1).

[0013]

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Z represents a group of nonmetallic atoms necessary for forming a heterocyclic ring containing a nitrogen atom, and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium ion.

2. 2. The silver halide according to 1, wherein the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer contains at least one compound selected from an amine compound and / or a quaternary onium compound. Image forming method for photographic photosensitive material.

3. 3. The method for forming an image of a silver halide photographic light-sensitive material according to 1 or 2, wherein an image is obtained by processing at a processing solution replenishment rate of 30 to 250 ml per m ^{2 of the} silver halide photographic light-sensitive material.

4. The image forming method according to any one of claims 1 to 3, wherein an image is obtained by processing with a solid processing agent containing a compound represented by the following general formula (2).

[0018]

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In the formula, R ²¹ and R ²² represent an alkyl group, an amino group, an alkoxy group, and an alkylthio group, respectively.
These may have a substituent and may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ²¹ and M ²² each represent a hydrogen atom or an alkali metal atom.

Hereinafter, the present invention will be described in detail.

First, the compound represented by the above general formula (1) of the present invention will be described.

In the general formula (1), the heterocyclic ring represented by Z is, for example, oxazole, benzoxazole, thiazole, benzothiazole, triazine, pyrimidine,
Each ring includes tetrazaindolizine, triazaindene, purine and the like, and is preferably a 5- to 6-membered heterocyclic ring to which a benzene ring may be condensed. M represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium ion. Further, the heterocyclic ring may have a substituent other than the -SM group described in the general formula (1), and examples of the substituent include a halogen atom, a sulfo group, a hydroxyl group, a lower alkyl group, And a phenyl group.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

[0024]

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[0025]

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In the present invention, the compound represented by the general formula (1) preferably has a structure represented by the general formulas (A) to (C).

First, the compound having the structure represented by formula (A) will be described.

[0028]

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In the general formula (A), R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group, a phosphono group, an amino group, a nitro group, Represents a cyano group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkoxy group, or the like, and R ₁ and R ₂ may be linked to form a saturated 5- to 6-membered ring.

An alkyl group, an aryl group, an aralkyl group,
The amino group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the sulfamoyl group, the alkoxy group, and the like may further have a substituent. As the substituent, the same groups as those described for R ₁ and R ₂ can be used. Can be listed.

[0031] either of R _1, R ₁ Preferred examples of R _2, R ₂ is a substituted having 1 to 10 carbon atoms, an unsubstituted alkyl group, a substituted having 6 to 12 carbon atoms, an unsubstituted aryl group And a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms, a nitro group, a cyano group, and a halogen atom. R
_{The case where 1} and R ₂ are linked to form a saturated 5- or 6-membered ring can also be mentioned as a preferable example.

As more preferred examples of R ₁ and R ₂ , R ₁ is a hydrogen atom or an amino group (dimethylamino group, diethylamino group, etc.) or a heterocyclic residue (morpholino group, N-methylpiperazinyl group, pyrrolidinyl group). group, a piperidinyl group, etc.) can be exemplified an alkyl group having as a substituent, substituted C1-10 as R _2, an unsubstituted alkyl group, a substituted having 6 to 12 carbon atoms, an unsubstituted aryl group Can be mentioned.

Specifically, R _{1 includes} a dimethylaminomethyl group, a morpholinomethyl group, an N-methylpiperazinylmethyl group, a pyrrolidinylmethyl group and the like. R _{2 represents} a methyl group, an ethyl group, a phenyl group, p-
Examples include a methoxyphenyl group.

The compounds represented by formula (A) are specifically shown below, but the invention is not limited thereto.

[0035]

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[0036]

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Next, the compound having the structure represented by formula (B) will be described.

[0038]

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In the general formula (B), Z ₂₁ and Y ₂₁ each represent a group of non-metallic atoms necessary for forming an unsaturated 5- or 6-membered ring (as the 5- or 6-membered ring, For example,
A ring such as benzene, pyrrole, imidazole, pyrazole, pyridazine and pyrimidine), and the compound represented by the general formula (B) is a compound condensed in a combination of 5 members and 6 members, and the condensed ring has a nitrogen atom. It has three or more and has at least one mercapto group as a substituent.

The compound represented by the formula (B) may have a substituent other than a mercapto group, and the substituent may be a halogen atom (for example, fluorine, chlorine, bromine atom), substituted or unsubstituted. A substituted alkyl group (especially those having 5 or less carbon atoms such as a methyl group and an ethyl group are preferable), and a substituted or unsubstituted alkoxy group having 5 or less carbon atoms (especially a methoxy group,
Those having 5 or less carbon atoms such as an ethoxy group and a butoxy group are preferred. ), A hydroxy group, a sulfo group, a substituted or unsubstituted allyl group (especially those having 5 or less carbon atoms), an amino group, a COOM ₂₁ group (M ₂₁ has the same meaning as M in the general formula [1]), Examples include a carbamoyl group and a phenyl group. In particular, it preferably has a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group.

Further, as the compound represented by the general formula (B), compounds represented by the following general formulas (a) to (f) are particularly preferable.

[0042]

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In the general formula (a), R ₂₁ , R ₂₂ , R ₂₃
Is a halogen atom, a substituted or unsubstituted alkyl group (especially those having 5 or less carbon atoms such as a methyl group or an ethyl group), a substituted or unsubstituted alkoxy group (particularly a methoxy group, an ethoxy group, a butoxy group, etc.) Those having 5 or less carbon atoms are preferred.), Hydroxy groups, sulfo groups, substituted and unsubstituted allyl groups (especially those having 5 or less carbon atoms), amino groups, and COOM ₂₁ groups (M ₂₁ is the general formula (Same as M in (1)), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group of the compound represented by the general formula (a) is preferably a hydroxy group, a COOM ₂₁ group, an amino group or a sulfo group.

[0044]

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In the general formula (b), R ₂₁ , R ₂₂ ,
R ₂₃ and R _{24 each} represent a halogen atom, a substituted or unsubstituted alkyl group (preferably having a carbon number of 5 or less such as a methyl group or an ethyl group), a substituted or unsubstituted alkoxy group (having a carbon number of 5 or less) Is preferred.), A hydroxy group, a sulfo group, a substituted or unsubstituted allyl group (especially those having 5 or less carbon atoms), an amino group, and a COOM ₂₁ group (M ₂₁ is the same as M in the general formula (1)). Synonymous), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group in the compound represented by the general formula (b) is preferably a hydroxy group, a COOM ₂₁ group, an amino group or a sulfo group.

[0046]

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In the general formula (c), R ₂₁ and R _{22 each} represent a halogen atom, a substituted or unsubstituted alkyl group (especially those having 5 or less carbon atoms such as a methyl group and an ethyl group),
Substituted or unsubstituted alkoxy group (especially those having 5 or less carbon atoms), hydroxy group, sulfo group, substituted or unsubstituted allyl group (especially those having 5 or less carbon atoms), amino group, COOM ₂₁ groups (M ₂₁ has the same meaning as M in formula (1)), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group of the compound represented by the general formula (c) is preferably a hydroxy group, a COOM ₂₁ group, an amino group or a sulfo group.

[0048]

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In the general formula (d), R ₂₁ and R _{22 each} represent a halogen atom, a substituted or unsubstituted alkyl group (particularly a methyl group, an ethyl group, or the like having 5 or less carbon atoms),
Substituted or unsubstituted alkoxy group (especially those having 5 or less carbon atoms), hydroxy group, sulfo group, substituted or unsubstituted allyl group (especially those having 5 or less carbon atoms), amino group, COOM ₂₁ groups (M ₂₁ has the same meaning as M in formula (1)), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group in the compound represented by the general formula (d) is preferably a water-soluble group such as a hydroxy group, a COOM ₂₁ group, an amino group or a sulfo group.

[0050]

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In the general formula (e), R ₂₁ , R ₂₂ ,
R ₂₃ and R ₂₄ are a halogen atom, a substituted or unsubstituted alkyl group (especially those having 5 or less carbon atoms such as a methyl group or an ethyl group), a substituted or unsubstituted alkoxy group (especially 5 or less carbon atoms). Are preferred.), A hydroxy group, a sulfo group, a substituted or unsubstituted allyl group (especially those having 5 or less carbon atoms), an amino group, a COOM ₂₁ group (M ₂₁ is a group represented by the general formula (1)). M), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group of the compound represented by the general formula (e) is preferably a hydroxy group, a COOM ₂₁ group, an amino group or a sulfo group.

[0052]

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In the general formula (f), R ₂₁ , R ₂₂ , R ₂₃
Each hydrogen atom, -SM ₂₁ group, hydroxy group, alkoxy group, -COOM ₂₂ group, an amino group, -SO ₃ M ₂₃ group or an alkyl group, at least one of R _21, R _22, R ₂₃ is The -SM ₂₁ group. M ₂₁ , M ₂₂ and M ₂₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group;
They may be the same or different.

In the above formula (f), R ₂₁ ,
The substituted or unsubstituted alkyl group and the substituted or unsubstituted alkoxy group represented by R ₂₂ and R ₂₃ are each a group having 1 to 5 carbon atoms, preferably a group having 1 to 3 carbon atoms. , R ₂₁ , R ₂₂ , and R ₂₃ represent a substituted or unsubstituted amino group, and a preferable substituent is an alkyl group having 5 or less carbon atoms.

In the above formula (f), the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compounds represented by formulas (a) to (f) are shown below, but the present invention is not limited to these.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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Next, the compound having the structure represented by formula (C) will be described.

[0064]

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In the general formula (C), Z ₃₁ and Y ₃₁ each represent a group of nonmetallic atoms necessary for forming an unsaturated 5- or 6-membered ring, and Z ₃₁ and Y ₃₁ together It contains three or more nitrogen atoms and has at least one mercapto group as a substituent.

The compound represented by the general formula (C) is preferably a compound represented by the following general formulas (g) and (h).

[0067]

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In the general formulas (g) and (h),
R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a hydrogen atom, a —SM ₃₁ group,
Hydroxy group, an alkoxy group, -COOM ₃₂ group, an amino group, -SO ₃ M ₃₃ group or an alkyl group, R _31,
At least one of R _32, R _33, R ₃₄ has the -SM ₃₁ group. M ₃₁ , M ₃₂ and M ₃₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different.

In the above formulas (g) and (h), the alkyl group and the alkoxy group represented by R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are groups each having 1 to 5 carbon atoms. , Which may further have a substituent, preferably a group having 1 to 3 carbon atoms, and R ₃₁ , R ₃₂ , R ₃₃ ,
The amino group represented by R ₃₄ represents a substituted or unsubstituted amino group, and a preferable substituent of the amino group is an alkyl group having 1 to 3 carbon atoms.

Specific examples of the compounds represented by formulas (g) and (h) are shown below, but the present invention is not limited thereto.

Specific examples of the compound represented by formula (g) are shown below, but the present invention is not limited to these.

[0072]

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Specific examples of the compound represented by formula (h) are shown below, but the present invention is not limited to these.

[0074]

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The preferred embodiment of the addition amount of the compound represented by the above general formula (1) to the backing layer of the present invention is 5 to 200 mg / m ² , and various factors such as reduction of the amount of eluted silver and photographic characteristics are provided. Is more preferably 7 to 15 in consideration of the condition of
0 mg / m ^2, and most preferably 10-100 mg / m ^2.

Next, the hydrazine derivative of the present invention will be described.

In the present invention, as the hydrazine derivative, a compound represented by the following formula (H) is preferable.

[0078]

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In the general formula (H), A represents an aryl group,
Represents a heterocycle containing at least one sulfur atom or oxygen atom, G is - (CO) n-group, a sulfonyl group, a sulfoxy _{group, -P (= O) R 2} - represents a group or an iminomethylene radical, n Represents an integer of 1 or 2; A ¹ and A ^{2 each} represent a hydrogen atom or one of which is a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group;
Is a hydrogen atom, each substituted, unsubstituted alkyl, alkenyl, aryl, alkoxy, alkenyloxy, aryloxy, heterocyclic oxy, amino,
Represents 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).

[0081]

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In the general formula (Ha), R ¹ represents an aliphatic group (for example, octyl group, decyl group), an aromatic group (for example, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (for example, pyridyl group) , A phenyl group, a furyl group), and those groups further preferably substituted with a substituent are preferably used. Further, R ¹ preferably contains at least one diffusion-resistant group or silver halide adsorption promoting group.

As the non-diffusible group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is inactive to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, alkylphenoxy group and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
A thione group, a heterocyclic group, a heterocyclic group having a thioamide group,
Heterocyclic group having a mercapto group or JP-A-64-904
And the adsorbing groups described in No. 39.

X represents a group substitutable for a phenyl group, and m
Represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different. A ³ and A ⁴ have the same meanings as A ¹ and A ² in formula (H), and are preferably both hydrogen atoms. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group,
G is preferably a carbonyl group. R ² is a hydrogen atom,
Alkyl group, alkenyl group, alkynyl group, allyl group,
Represents a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group, or an oxycarbonyl group. Most preferred R ²
Are -COOR ³ groups and -CON (R ⁴ ) (R ⁵ )
Wherein R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group,
Represents an alkynyl group, an aryl group or a heterocyclic group, and R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compounds represented by formulas (H) and (Ha) are shown below, but the invention is not limited thereto.

[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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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 of the present invention can be synthesized by a known method. For example, US Pat.
No. 9,248, column 59 to column 80, can be synthesized by the method as described.

The addition amount may be any amount as long as it makes the contrast high.
The optimum amount 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 in the range of 10 ^-6 to 10 ^-1 mol per mol of silver halide. , Preferably in the range of 10 ^-5 to 10 ^-2 mol.

The hydrazine derivative of the present invention is added to a silver halide emulsion layer or a layer adjacent thereto.

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

[0098]

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In the general formula (Na), R ³¹ , R ³² , R
³³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group. R ³¹ , R ³² and R ³³ 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 silver halide adsorbents include a heterocyclic group, a mercapto group, a thioether group, a thione group and a thiourea group. Particularly preferred as the general formula (Na) is a compound having at least one thioether group as a silver halide adsorbent in the molecule.

Hereinafter, specific examples of the compound represented by formula (Na) will be described.

[0102]

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[0103]

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[0104]

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[0105]

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In the general formula (Nb), Ar represents a substituted or unsubstituted aromatic or heterocyclic group. ^R34 represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, but Ar and ^R34 may be connected to each other 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 examples of the compound represented by formula (Nb) are shown below.

[0108]

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[0109]

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Specific examples of other preferred compounds are described in JP-A-6-258751, page 13 (13), “0062” to (1).
5) (2-1) to (2) described on page “0065”
-20) and 3-1 to 3-6 described in JP-A-6-258751, page (15), “0067” to page (16), “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, quaternary onium salt compounds preferably used in the silver halide photographic light-sensitive material of the present invention will be described.

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

[0115]

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In the general formula (P), Q represents a nitrogen atom or a phosphorus atom, R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ each represent a hydrogen atom or an organic group, and X ⁻ represents an anion. Also, R
₄₁ to R ₄₄ may combine with each other to form a ring.

As the substituent represented by R _{41 to} R ₄₄ , an alkyl group (for example, methyl, ethyl, propyl, butyl,
Hexyl, cyclohexyl, etc.), alkenyl group (eg, allyl, butenyl, etc.), alkynyl group (eg, propargyl, butynyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (For example, piperidinyl, piperazinyl, morpholinyl, pyridyl, furyl, thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl, etc.), an amino group and the like. Examples of the ring that R _{41 to} R ₄₄ can form by linking 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, and a tetrazole ring. The groups represented by R _{41 to} R ₄₄ may 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 ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ , 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 preferably used in the present invention include the following general formulas (Pa) and (P)
Compounds represented by b) and (Pc) or compounds represented by the following general formula (T) can be used.

[0120]

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In the general formulas (Pa), (Pb) and (Pc), A ¹ , A ² , A ³ , A ⁴ and A ^{5 each} represent a nonmetallic atom group necessary for completing a nitrogen-containing heterocyclic ring. Represents an oxygen atom,
It may contain a nitrogen atom and a sulfur atom, and the nitrogen heterocyclic ring may be condensed with a benzene ring. A ¹ , A ² , A ³ , A ⁴
And the nitrogen-containing heterocycle composed of A ⁵ may have a substituent and may be the same or different. As a substituent, 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,
Sulfo group, carboxy group, hydroxyl group, alkoxy group, aryloxy group, amide group, sulfamoyl group,
A carbamoyl group, a ureido group, an amino group, a sulfonamide group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, and an arylthio group.

Preferred examples of the nitrogen-containing heterocyclic ring represented by A ¹ , A ² , A ³ , A ⁴ and A ⁵ include 5- to 6-membered rings (rings such as pyridine, imidazole, thiazole, oxazole, pyrazine and pyrimidine). A more preferred example is a pyridine ring.

Bp 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, for example, a hydrogen atom alkyl group or an aryl group) alone or in combination. Bp 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, A ¹ ,
The substituents have the same meanings as the substituents for A ² , A ³ , A ⁴ and A ⁵ . R ¹ , R ² and R ⁵ are preferably each an alkyl group having 4 to 10 carbon atoms. More preferably, a substituted or unsubstituted aryl-substituted alkyl group is exemplified.

[0125] Xp ^- is a counter ion necessary to balance the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. np represents the number of counter ions required to balance the charge of the entire molecule, and np is 0 in the case of an internal salt.

[0126]

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In the triphenyltetrazolium compound represented by the general formula (T), the substituents R ⁶ , R ⁷ ,
R ⁸ 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 at 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) and the like, all of which are represented by the general formula (T)
Is useful as a substituent of the compound of

Examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid, sulfonic acid and carboxylic acid. Acid radicals of an organic acid such as an anionic activator, specifically a lower alkylbenzenesulfonic acid anion such as a p-toluenesulfonic acid anion;
-Higher alkylbenzenesulfonic acid anions such as dodecylbenzenesulfonic acid anion, higher alkyl sulfate anions such as lauryl sulfate anion, boric acid anions such as tetraphenylboron, dialkylsulfosuccinates such as di-2-ethylhexylsulfosuccinate anion; Examples include anions, higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid root such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium salt compound will be shown below, but the present invention is not limited thereto.

[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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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.
The compound can be easily synthesized with reference to the methods described in 335 to 483.

The addition amount of these quaternary onium salt compounds is as follows:
The amount is usually 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.

Next, the compound represented by formula (2) will be described.

As the compound represented by the general formula (2), it is preferable to use a compound represented by the following general formula (2-a) in which R ²¹ and R ²² are bonded to each other to form a ring.

[0146]

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In the formula, R ²³ is a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group,
Or a sulfo group, a carboxyl group, an amide group, or a sulfonamide group, Y ²¹ represents O or S, and Y ²² represents O, S
Or NR ²⁴ . R ²⁴ represents a substituted or unsubstituted alkyl group or aryl group.

Specific examples of the compounds represented by formulas (2) and (2-a) are shown below, but the invention is not limited thereto.

[0149]

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[0150]

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[0151]

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[0152]

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The solid processing agent preferably used in the present invention can be used in combination with a dihydroxybenzene-based developer in addition to the compound represented by the general formula (2).

The dihydroxybenzene-based developer mentioned here is a compound represented by the following general formulas (I) to (III).

[0155]

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In the general formulas (I) to (III), R ₅ and R
₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a halogen atom or a sulfo group.

Examples of the dihydroxybenzene-based developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, and hydroquinonesulfonic acid, with hydroquinone being particularly preferred.

The amount of the dihydroxybenzene-based developing agent (HQ
Mol) and the amount (B mol) of the compound represented by the general formula (2) (B / HQ) are preferably from 0 to 100, more preferably from 50 to 100.

The developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

Each part granule of the developer and the fixing agent used for the solid processing agent is preferably coated.
Sugars or water-soluble polymer compounds preferably used for coating include sugar alcohols and monosaccharides (eg, glucose,
Galactose, etc.), disaccharides (eg, maltose, sucrose, lactose, etc.), polysaccharides, polyalkylene glycols, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl acetate, aminoalkyl methacrylate copolymer, methacrylic acid-
Examples include methacrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, and vinyl polymers having a betaine structure. Among these, sugar alcohols, polysaccharides and polyalkylene glycols represented by the following general formula (G) are preferred.

[0161]

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In the general formula (G), l, m and n each represent an integer of 0 to 1000, and 1 + m + n is 10 or more.

Preferred specific examples of the sugar alcohol include threitol, erythritol, arabitol, ribitol, xylitol, sorbitol, mannitol, iditol, talitol, galactitol, and allozlicitol.

Preferred examples of the polysaccharide include pullulan, methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose succinate, carboxymethylethylcellulose, dextrins, cyclodextrin Dextrins,
Starch degradation products and the like.

Particularly preferred starch degradation products include Pine Flow and Paindex manufactured by Matsutani Chemical.

Specific examples of preferred compounds represented by formula (G) include the following compounds.

[0167]

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In the above compounds, l, m and n have the same meanings as l, m and n in the general formula (G).

Of these, polyethylene glycol represented by the compound example (1) is particularly preferred. The average molecular weight is preferably from 1,000 to 10,000. Specific examples include polyethylene glycol # 2000, # 4000, and # 6000 manufactured by Kanto Chemical.

The granulation method preferably used in the present invention includes rolling granulation, extrusion granulation, spouted bed granulation, fluidized bed granulation, pulverized granulation, stirring granulation, and compression granulation. Can be applied. In addition, as a method of coating the saccharide or the water-soluble polymer compound on the granules in the present invention, the granules granulated by any method can be coated with pan coating, tumbling coating, fluid coating and the like.

A commercially available fluidized bed granulator can be used.
More specifically, Powrex multiplex series,
Examples include the GPCG series, WST / WSG series, Fujimaru's New Malmerizer series, Ogawara's Mixgrade series, Freund's Spiral flow series, and flow coater series.

The two-part granules formed from a developer part containing the compound represented by the general formula (2) and an alkaline compound or a fixing part containing at least one of thiosulfates and thiocyanates are 1 without localization
Present in seed moldings. In order to uniformly mix the two part granules, a commercially available mixer is used, but a cross rotary mixer or a V-type mixer is preferable in view of the effects of the present invention.

The above-mentioned molded product is obtained by solidifying granules, powders, crystals and a mixture thereof into a predetermined shape, and is preferably a so-called tablet characterized by being molded by compression. For the production of tablets, a commercially available single-shot tableting machine, single-shot double tableting machine, rotary tableting machine and the like are used. The compression pressure at the time of compression is preferably 0.5 to ³ ton / cm ² . If it is less than 0.5 ton / cm ² , fine powder is likely to be generated at the time of transportation and the like, and if it exceeds 3 ton / cm ² , the effects of preservability and solubility are reduced.

The content of the saccharide or the water-soluble polymer compound is preferably 0.2% by weight to 20% by weight based on the weight of the part granules to be coated. Further, the particle size distribution of each part granule is preferably such that granules having a particle size of 149 μm or less are 20% by weight or less based on the weight of each part granule.
Granules having a particle size of 000 μm or more
It is preferably 0% by weight or less. The measurement of the particle size in the present invention is based on a sieving method using a JIS standard sieve. That is, 149 μm (100 mesh) or 100
It is determined by measuring the weight of the powder that has passed through a 0 μm (16 mesh) sieve and the powder that has not passed.

In the processing of the light-sensitive material of the present invention, the processing is carried out while replenishing a fixed amount of processing liquid in proportion to the area of the light-sensitive material in order to reduce the amount of waste liquid. In the present invention, the processing solution replenishing amount is preferably from 30~250ml / m ^2, more preferably from 30 to 200 ml / m ^2.

The processing solution replenishing amount indicates the amount of the replenishing solution. Specifically, this is the replenishment amount of each solution when replenishing the same solution as the developing-fixing mother liquor, and the respective concentrated solution and water when replenishing the developing-fixing concentrated solution with a solution diluted with water. The total amount is the total amount of each solid processing agent volume and water volume when the solid processing agent is replenished with a solution in which the solid processing agent is dissolved in water. Is the total of the volume of the solid processing agent and the volume of water. 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. The development
The fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents.

In the case of a solid processing agent, the amount of the processing agent to be charged at one time is preferably from 0.1 to 50 g, and the solid processing agent in this range is directly charged into the processing tank of the automatic developing machine and slowly dissolved. Processing does not affect photographic performance. 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.

The temperature of the developing-fixing, washing and / or stabilizing bath is preferably between 10 ° C. and 50 ° C., and each may be separately adjusted.

In the processing of the light-sensitive material, washing is performed after the development-fixing processing. The washing layer may be a system in which fresh water is supplied at a rate of several liters per minute depending on the processing, or the washing water is circulated, Or a method of reusing after treating with 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. 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.

In the drying zone of the automatic developing machine, a method of drying using warm 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 radiation of 150 ° C. or more is used. Objects (for example, tungsten, carbon, nichrome, zirconium oxide, yttrium oxide,
A substance that emits infrared rays by directly generating heat through a mixture of thorium oxide or silicon carbide and radiating heat, or transferring heat energy from a resistance heating element to a radiator such as copper, stainless steel, nickel, or various ceramics to generate heat and generate infrared rays ), Or those provided with a known drying means such as a dehumidifier, a microwave generator, and a water-absorbent resin. Further, a control mechanism for a dry state may be provided.

The average grain size of the silver halide preferably used in the light-sensitive material of the present invention is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm. The shape of the silver halide grains is not particularly limited, and may be any of a tabular shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedral shape, and any other shapes. Further, it is preferable that the particle size distribution is narrower, and in particular, 90% of the total number of particles, preferably 9
A so-called monodisperse emulsion containing 5% is preferable.

In the method for producing an emulsion, the method of reacting a soluble silver salt with a soluble halide 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 (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 the silver halide emulsion, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt, osnium salt, iron salt may be formed in at least one of the steps of forming or growing grains. , Copper salts, platinum salts, palladium salts and the like are preferably added. 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.

On the surface of the silver halide grains, the halogen composition can be controlled 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, types and amounts of dopants, distributions of lattice defects, and the like.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

The light-sensitive material of the present invention may be appropriately selected from commonly used chemical sensitization methods such as sulfur sensitization, selenium or tellurium sensitization, reduction sensitization and noble metal sensitization. . Further, these chemical sensitizations 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.

A wide variety of selenium compounds can be used as the selenium sensitizer. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N-dimethylselenourea, N, N,
N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-
Trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides ( For example, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophos) And selenides (such as triphenylphosphine selenide, diethyl selenide and diethyl diselenide). In particular, preferred selenium sensitizers include selenoureas, selenamides, and selenoketones, selenides. As the selenium sensitizer, triphenylselenophosphine and the like are preferably used.

As a method for adding these sensitizers, if they are water-soluble, they can be added as they are, but if they are hardly soluble in water, various methods can be adopted. For example, there is a method in which a sulfur sensitizer and / or a selenium sensitizer and / or a tellurium sensitizer are sufficiently mixed in advance with a gelatin solution and then added. Alternatively, a method of dissolving in a low-boiling organic solvent in which a sensitizer is dissolved and then emulsifying and dispersing in the presence of a surfactant to add the sensitizer can also be adopted.
In this method, it is preferable to remove the low-boiling organic solvent after emulsification and dispersion. Further, a method disclosed in Japanese Patent Application Laid-Open No. 4-140739 is also possible in which the compound is added in the form of an emulsified dispersion of a mixed solution with a water-insoluble and organic solvent-soluble polymer. Also, a method of arbitrarily dispersing the average particle diameter from 0.01 to 6 μm by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion, or the like can be adopted.

The gold sensitization method is a typical one of the noble metal sensitization methods, and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

In the present invention, an oxidizing agent for silver can be used in the production process of the photosensitive material. Examples of the oxidizing agent that can be used include inorganic oxidizing agents such as hydrogen peroxide (water) and hydrogen peroxide adducts (eg, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H _{2)
O 2, Na 4 P 2 O} 7 · 2H 2 O 2, 2Na 2 SO 4 · H 2 O 2 ·
2H ₂ O, etc.), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K
_{2 C 2 O 6, K 4} P like ₂ O _8), peroxy complex compounds (e.g., _{K 2 [Ti (O 2)} C 2 O 4] · 3H 2 O, 4K 2 SO 4
・ Ti (O ₂ ) ・ OH ・ SO ₄・ 2H ₂ O, Na ₂ [VO
(O ₂ ) (C ₂ O ₄ )] 2.6H ₂ O, permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ C)
oxyacids such as rO), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and high-valent metal salts (eg, potassium ferricyanide)
And thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T, chloramine). B, etc.).

Particularly preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, inorganic oxidizing agents for halogen elements, quinones and organic oxidizing agents which release active halogens.

The oxidizing agent is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. More preferred is 10 ^-6 to 10 ^-2 mol, and particularly preferred is 10 ^-5 to 10 ^-3 mol.

The light-sensitive material of the present invention can be spectrally sensitized to a desired wavelength by a sensitizing dye. Sensitizing dyes that can be used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, hemioxonol dye, and the like.
Any of nuclei generally used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is,
Pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc., these nuclei are fused with an alicyclic hydrocarbon ring, and these nuclei are fused with an aromatic hydrocarbon ring, that is, indolenine nucleus, benzindolenin 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.

The merocyanine or the complex merocyanine includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus and a 2-thiooxazolidine-nucleus as nuclei having a ketomethylene structure.
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic ring such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied. Specifically, research and
Disclosure (RD) 17643 (1978/1
February issue) page 2-3, U.S. Pat. No. 4,425,425,
No. 4,425,426 can be used. The sensitizing dye is disclosed in U.S. Pat.
The dissolution may be performed by using ultrasonic vibration described in No. 34.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.
Useful supersensitizing dye combinations and supersensitizing substances are described in (RD) 17643), page 23, IV, J.

The light-sensitive material of the present invention can be prepared by the following steps:
Various compounds can be incorporated for the purpose of preventing fog during storage or photographic processing or stabilizing photographic performance. That is, azoles (eg, benzothiazolium salts), nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines (e.g., thioketo compounds such as oxazolinethione), azaindenes (e.g., triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1, 3,3a, 7-tetrazaindenes), pentazaindenes and the like, many of which are known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, potassium bromide and the like. Can be added.
Particularly preferred are a substituted or unsubstituted heterocyclic or fused heterocyclic ring containing any of N, O, S and Se, and a water-soluble halide.

The photographic emulsion layer and the non-photosensitive hydrophilic colloid 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, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'- Methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazole , Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, isocyanates, carboxyl group-activated hardeners and the like can be used alone or in combination.

The emulsion layer and / or the non-photosensitive hydrophilic colloid layer may contain various known surfactants for various purposes such as coating aids, antistatic, slipperiness improvement, emulsification dispersion, adhesion prevention and photographic property improvement. An agent may be used.

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

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

The photographic emulsion may contain a dispersion of a water-insoluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability, reducing silver sludge, and the like. For example, alkyl (meth)
Acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like as a monomer component can be used. Further, a monomer having a plurality of ethylenically unsaturated groups may be used as a monomer component. These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group, and 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 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, a carbamoyl group, an amino group, a sulfonyl group , A sulfoxy group, an iminomethylene group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an arbitrary group bonded via an aryloxy group, etc.), a cation group, etc. Is also good. 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.

In the light-sensitive material of the present invention, various other additives are used. For example, desensitizers, plasticizers, slip agents,
Development accelerators, oils, colloidal silica and the like can be mentioned.

As these additives and the above-mentioned additives, those described in (RD) No. 17643, pp. 22 to 31, etc. can be used.

In the light-sensitive material of the present invention, the photographic constituent layer is coated on one side 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 pigments) or polyethylene or Paper supports and the like coated with a polymer such as polyethylene terephthalate. These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

[0209]

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

[0210] Example 1 (Preparation of Silver Halide Emulsion A ₁₎ co-precipitation method 70 mol% of silver chloride with an average diameter rest has a silver bromide 0.0
9 μm silver chlorobromide core particles were prepared. At the time of preparation of 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 simultaneously mixed while maintaining the same at ℃, pH 3.0, and silver potential (EAg) 165 mV. The core particles were shelled using a double jet method with EAg reduced to 125 mV with saline. At that time, 20 μg of K ₃ RhCl ₆ was added to the halide solution per 1 mol of silver. Further, KI conversion was performed using silver iodide fine particles, and the obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (silver chloride 7) having an average diameter of 0.15 μm.
0 mol%, silver iodobromide 0.2 mol%, and the remainder was silver bromide). Then, JP-A-2-2801
No. 39 (denatured gelatin wherein amino groups in the gelatin are substituted with phenylcarbamyl).
The salt was desalted using Exemplified compound G-8) on page 287 (3) of No. 280139. The EAg after desalting was 190 mV at 50 ° C.

To the obtained emulsion, potassium bromide (100 mg per mol of silver) and citric acid were added to adjust the pH to 5.6.
The EAg was adjusted to 123 mV, and 170 mg of sodium N-chloro-p-toluenesulfonamide trichloride (chloramine T) was added to 1 mol of silver for reaction. Then, a solid-dispersed inorganic sulfur (S8) compound (dispersing machine PM
-200 mg of saponin added and dispersed to an average of 0.5 µm using Seishin Enterprise Co., Ltd.) in an amount of 0.6 mg per mol of silver and 6 mg of chloroauric acid.
After 120 minutes of chemical ripening at 200 ° C., 200 mg of the following sensitizing dye d-1 and 150 mg of d-10 were added at 40 ° C.
After adding 600 mg of 1-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per mol of silver, 20 mg of 1-phenyl-5-mercaptotetrazole and 300 mg of potassium iodide, the pH was adjusted to 5 with citric acid. .1
It was adjusted to give the silver halide emulsion A _1.

[0212]

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(Preparation of photosensitive 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 further prepared so that the amount of gelatin became 0.3 g / m ^2. The silver halide emulsion layer of Formula 2 was formed on the upper layer so that the amount of silver was 3.3 g / m ² , and the amount of gelatin was 1 g / m ² .
200m by curtain coating method so that it becomes 0g / m ²
The emulsion layer side was simultaneously coated at a rate of / min, cooled at -1 ° C, and dried. On the undercoat layer on the side opposite to the emulsion layer side, a backing layer of the following formulation 4 was prepared with 1.5 g of gelatin.
/ M ^2, and a backing protective layer of the following formulation 5 on the emulsion layer side and the backing layer side at a speed of 200 m / min by a curtain coating method so that the amount of gelatin becomes 0.8 g / m ^2. At the same time, and cooled and set at -1 ° C, and dried. 11-19 were obtained.

Formulation 1 (Gelatin Undercoat Layer) Gelatin 0.3 g / m ² Fungicide Z 0.5 mg / m ² Solid Disperse Dye 1-25 30 mg / m ² Compound t-5 10 mg / m ² Formula 2 (Halogenated Composition of silver emulsion layer) Silver halide emulsion A ₁ silver amount 3.3 g / m ² equivalent hydrazine compound Exemplified H-30 10 mg / m ² amine compound described in Table 1 Surfactant S1 1.7 mg / m ² DBS ( Sodium dodecylbenzenesulfonate) 50 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 (ethylenediaminetetraacetic acid · 2Na) 50 mg / m ² polymer latex L1 0.25 g / m ² composite latex L6 1.0 g / m ² dye k 10 mg / ² gelatin coating solution pH using phthalated gelatin 4.8
Met.

Formulation 3 (Emulsion protective layer composition) Gelatin 1.0 g / m ² Surfactant S1 12 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 Surfactant S1 30 mg / m ² Surfactant b 20 mg / m ² Sliding agent (silicone oil) 10 mg / m ² Compound p 15 mg / m ² Composite latex L6 0.3 g / m ² 1 , 3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h4 60 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ² KBr 20 mg / m ² 2-Mercaptohypoxanthine 15 mg / m ² formulation 4 (backing layer composition) gelatin 1.5 g / m ² surfactant S1 5 mg / m ² polymer latex L 0.3 g / m ² Colloidal silica (average particle size 0.05μm) 100mg / m ² of sodium polystyrenesulfonate 10 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100mg / m ² 1- phenyl - 5-mercaptotetrazole 10 mg / m ² Hardener h3 100 mg / m ² Zinc hydroxide 15 mg / m ² EDTA 50 mg / m ² Prescription 5 (backing protective layer) Gelatin 0.8 g / m ² Matting agent: average particle size 5 μm Monodispersed polymethyl methacrylate 50 mg / m ² matting agent: average particle size 3 μm amorphous silica 12.5 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant S1 1 mg / m ² dyes f1 65 mg / m ² dye f2 15 mg / m ² dye f3 100 mg / m ² surfactant b 20 m / M ² KBr 20mg / m ² hardener h2 20 mg / m ² Sodium polystyrenesulfonate 10 mg / ^{m 2}

[0216]

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[0219]

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[0218]

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The sample thus obtained was subjected to step exposure by a laser sensitometer using a 633 nm He-Ne laser as a light source while changing the light amount in 1.5 × 10 ⁻⁷ seconds, and Konica Corporation Automatic developing machine GR-26SR
Using what was possible remodeled Ichiyoku processing (development - fixing processing tank 35L), the photosensitive material 1 m ² per treatment liquid 250
The mixture was treated under the following conditions using a treating agent having the following formulation while replenishing ml. A densitometer P is used for the obtained developed sample.
The blackening density was measured with DA-65 (manufactured by Konica Corporation).

At the start of running and when the photosensitive material is 200 m ²
Treatment (blackening ratio 50%: one unexposed sample and one sample exposed entirely)
The following evaluation was performed on the samples after running in which the sheets were alternately processed).

(Preparation of treatment agent for one-bath treatment) Preparation of treatment liquid A (for one liter) Sodium sulfite 25 g Sodium carbonate 11.2 g 1-phenyl-4-hydroxyethyl-4-methyl-3-pyrazolidone 0.7 g KBr 2 g Diethylenetriaminepentaacetic acid / 5Na 3 g Benzotriazole 0.26 g Hydroquinone 30 g Mannit 10 g Compound of general formula (1) described in Table 1 Preparation of treatment liquid B (for 1 liter) Sodium sulfite 15 g Sodium carbonate 10 g 56.8 g ammonium thiosulfate Sodium acetate 18.5 g Mannit 10 g Powder sorbite 5 g Each of the above-mentioned treatment liquids A and B was mixed with a commercially available rotary mixer in an amount of 5 liter each to prepare 100 liters.

A developing-fixing mother liquor was prepared using 35 liters of the processing solution thus prepared.

Processing Conditions Processing Temperature (° C.) Time (second) Replenishment Rate (ml / m ² ) Development-Fixing 35 30 250 Washing 35 30 Drying 48 20 (Evaluation of Sensitivity) The obtained developed sample was subjected to a densitometer PDA-
65 (manufactured by Konica Corporation).

The sensitivities in the table indicate the values of Sample No. Concentration of 3.0
Is expressed as a relative sensitivity when the sensitivity at 100 is taken as 100.

(Evaluation of Silver Stain) The degree of silver stain of the development-fixing layer after running was visually evaluated.

5 is a good level and 1 is a poor level. The practically usable level was set to 3.

The results are shown in Table 1.

[0228]

[Table 1]

From Table 1, it can be seen that the photosensitive material for plate-making scanner of He-Ne laser light source printing obtained by the image forming method of the photosensitive material of the present invention has high sensitivity and little silver stain even after processing a large amount of the photosensitive material. Understand.

[0230] Example 2 (Preparation of Silver Halide Emulsion B ₁₎ co-precipitation method 70 mol% of silver chloride with an average diameter remainder containing silver bromide 0.
09 μm silver chlorobromide core particles were prepared. At the time of core particle preparation, 36 ° C., pH 3.0, silver potential (EAg) 120 m
While maintaining V, the aqueous silver nitrate solution and the water-soluble halide solution were simultaneously mixed. EAg was added to the core particles with salt for 100 m.
V and shelled using a double jet method. At that time, 38.2 µ of K ₃ RhCl ₆ was added per mole of silver to the halide solution.
g was added. The obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide having an average diameter of 0.20 μm (silver chloride: 70 mol%, silver iodobromide: 0.2 mol%, the rest being bromide). (Composed of silver). Thereafter, 70 mg of the following sensitizing dye d-3 was added per 1 mol of silver. Then, desalting is carried out by using a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, compound G-8 on page 287 (3) of JP-A-2-280139). did. Thereafter, at 40 ° C., 90 mg of chloramine T was added per mole of silver. The EAg of the obtained emulsion was 177 mV at 40 ° C., and the pH was 5.6.

The resulting emulsion was reacted with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at a concentration of 60 mg per mole of silver and 100 mg of KBr, and then inorganic sulfur (S8 ) Compound (Seisin Enterprise Co .; Saponin added using PM-1200 and dispersed to an average of 0.5 μm) and chloroauric acid 1.5 × 1
0 ^-5 mol was added was 120 minutes chemical ripening at a temperature 60 ° C..

Thereafter, 4-hydroxy-
6 methyl-1,3,3a, 7-tetrazaindene is added to 40
0 mg and potassium iodide 100 mg were added, and at 40 ° C., 300 mg of sensitizing dye d-11 was added. Then, the pH was adjusted to 5.1 by adding citric acid, and silver halide emulsion B was added.
₁ was prepared.

[0233]

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[0234] (Preparation of Silver Halide Emulsion B ₂₎ with respect to the silver halide emulsion B _1, the reaction temperature was the particle diameter 0.28μm raised to 45 ° C., per mole of silver of K ₃ RhCl ₆ of the shell portion except that the 10μg in exactly the same manner to prepare a silver halide emulsion B _2. When the same chemical sensitization is performed,
Emulsion of B ₂ was higher 30% sensitivity than Emulsion of B _1.

(Preparation of Photographic Material for Printing and Plate Making) On a support, a gelatin undercoat layer having the following formulation 6 was prepared with a gelatin content of 0.1%.
3 g / m ² , and the silver halide emulsion layer 1 of the following formula 7 was prepared by mixing 0.3 g / m ² of silver and 0.3 of gelatin.
g / m ² , a gelatin intermediate layer of Formula 8 on the upper layer, and a silver halide emulsion layer 2 of Formula 9 on the upper layer so that the amount of gelatin is 0.8 g / m ^2. .0
g / m ² and the amount of gelatin is 1.5 g / m ^2.
/ M ² , 200m / m by curtain coating method
The emulsion layer side was simultaneously coated at a speed of "in", and cooled and dried at -1 ° C.

Further, on the undercoat layer opposite to the emulsion layer side,
The amount of gelatin in the backing layer of the following formulation 11 was 1.5 g /
such that m ^2, thereon, a backing protective layer having the following formulation 12 so that the amount of gelatin is 1.0 g / m ^2,
The backing layer side was simultaneously coated at a speed of 200 m / min by a curtain coating method, cooled at -1 ° C., dried and dried. 21-29 were obtained.

Formulation 6 (Gelatin undercoat layer composition) Gelatin 0.3 g / m ² Surfactant S1 0.4 mg / m ² Compound O 3 mg / m ² Formulation 7 (Composition of silver halide emulsion layer 1) Gelatin 0. 3 g / m ² silver halide emulsion B ₂ silver 0.3 g / m ² corresponding weight polymer latex L2 (particle size 0.25μm) 0.1g / m ² solid disperse dye 1-24 30 mg / m ² compound t-6 10 mg / m ² formulation 8 (gelatin intermediate layer composition) gelatin 0.8 g / m ² saponin 80 mg / m ² hydroquinone 0.5 g / m ² fungicide Z 0.5 mg / m ² dye f9 5 mg / m ² formulation 9 (halogen Composition of silver halide emulsion layer 2) Silver halide emulsion B ₁ Silver amount 3.0 g / m ² equivalent Hydrazine compound H-31 7 mg / m ² Surfactant S1 5 mg / m ² 2-mercaptohypoxanthine 1 mg / m ² Nicochi Acid amide 1 mg / m ² gallate n- propyl ester 50 mg / m ² mercaptopyrimidine 1 mg / m ² Polymer latex L2 (particle size ^{0.25μm) 0.5g / m 2 EDTA 50mg} / m 2 Sodium polystyrenesulfonate 15 mg / m ² Composite latex L6 1.0 g / m ² Gelatin is phthalated gelatin and the coating solution pH is 5.0.
Met.

Formulation 10 (Emulsion protective layer composition) Gelatin 0.6 g / m ² surfactant S1 12 mg / m ² surfactant b 0.6 mg / m ² Quaternary onium salt compound Listed in Table 2 0.2 g of composite latex L6 / M ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h4 80 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Fungicide Z 0.5 mg / m ² Dye f6 50 mg / m ² Formulation 11 (Backing layer composition) Gelatin 1.5 g / m ² Polymer latex L3 0.3 g / m ² Composite latex L6 0.5 g / m ² Dye f1 40 mg / m ² Dye f2 7 mg / m ² Dye f3 60 mg / m ² 1− Phenyl-5-mercaptotetrazole 10 mg / m ² Hardener h3 100 mg / m ² EDTA 50 mg / m ² Formulation 12 (backing protective layer) Gelatin 1.0 g / m ² matting agent: monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² matting agent: average particle size 3 μm amorphous silica 12.5 mg / m ² dye f1 40 mg / m ² dye f2 7 mg / m ² dye f3 60 mg / m ² hardener h1 100 mg / m ² surfactant S1 6 mg / m ² sodium polystyrenesulfonate 10 mg / m ² KI 15 mg / m ² amine compounds exemplified Na-21 15 mg / ^{m 2}

[0239]

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The obtained sample was brought into close contact with a step wedge, exposed to tungsten light at 3200 ° K. for 3 seconds, and the compound of the general formula (1) shown in Table 2 was used, except that the replenishing amount of the processing solution was changed to 150 ml. Was processed and evaluated under the same conditions as in Example 1. Note that the sensitivity is the same as that of Sample No. 2. concentration of 21
It was expressed as a relative sensitivity when the sensitivity at 0 was taken as 100.

The results are shown in Table 2.

[0242]

[Table 2]

[0243] The image forming method prepress photographic light-sensitive material obtained in the light-sensitive material of the present invention, even after the photosensitive material was treated in large quantities at a low replenishing amount of the photosensitive material 1 m ² per treatment liquid 150 ml, high sensitivity Katsugin It turns out that dirt is favorable.

Example 3 (Preparation of Silver Halide Emulsion C) An average thickness of 0.07 mol% containing silver chloride and the remainder was silver bromide using a double jet method.
Silver chlorobromide core particles having a 5 μm average diameter of 0.15 μm were prepared. During the preparation of the core particles, 8 × 10 ⁻⁸ mol of K ₃ RuCl ₆ was added per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The emulsion thus obtained had a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (silver chloride 9) having an average thickness of 0.10 μm and an average diameter of 0.25 μm.
0 mol%, silver iodobromide 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 resulting emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5%. .6, adjust to EAg123mV,
5 mg of chloroauric acid and 0.5 mg of sulfur were added per mole of silver, and the mixture was chemically ripened at a temperature of 60 ° C. for 120 minutes.
After aging, 4-hydroxy-6-methyl-1,3,3a
7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was added to 3 ×
10 ^-4 mol and gelatin were added, and silver halide emulsion C was added.
Was prepared.

(Preparation of photosensitive material for plate making scanner using red semiconductor laser light source printing) On a PET support, a gelatin subbing layer having the following formulation 13 was coated so that the amount of gelatin became 0.3 g / m ^2. The silver halide emulsion layer of Formulation 14 was adjusted so that the silver amount was 3.0 g / m ² and the gelatin amount was 1.5 g / m ^2. as will become m ^2, formulated thereon 1
The upper layer of the protective layer No. 6 was simultaneously coated on the emulsion layer side at a speed of 200 m / min by a curtain coating method so that the amount of gelatin was 0.5 g / m ² , and cooled and set at -1 ° C. and dried.

On the undercoat layer opposite to the emulsion layer, a backing layer of the following formula 17 was coated with a gelatin having an amount of 0.6 g / m ^2.
So that the polymer layer of the following formula 18 is
Further, a backing protective layer having the following formulation 19 was coated simultaneously with the curtain coating method at a speed of 200 m / min so as to have a gelatin amount of 0.4 g / m ² , cooled at -1 ° C. and dried. Sample No. 31-39 were obtained.

Formulation 13 (Composition of gelatin undercoat layer) Gelatin 0.3 g / m ² Surfactant S1 0.4 mg / m ² Compound O 3 mg / m ² Formulation 14 (Silver halide emulsion layer composition) Silver halide emulsion C silver amount 3.0 g / m sensitized ² sensitization sensitizing dye d-5 6mg / m so that the ^second dye d-2 3 mg / m ² hydrazine compound H-30 10mg / m ² amine compound Na-21 10mg / m ² Quaternary onium salt compound Table 3 Compound e 100 mg / m ² Composite latex L6 1.0 g / m ² 2-mercaptohypoxanthine 2 mg / m ² EDTA 50 mg / m ² Formulation 15 (Emulsion protective layer lower layer composition) Gelatin 0. 5 g / m ² Polymer latex L1 0.25 g / m ² Fungicide Z 0.5 mg / m ² Formulation 16 (Emulsion protective layer upper layer composition) Gelatin 0.5 g / m ² Matting agent: Average particle size 3. 5 μm monodisperse silica 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant b 20 mg / m ² Compound p 30 mg / m ² Composite latex L6 0.5 g / m ² Hardener h2 130 mg / m ² Formula 17 (backing layer composition) Gelatin 0.6 g / m ² Polymer latex L3 0.3 g / m ² Sodium polystyrene sulfonate 20 mg / m ² Formula 18 (hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic) Acid = 97: 3) 1.0 g / m ² Hardener h1 6 mg / m ² Prescription 19 (backing protective layer) Gelatin 0.4 g / m ² KBr 20 mg / m ² Matting agent: monodisperse poly with an average particle size of 5 μm methyl methacrylate 50 mg / m ² surfactant b 20 mg / m ² dye ^{k 40mg / m 2 H- (OCH} 2 CH 2) 68 OH 50mg / m ² hardener h1 20mg / ^{m 2}

[0249]

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[0250]

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The sample thus obtained was subjected to a 1.5-mm laser sensitometer using a red semiconductor laser as a light source.
Step exposure is performed while changing the light amount in × 10 ⁻⁷ seconds,
Using the solid processing agent of the following formulation, the replenishment amount of the processing solution is 70 m
The processing and evaluation were performed in the same manner as in Example 1 except that 1 / m ² was used. Note that the sensitivity is the same as that of Sample No. The sensitivity was expressed as a relative sensitivity when the sensitivity at a density of 3.0 was set to 100.

Preparation of Solid Treatment Agent for One-Bath Treatment Preparation of Granule A (for 1 L) Sodium sulfite 23 g Sodium carbonate 12 g 1-phenyl-4-hydroxyethyl-4-methyl-3-pyrazolidone 0.7 g KBr 5 g Diethylenetriamine 5 Acetic acid / 5Na 3g Benzotriazole 0.26g Compound of general formula (2) (Exemplary 2-41) 80g Hydroquinone 5g Mannit 10g Compound of general formula (1) listed in Table 3 The mixture was mixed for 3 minutes, crushed well, and 5% of the total weight of water was gradually added. The obtained granules were transferred to a fluid bed dryer and dried at an air supply temperature of 60 ° C. for about 2 hours. The granules thus obtained were again placed in a commercially available granulator and sized with a 5 mm mesh.

Preparation of Granules B (for 1 L) Sodium sulfite 20 g Sodium carbonate 10 g Ammonium thiosulfate 58 g Sodium acetate 15 g Mannit 10 g Powdered sorbite 5 g The above materials were put in a commercially available stirring granulator, mixed for 3 minutes, and crushed well. , 5% of the total weight of water was gradually added. The obtained granules were transferred to a fluid bed dryer and dried at a supply air temperature of 60 ° C. for about 2 hours. The granules thus obtained were again placed in a commercially available granulator and sized with a 5 mm mesh.

The granules A and B were placed in a fluid bed granulator GPCG-5, manufactured by Powrex Co., Ltd. in an amount of 5 liters.
It was made to flow at an air supply temperature of 60 ° C. and an air flow of 8 m ³ / min. The surface of the granules was coated by spraying 20 g of a 30% aqueous solution of sorbitol per liter with a two-fluid spray. The resulting surface-coated granules are called a and b.

The two types of granules a and b obtained by the above operation were prepared for each 15 liters, and 2% by weight of the combined weight of sodium 1-octanesulfonate was added thereto. Mix for 10 minutes with a mixer. This mixer was tableted with an oil press at a diameter of 30 mm, a filling amount per tablet of 10 g, and a tableting pressure of 1 ton / cm ² .

Of the solid processing agents thus obtained, 3
A developing-fixing mother liquor was used using 5 liters.

Processing conditions Processing temperature (° C.) Time (second) Replenishment rate (ml / m ² ) Developing-fixing 35 20 70 Washing 35 20 Drying 48 20 The results obtained are shown in Table 3.

[0258]

[Table 3]

[0259] red semiconductor laser light source graphic arts scanner photosensitive materials obtained by the image forming method of the light-sensitive material of the present invention, ultra-sensitive material 1 m ² per treatment liquid 70ml using a solid processing solution to the ascorbic acid and developing agent Even after processing a large amount of the light-sensitive material with a low replenishment amount, high sensitivity and good silver stain are obtained.

[0260]

According to the method for forming an image of a silver halide photographic light-sensitive material of the present invention, an image forming method which has a high sensitivity even with a low replenishment process and a remarkably reduced silver sludge can be obtained by a simple solid processing solution having a simple preparation. Obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/38 G03C 5/38

Claims (4)

[Claims] 1. A silver halide photographic material containing at least one hydrazine derivative in a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer is simultaneously developed and fixed with one processing solution. An image forming method for obtaining an image, wherein the processing solution contains at least one compound represented by the following general formula (1). Embedded image Z represents a group of non-metallic atoms necessary to form a heterocyclic ring containing a nitrogen atom, and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium ion. 2. The method according to claim 1, wherein the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer contain at least one compound selected from an amine compound and / or a quaternary onium compound. 2. The method for forming an image of a silver halide photographic material according to item 1. 3. The image formation of a silver halide photographic light-sensitive material according to claim 1 or 2, wherein an image is obtained by processing at a processing solution replenishment amount of 30 to 250 ml per m ^{2 of the} silver halide photographic light-sensitive material. Method. 4. The image forming method according to claim 1, wherein an image is obtained by processing with a solid processing agent containing a compound represented by the following general formula (2). Embedded image In the formula, R ²¹ and R ²² each represent an alkyl group, an amino group,
Represents an alkoxy 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 represents -CO- or-
Represents CS-. M ²¹ and M ²² each represent a hydrogen atom or an alkali metal atom.