JPH10237041A - Compound and silver halide photographic light-sensitive material using the same and its treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound large in a gelatin-hardening action, not having a post film-hardening property, useful as a film-hardening agent, and capable of providing silver halide photographic light sensitive materials containing the film-hardening agent. SOLUTION: A compound of formula I [R1 -R4 are each H, a monovalent organic group; A, A' are each CONR5 (R5 is H, an alkyl, an aryl), O, S, etc.; J is an alkylene or arylene having at least one substituent such as hydroxyl, carboxyl or sulfonyl group, wherein J does not have the hydroxyl group as the substituent, when A, A' are each CONR5 ], e.g. a compound of formula II. The compound of formula II is easily obtained by dropwisely adding chloroacetyl chloride to a compound of formula III, adding 2-mercaptoethanol to the obtained compound, further dropwisely adding hydrogen peroxide water, and subsequently reacting the product with thionyl chloride and triethylamine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound, a silver halide photographic material using the same, and a processing method therefor. Specifically, the present invention relates to a novel hardener and a silver halide for printing plate making using the same. The present invention relates to a photographic material and a processing method thereof.

[0002]

2. Description of the Related Art In general, a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material) comprises a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, an undercoat layer, an antihalation layer, an ultraviolet absorbing layer, Various photographic constituent layers such as an antistatic layer and a backing layer are formed on a support such as glass, paper, or a synthetic resin film.

[0003] These photographic constituent layers are formed by coating an aqueous coating solution containing gelatin as a main component of a binder and a hydrophilic polymer or a water-dispersible polymer.

[0004] Accordingly, the mechanical strength is extremely weak as it is. For example, a gelatin film has a low melting point and is excessively water-swellable. Further, the latex film has disadvantages such as extremely poor adhesion to the support and easy peeling of the film.

For this reason, a compound called a hardener is added to a photographic component layer to improve its mechanical strength.

Hitherto, many compounds have been widely known as hardeners for silver halide photographic materials or developing solutions.

Aldehyde compounds such as, for example, formaldehyde and glutaraldehyde, US Pat.
No. 303, No. 3,288,775, No. 3,951,9
No. 40, British Patent Nos. 974,723 and 1,167,2
No. 07, etc., compounds having a reactive halogen atom, ketone compounds such as diacetyl and cyclopentadione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3,5- Triazine, di-
Vinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, described in U.S. Pat. Nos. 3,232,763 and 3,635,718, British Patent 994,809, etc. Compounds having a reactive olefin of US Pat. Nos. 3,539,644 and 3,6
42,486, JP-B-49-13563, 53-
Nos. 47271 and 56-48860, JP-A-53-5
No. 7257, No. 61-128240, No. 62-427
No. 5, 63-53441, 63-264572, etc .; vinylsulfonyl compounds; N-hydroxymethylphthalimide; N-methylols described in U.S. Pat. Nos. 2,732,316 and 2,586,168. Compounds, isocyanates described in U.S. Pat. No. 3,103,437, U.S. Pat. Nos. 2,983,611 and 3,10
7,280 and the like, aziridine compounds described in U.S. Pat. Nos. 2,725,294 and 2,725,295, and carbodiimide compounds described in U.S. Pat. No. 3,100,704 and the like. Compounds, US Patent 3,091,5
No. 37, etc., US Pat.
Nos. 1,313 and 3,543,292 disclose organic hardeners such as isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, and dioxane derivatives such as dihydroxydioxane and dichlorodioxane. I have. Chromium alum, zirconium sulfate, chromium trichloride and the like are known as inorganic hardeners.

[0008] However, these known hardeners, when used in photosensitive materials, have insufficient curing action;
Causes a long-term change in the hardening action called "post-hardening" caused by a slow hardening reaction to gelatin, and adversely affects the performance of photosensitive materials (especially increase in fog, decrease in sensitivity or maximum density, soft gradation) ), Or other coexisting photographic additives,
All had some disadvantages, such as those that reduced the effectiveness of other photographic additives (e.g., couplers in internal color emulsions) and caused staining.

The hardening action on gelatin is relatively fast,
As a hardener having a low post-hardening, JP-A-50-3854
No. 0, compounds having a dihydroquinoline skeleton, N-carbamoylpyridinium salts described in JP-A-51-59625, JP-A-62-262854, JP-A-62-264044, and JP-A-63-184741; 3
Acylimidazoles described in No. 8655, JP-B-53
Compounds containing two or more N-acyloxyimino groups in the molecule described in JP-A-22089;
No. 0, compounds having an N-sulfonyloxyimide group, compounds described in JP-A-58-113929, compounds having a phosphorus-halogen bond, and compounds described in JP-A-60-225148.
And the chloroformamidinium compounds described in JP-A Nos. 61-240236 and 63-41580 are known.

Of these, the above-mentioned N-carbamoylpyridinium salts have the characteristic that they have a fast curing action and therefore have a small amount of after-hardening. Particularly when they are applied to a silver halide photosensitive material for printing plate making, In order to obtain a sufficient hardening, a relatively large amount of addition is required, and there is a disadvantage that color contamination occurs after photographic processing.

Heretofore, the above-mentioned vinylsulfonyl compound has been known as a hardening agent which does not cause color contamination during the hardening reaction. However, when the vinylsulfonyl compound is applied to a light-sensitive material, it has a disadvantage that its curing action is slow and its water solubility is low.

US Pat. No. 5,411,856 describes a vinylsulfonyl-based hardener which has improved these disadvantages. However, the hardening speed is still insufficient and a hardening reaction having a fast curing reaction is performed. Agent was desired.

Further, in recent years, a developer having a relatively low pH has been used from the viewpoint of storage stability or safety of the developer. However, JP-A-8-23
As described in No. 4370, when processed with a developer having a pH of less than 10.5, when a conventionally known hardener is used, it has disadvantages such as deterioration of photographic performance and color contamination. I was

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material using a hardener which has a fast hardening action on gelatin and has no post-hardening. Another object of the present invention is to provide a silver halide photographic light-sensitive material hardened with a hardener which does not cause color contamination after processing and does not adversely affect photographic performance. It is a further object of the present invention to provide a method for processing a silver halide photographic material containing the above-mentioned hardener which does not cause color contamination after processing with a low pH developer.

[0015]

The above objects of the present invention have been attained by the following constitutions.

A compound represented by the following general formula [I]:

[0017]

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Where R₁, R_Two, R_Three, R_FourIs a hydrogen atom
Or a monovalent organic group. A and A 'are -CONR_Five−,
-O-, -S (O)_m-, -NR₆-, -NR₇CO-,
-SO _TwoNR₈-, -NR₉CONR_Ten-Represents R_Five, R
₆, R₇, R₈, R₉, R_TenRepresents a hydrogen atom, an alkyl group or
M represents an integer of 0 to 2; J is less
And one hydroxyl group, carboxyl group, sulfo
Group, mercapto group, quaternary ammonium group as a substituent
Represents an alkylene group or an arylene group. However,
A and A 'are both -CONR_FiveWhen-, J is hydroxy
It does not have a sil group as a substituent.

A compound represented by the following general formula [Ia].

[0020]

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[0021] In the _{formula, R 1, R 2, R} 3, R 4, R 5 is R ₁ in the general formula _{[I], R 2, R 3, R} 4, the same meaning as R _5. J represents an alkylene group or an arylene group having at least one carboxyl group, sulfo group, mercapto group or quaternary ammonium group as a substituent.

In a silver halide photographic light-sensitive material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, at least one of the hydrophilic colloid layers has the general formula [I] A silver halide photographic material, which is hardened with a compound represented by the formula:

In a silver halide photographic material having a hydrophilic colloid layer including a silver halide emulsion layer, the silver halide emulsion layer and / or the hydrophilic colloid layer contains at least one tetrazolium compound. The silver halide photographic material as described in the above item, which is characterized in that:

In a silver halide photographic material having a hydrophilic colloid layer including a silver halide emulsion layer, it is preferable that the silver halide emulsion layer and / or the hydrophilic colloid layer contain at least one hydrazine derivative. The silver halide photographic material as described in the above item, which is characterized in that:

The silver halide photographic material as described in any one of the above items, wherein the hydrophilic colloid layer containing the silver halide emulsion layer contains at least one carboxyl group-active hardener. A silver halide photographic light-sensitive material, characterized in that:

The silver halide photographic light-sensitive material as described in any one of the above items 1 to 5, wherein the pH is 7.5 to 10.5.
A method for processing a silver halide photographic light-sensitive material, wherein the processing is carried out using a developing solution.

Hereinafter, the present invention will be described in detail.

In the general formula [I] according to the present invention,
R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a linear or branched alkyl group or a cyclic alkyl group (for example, methyl,
Groups such as ethyl, iso-propyl, cyclohexyl),
An aryl group (for example, a phenyl group or the like) is exemplified. R
_{1 to} R ₄ are preferably a hydrogen atom.

A and A 'represent -CONR _5- , -O-, -S
(O) _m- , -NR _6- , -NR ₇ CO-, -SO ₂ NR ₈
—, —NR ₉ CONR ₁₀ —, wherein R ₅ , R ₆ , R ₇ ,
R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or an alkyl group (for example,
Represents a methyl, ethyl, iso-propyl, etc.) or aryl group (eg, a phenyl group), and m represents an integer of 0 to 2. _{Preferably, -CONR 5 -, - O -} , - S (O) m
-, -NR ₇ CO-, more preferably -CO
Represents NR _5- . J represents an alkylene group having at least one hydroxyl group, carboxyl group, sulfo group, mercapto group, quaternary ammonium group as a substituent, or an arylene group. Preferably, a hydroxyl group,
It represents a carboxyl group, more preferably a carboxyl group. -COOM The carboxyl group referred to herein, -SO ₃ M and a sulfo group, the mercapto group is represented by -SM,
M represents a hydrogen atom or an alkali metal (sodium, potassium, etc.).

The quaternary ammonium group includes triethylammonium, tributylammonium, pyridinium and the like. Examples of the alkylene group include methylene, ethylene,
Each group such as propylene may be mentioned, and these groups may further have a substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, iso-propyl, etc.) and an alkoxy group (eg, methoxy group). , Ethoxy, etc.), amino groups (amino, dimethylamino, carboxyethylamino, etc.), halogen atoms (chlorine, bromine, etc.), amide groups (acetylamino, benzamino, etc.), carbamoyl groups (carbamoyl, methylcarbamoyl, ethylcarbamoyl), Examples include an aryloxy group (phenoxy, 4-carboxyphenoxy, naphthoxy, etc.), a cyano group, a nitro group and the like.

Examples of the arylene group include a phenylene group. These groups may further have a substituent.
Examples of the substituent include an alkyl group (eg, methyl, ethyl, isopropyl, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), an alkoxyacetyl group (eg, methoxymethyl, methoxyethyl, etc.), a halogen atom (chlorine, etc.). , Bromine and the like), acetoxyl group and the like.

The following are specific examples of the compound represented by the general formula [I], but the present invention is not limited thereto.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Hereinafter, a method for synthesizing the compound represented by the general formula [I] of the present invention will be described.

<Synthesis of Compound [I-1]> Synthesis Scheme 1

[0041]

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Compound 19.7 g and sodium hydroxide 8.
0 g was dissolved in 80 ml of ethanol, and chloroacetyl chloride was added dropwise while stirring at 0 to 5 ° C. After the dropwise addition, the temperature was gradually raised to room temperature, and then the inorganic salt was filtered and concentrated. The resulting crude crystals were recrystallized from methanol,
8.8 g of compound 2 were obtained. (Yield 84%) Next, 13.9 g of 2-mercaptoethanol sodium salt was added to 70 ml of methanol, and stirred at 20 ° C.
In the following, 18.8 g of Compound 2 was added, and the mixture was heated under reflux for 5 hours. After filtering the inorganic salt, the mixture was concentrated to give a waxy solid. This was dissolved in 40 ml of water, 1 g of sodium tungstate was added thereto, and 35% hydrogen peroxide solution 20 was added with stirring.
Then, the mixture was further reacted at 80 ° C. for 3 hours. After the reaction solution was concentrated and cooled, crystals were precipitated. The crude crystals were recrystallized from methanol-water to obtain 17.9 g of Compound 3. (Yield 63%) Next, compound 3 was added to 40 ml of dimethylformamide.
After dissolving 6.8 g, 9.8 ml of thionyl chloride was added dropwise thereto, and the mixture was heated and refluxed at 80 ° C. for 1 hour. After evaporating excess thionyl chloride under reduced pressure, concentrating and cooling, crystals were precipitated. After washing with acetone and drying, 11.0 g of compound 4 was obtained. (Yield 60%) Further, 9.3 g of compound 4 was added to dimethylformamide 5
The mixture was dissolved in 0 ml, and 5.6 ml of triethylamine was added while stirring at room temperature. After standing overnight, the salt was filtered and concentrated under reduced pressure to obtain 5.7 g of the compound [I-1]. (Yield 73%) This was confirmed by NMR and IR spectra.

<Synthesis of Compound [I-27]> Synthesis Scheme 2

[0044]

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12.7 g of 2-mercaptoethanol sodium salt was added to 70 ml of methanol, and 14.4 g of compound 5 was added at 20 ° C. or lower while stirring, and the mixture was heated under reflux for 5 hours. After filtering the inorganic salt, the mixture was concentrated to give a waxy solid. This was dissolved in 40 ml of water, 1 g of sodium tungstate was added, 20 ml of 35% aqueous hydrogen peroxide was added dropwise with stirring, and the reaction was further performed at 80 ° C. for 3 hours. After the reaction solution was concentrated and cooled, crystals were precipitated. The crude crystals were recrystallized from methanol-water to obtain 19.8 g of Compound 6. Next, compound 6 was added to 40 ml of dimethylformamide.
Dissolve 7.5 g, add 9.8 ml of thionyl chloride dropwise thereto, and heat to reflux at 80 ° C. for 1 hour. After removing excess thionyl chloride under reduced pressure, concentrating and cooling, crystals precipitate. After washing with acetone and drying, 13.0 g of compound 7 was obtained. (Yield 68%) Further, 11.0 g of the compound 7 is dissolved in 50 ml of dimethylformamide, and 5.6 ml of triethylamine is added while stirring at room temperature. After standing overnight, the precipitate was filtered and concentrated under reduced pressure to obtain 7.5 g of compound [I-27]. This was confirmed by NMR and IR spectra.

Compounds other than those described above can be easily synthesized by the above method or a method analogous thereto.

The hardener represented by the general formula [I] of the present invention may be contained in a silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer. Both may be contained. Specific examples of the layer to be contained include a photosensitive or non-photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, an antistatic layer, a development control layer, an undercoat layer, an antihalation layer, and a backing layer. It is a photographic constituent layer contained.

The hardener represented by the general formula [I] of the present invention is preferably dissolved in water or a water-soluble organic solvent (for example, methanol, acetone, ethanol, etc.) and added to a coating solution to form a known hardener. To obtain a photosensitive material. The amount of the compound represented by the general formula [I] is not uniform depending on the type of the compound or the coating solution, but is usually per gram of dry weight of gelatin in the constituent layers of the photosensitive material used. The range is preferably from 0.01 to 2.0 mmol, more preferably from 0.03 to 1.0 mmol.

The hardener represented by the general formula [I] of the present invention may be used in combination with other known hardeners, and the ratio of the added amount may be arbitrarily changed depending on the purpose. Can be.

The silver halide photographic material of the present invention containing a hardener represented by the general formula [I] includes the following general formula (T)
It is preferable to contain at least one of the tetrazolium compounds represented by

[0051]

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The substituents R ₁₁ , R ₁₂ and R ₁₃ of the phenyl group in the tetrazolium compound represented by the above general formula (T) are those having a hydrogen atom or a Hammett's sigma value (σ _P ) indicating electron-withdrawing degree which is negative. Is preferred.

The Hammett's sigma value for phenyl substitution is described in many literatures, for example, Journal of Medical chemistry.
Chemistry) Volume 20, page 304, 1977
Year, C. As a group having a particularly preferable negative sigma value, for example, a methyl group (σ _P = −0.17 or less, a σ _P value in any case) and an ethyl group ( -0.15), a cyclopropyl group (-0.21), an n-propyl group (-0.1
3), isopropyl group (-0.15), cyclobutyl group (-0.15), n-butyl group (-0.16), is
o-butyl group (-0.20), n-pentyl group (-0.
15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.22)
7), an ethoxy group (-0.24), a propoxy group (-
0.25), butoxy group (-0.32), pentoxy group (-0.34) and the like, all of which are useful as substituents of the compound of the general formula (T) of the present invention.

In the formula, n _T represents 1 or 2, and X _T ^nT−
As the anion represented by, for example, chloride ion, bromide ion, halide ion such as iodide ion, nitric acid,
Acid radicals of inorganic acids such as sulfuric acid and perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anion, p- Higher alkylbenzene sulfonic acid anions such as dodecylbenzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenylboron; dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anion. And polyether alcohol sulfate anions such as cetyl polyethenoxy sulfate anion; higher aliphatic anions such as stearic acid anion; and polymers having an acid root such as polyacrylate anion.

Hereinafter, specific examples of the compound represented by formula (T) are shown below, but the tetrazolium compound is not limited thereto.

[0056]

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The above tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, Vol. 55, pp. 335-483.

The tetrazolium compound used in the present invention can be produced by a known method, for example, a chemical review (Chemi).
cal Reviews) 55, 335-48.
It can be synthesized by the method described on page 3. The amount of addition may be an amount that makes the contrast high, and 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. It is in the range of 10 ^-6 to 10 ^-1 mol per mol, preferably in the range of 10 ^-5 to 10 ^-2 mol. The tetrazolium compound is preferably added to the silver halide emulsion layer, which is the hydrophilic colloid layer of the present invention, or a layer adjacent thereto.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention preferably contains a hydrazine derivative. The hydrazine derivative preferably used in the present invention is a compound represented by the following general formula (H).

[0060]

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In the formula, A represents an aryl group, a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) n-group, sulfonyl group, sulfoxy group, -P
(＝ O) R ₁₅ — or an iminomethylene group;
Represents integer of 1 or 2, A _1, A ₂ are both a hydrogen atom and the other or one hydrogen atom or a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group,, R ₁₄ represents hydrogen Represents an atom, each substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₁₅ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group,
Represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or an amino group.

In the present invention, the hydrazine compound is preferably a compound represented by the above formula (H), and more preferably a compound represented by the following formula (Ha).

[0063]

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In the formula, R ₁₆ is 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, chenyl group, Furyl group),
As these groups, those further substituted with a suitable substituent are preferably used. Further, R ₁₆ preferably contains at least one ballast group or silver halide adsorption promoting group.

As the diffusion-resistant 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 relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof 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.

X represents a group substitutable for a phenyl group,
l represents an integer of 0 to 4, and when 1 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.

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 ₁₇ 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 ₁₇ includes —COOR ₁₈ group and —CON
(R ₁₉ ) (R ₂₀ ) groups (R ₁₈ represents an alkynyl group or a saturated heterocyclic group; R ₁₉ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; R ₂₀ 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.

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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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 used in the present invention is
It can be synthesized by a known method, for example, by the method described in US Pat. No. 5,229,248, column 59 to column 80.

The amount of addition may be an amount which makes the contrast high (the amount of the contrast enhancement), and 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, etc. Generally, 10 ^-6 to 10 ^-1 per mol of silver halide
Molar range, preferably from 10 ^-5 to 10 ^-2 mol. The above hydrazine derivative is preferably added to a hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention, that is, a silver halide emulsion layer or a layer adjacent thereto.

In the present invention, at least one carboxyl group-active hardener represented by the following general formula [II] is used in combination in the hydrophilic colloid layer containing the compound represented by the general formula [I]. Is preferred.

[0083]

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In the formula, R ₂₁ and R ₂₂ each represent an alkyl group or an aryl group, and R ₂₁ and R ₂₂ may combine with each other to form a ring. R ₂₃ represents a hydrogen atom or a monovalent substituent.

L ₁ represents a single bond or a divalent linking group. L ₂
It is a single bond, an oxygen atom or -N (R ₂₄₎ - represents, R ₂₄
Represents a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group.

In the compound represented by the general formula [II],
As R ₂₁ and R ₂₂ , linear, branched, or cyclic carbon atoms having 1 to 1
20 alkyl groups (eg, methyl, ethyl, butyl,
Cyclohexyl, 2-ethylhexyl, dodecyl group, etc.), an aryl group having 6 to 30 carbon atoms (for example, phenyl,
Naphthyl group). R ₂₁ and R ₂₂ may have a substituent. Examples of the substituent include a chain or cyclic alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, i
-Propyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl,
4-carboxybutyl, 2-methoxyethyl, benzyl, phenethyl, 4-carboxybenzyl, 2-diethylaminoethyl, etc.), alkenyl having 2 to 8 carbon atoms (vinyl, acryl, etc.), alkoxy group having 1 to 8 carbon atoms (methoxy , Ethoxy, propoxy, butoxy, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), amino groups having 0 to 10 carbon atoms (amino, dimethylamino, diethylamino, carboxyethylamino, etc.), ester groups having 2 to 10 carbon atoms (Methoxycarbonyl, ethoxycarbonyl, etc.), amide group having 1 to 10 carbon atoms (acetylamino, benzamide, etc.), carbamoyl group having 1 to 10 carbon atoms (carbamoyl, methylcarbamoyl, ethylcarbamoyl, etc.), 6 to 10 carbon atoms Aryl groups (phenyl, naphthyl, 4-
Carboxyphenyl, 3-carboxyphenyl, 3,5
-Dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl, etc.), an aryloxy group having 6 to 10 carbon atoms (phenoxy, 4-carboxyphenoxy, 4-methylphenoxy, naphthoxy, etc.), 1 carbon atom Alkylthio group (methylthio, ethylthio, octylthio, etc.), arylthio group having 6 to 10 carbon atoms (phenylthio, naphthylthio, etc.), 1 carbon atom
10 to 10 acyl groups (acetyl, benzoyl, propanoyl, pivaloyl, etc.), 1 to 10 carbon atoms sulfonyl group (methanesulfonyl, benzenesulfonyl, etc.), 1 to 10 carbon atoms ureide group (ureido, methylureide, etc.), carbon Urethane groups of several 2 to 10 (methoxycarbonylamino, ethoxycarbonylamino, etc.), cyano groups,
Hydroxyl group, nitro group, heterocyclic group (5-carboxybenzoxazole, pyridine, sulfolane, furan,
Residues such as pyrrole, pyrrolidine, morpholine, piperazine, and pyrimidine), and are preferably a hydrogen atom, an alkyl group, an alkoxy group, an ester group, a halogen atom, a cyano group, and a hydroxyl group.

It is also preferred that R ₂₁ and R ₂₂ combine to form a ring together with the nitrogen atom, and a particularly preferred example is the case where a morpholine ring and a pyrrolidine ring are formed. R ₂₃ represents a hydrogen atom or a substituent. Examples of the substituent include those described above as substituents for the aryl group and the heterocyclic ring, with a hydrogen atom being particularly preferred.

L ₁ represents a single bond, an alkylene group having 1 to 20 carbon atoms (for example, methylene group, ethylene group, propylene group), an arylene group having 6 to 20 carbon atoms (for example, phenylene group) and a combination thereof. The resulting divalent group (for example, para-xylene group), acylamino group (for example,-
NHCOCH ₂ — group), sulfonamide group (eg, —N
It represents a divalent group such as HSO ₂ CH ₂ —). Among them, preferred are a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group.

L ₂ is a single bond or —O—, —N
(R ₂₄ ) —, wherein R ₂₄ is a hydrogen atom or a carbon number of 1 to 2
An alkyl group having 0 carbon atoms (eg, a methyl group, an ethyl group, a benzyl group); an aryl group having 6 to 20 carbon atoms (eg, a phenyl group); and an alkoxy group having 1 to 20 carbon atoms (eg, a methoxy group). However, a hydrogen atom is particularly preferred.

The carboxyl group-active hardener used in the present invention is a known compound, for example, US Pat.
Nos. 6,095 and 3,321,313;
No. 51945, No. 49-53819, No. 50-385
No. 40, No. 50-120616, No. 50-15435
No. 0, No. 51-59625, No. 51-126125
No. 51-84850, No. 52-48311, No. 52-54427, No. 52-6755, No. 52-9
No. 3469, No. 52-93470, No. 53-1138
No. 58, No. 53-118486, No. 54-4954
No. 54-27422, No. 55-155346,
No. 56-43353, No. 56-36645, No. 56
-110762, 56-110928, 57-
No. 26844, JP-A-57-44140, and JP-A-58-44
113929, JP-A-60-225148, 61-96
No. 41, No. 61-100743, No. 61-12824
No. 1, No. 61-240236, No. 61-36269
No., No. 61-112056, No. 62-68866,
62-68867, 62-234152, 6
2-181269, 62-262854, 62-
No. 264004, No. 63-229450, No. 63-6
Nos. 4041, 63-135935 and 63-415
No. 80, 63-184741 and JP-A-2-2737
No. 34 and other publications, and these compounds can be applied to the present invention.

Specific examples of the carboxyl group-active hardener represented by the general formula [II] are shown below, but the present invention is not limited thereto.

[0092]

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The above-mentioned carboxyl group-active hardener may be contained in the hydrophilic colloid layer according to the present invention in combination with the compound of the above general formula [I]. Photographic constituent layers containing gelatin, such as a light-sensitive or light-insensitive silver halide emulsion layer, an intermediate layer, a filter layer, an antistatic layer, a development control layer, an undercoat layer, an antihalation layer, and a backing layer.

The carboxyl group-active hardener is preferably dissolved in water or a water-soluble organic solvent (preferably methanol, acetone, ethanol or the like) and added to the coating solution to be contained.

The amount of the above-mentioned carboxyl group-active hardening agent to be used is not uniform depending on the type of the compound or the coating solution, but it is usually from 0.01 to 2.0 per gram of dried gelatin used. A range of 0 mmol is preferred, and a range of 0.03-1.0 mmol is more preferred.

In the present invention, when used in combination with the compound represented by the general formula [I], the carboxyl group-activating hardener is used in an amount of 0.01 to 100 to the compound represented by the general formula [I].
Equivalent, preferably 0.1 to 10 equivalents, more preferably 1.0 equivalent. The layer to be added may be the same layer as the compound represented by the general formula [I] or may be a separate layer.

The silver halide photographic light-sensitive material of the present invention may be further hardened with other known hardeners. Specific examples of known hardeners that can be used in combination include, for example, formalin, glyoxal, and succin. Aldehyde-type compounds such as aldehydes, 2,4-described in JP-B-47-6151.
Acid-releasing triazine compounds such as sodium dichloro-6-hydroxytriazine and the like.

The developer used in the present invention contains p
Preferably, H is treated at 7.5 to 10.5. Preferably, the pH is 8.5 to 10.4. This pH is lower than the normal developer pH, and this pH is considered from the viewpoint of storage stability of the developer, safety in handling, and pollution.
Region is preferred. The pH is adjusted with a pH buffer or hydrochloric acid,
It is appropriately adjusted with sulfuric acid or the like.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention may have any silver halide composition, for example, any of silver chloride, silver bromide, silver iodobromide and silver chloroiodobromide. May be used. The halogenated grains may be of any crystal type as long as they have the structure of the present invention, and may be, for example, single crystals such as cubic, octahedral, and tetrahedral, and may have various shapes. It may be a crystal grain.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (1
Emulsion, December 978), pp. 22-23.
Preparation and Types ”, or the method described in (RD) No. 18716 (November 1979), page 648.

That is, under solution conditions such as an acidic method, an ammonia method, and a neutral method, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, and a control double jet method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has an aspect ratio (grain size) / (grain thickness) of 3
The above tabular grains may be used.

The preferred tabular grains have an aspect ratio of 5 to 50, more preferably 5 to 20. Also, the equivalent spherical diameter of the particles is 0.2 μm to 3 μm.
0 μm, more preferably 0.4 μm to 10 μm. Further, the thickness of the particles is preferably 0.5 μm or less,
More preferably, it is 0.3 μm or less.

The advantages of such tabular grains are as described in, for example, British Patent 2,112,157 because they can improve the spectral sensitization efficiency and the graininess and sharpness of an image.
Nos. 4,414,310 and 4,434,2
No. 26, etc., and emulsions can be prepared by the methods described in these publications.

The crystal structure of silver halide may have a different silver halide composition between the inside and the outside, or may have a layered structure. A particularly preferred embodiment of the emulsion is a silver halide grain having substantially two distinct layered structures (core / shell structure) comprising a high iodine core portion and a low iodine shell layer.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, (RD) No. 17643 (December 1978
Month), (RD) No. 18716 (November 1979)
And (RD) No. 308119 (December 1989)
Various compounds described in (1) can be used.
The types and locations of the compounds described in these three (RD) are described below.

[0108]

[Table 1]

The support used in the silver halide photographic light-sensitive material of the present invention is preferably a transparent plastic support. As the plastic support, for example, a support made of polyethylene terephthalate, polyethylene naphthalate, triacetate cellulose, a polystyrene compound, or the like is used. Further, a support of a stretched film (SPS) made of a styrene polymer having a syndiotactic structure or a composition containing the same may be used.

The silver halide photographic light-sensitive material to which the present invention can be applied is not particularly limited. Examples thereof include a direct or indirect X-ray film, a reversal film for reproduction, and a CT film.
Examples include films for imagers, films for laser imagers, various films for printing plate making, and various films for color.

When the silver halide photographic light-sensitive material of the present invention is applied to, for example, printing plate making, it is preferable that the following compounds are contained in the constituent layers of the silver halide photographic light-sensitive material.

(1) Solid-dispersed fine particles of a dye Compounds described in pages (3) to (16) of JP-A-7-5629 (2) Compounds having an acid group JP-A-62-237445 (8) Compounds described in the lower right column of pages 25 to 25 (3) Acidic polymer Compounds described in pages 10 to 17 of JP-A-6-186659 (4) Sensitizing dye JP-A-5-224330 ( 3) Compounds described on pages (13) to (13) Compounds described on pages (11) to (22) of JP-A-6-194771 Compounds described on pages (2) to (8) of JP-A-6-242533 Compounds described in JP-A-6-337492, pages (3) to (34) JP-A-6-337494, compounds described in pages (4) to (14) (5) Supersensitizers JP-A-6-347938 Compounds described on pages (3) to (16) (6) Pyridinium compound: Compound described in JP-A-7-110556, pages (5) to (29) (7) Redox compound Compound described in JP-A-4-245243, pages (7) to (22) In the method for processing a silver halide photographic light-sensitive material of the present invention, any of known photographic processing agents can be used, for example, XX to XX of RD-17643 described above.
I, pp. 29-30 or XX-XXI, 101 of 308119
Processing with a processing solution as described on pages 1 to 1012 may be performed. This processing may be either black-and-white photographic processing for forming a silver image or color photographic processing for forming a dye image. The processing temperature is usually in the range of 18 ° C to 50 ° C.

Examples of the developer in black-and-white photographic processing include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), and aminophenols (eg, N-methyl-P-aminophenol). Etc. can be used alone or in combination. In the developer, for example, known preservatives, alkaline agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants, defoamers, colorants, water softeners, An agent, a viscosity imparting agent and the like may be used as necessary.

When a dye is formed by color photographic processing, for example, a color processing such as a negative-positive method or a color reversal method may be performed. Color developing solutions include phenylenediamines (e.g., 4-amino-N, N-dimethylaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-3-N-dimethylaniline) as primary aromatic amine developers known as color developing agents. Amino-3-methyl-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-hydroxyethylaniline).

In the color developer, for example, known preservatives, organic solvents, pH buffering agents, antifoggants, development accelerators, surfactants, defoamers, water softeners, polycarboxylic acid type chelating agents, It may contain an antioxidant and the like. After color development, normal bleaching processing may be performed, or bleach-fixing processing in which bleaching is performed simultaneously with fixing may be performed.

In the processing method of the present invention, after the silver halide photographic material of the present invention is exposed, it is processed with a developer containing the above-mentioned known materials.

[0117]

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

Example 1 On a triacetylcellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare multilayer color photographic light-sensitive material samples IA to IE, II
-A to II-E, III-A to III-E, and IV-A were produced.

[0119] The addition amount is particularly shows the number of grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling organic solvent (Oil-1) 0.12 Gelatin 1.53 Second layer: Intermediate layer Antifouling agent (SC-1) 0.06 High-boiling organic solvent (Oil-2) 0.08 Gelatin 0.80 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 0.38 μm, iodine Silver iodide bromide emulsion (average grain size: 0.27 μm, silver iodide content: 2.0 mol%) 0.15 Sensitizing dye (SD-1) 8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-4 sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.025 Boiling point solvent (Oil-1) 0.49 Gelatin 1.14 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0.89 Silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 8.0 mol%) 0.22 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye (SD-3) 1.6 × 10 ^-4 cyan coupler (C-1) 0.45 colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 High boiling point solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: Highly sensitive red-sensitive layer Silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol%) ) 1.27 sensitizing dye (SD-1) 1.3 × 10 -4 sensitizing dye (SD-2) 1.3 × 10 -4 sensitizing dye (SD-3) 1.6 ^10-4 Cyan coupler (C-2) 0.20 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling solvent (Oil-1) 0.57 Gelatin 1.10 The Sixth layer: Middle layer Color stain inhibitor (SC-1) 0.075 High boiling organic solvent (Oil-2) 0.095 Gelatin 1.00 Seventh layer: Middle layer Gelatin 0.45 Eighth layer: Low sensitivity green Sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content: 8.0 mol%) 0.64 Silver iodobromide emulsion (average grain size: 0.27 μm, silver iodide content: 2.0) 0.21 Sensitizing dye (SD-4) 7.4 × 10 ^-4 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.19 Magenta coupler (M -2) 0.49 Colored magenta coupler (CM-1) 0.12 High boiling solvent Oil-2) 0.81 Gelatin 1.89 Ninth layer: Medium-sensitive green-sensitive layer Silver iodobromide emulsion (average grain size: 0.59 μm, silver iodide content: 8.0 mol%) 0.76 Sensitizing dye (SD-6) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (M-1) 0 0.043 Magenta coupler (M-2) 0.10 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.37 gelatin 0.76 10th layer: high-sensitivity green-sensitive layer silver iodobromide emulsion (average grain size: 1.00 μm, silver iodide content: 8.0 mol%) 1.46 sensitizing dye (SD- 6) 0.93 × 10 ^-4 sensitizing dye (SD-7) 0.97 × 10 ^-4 sensitizing dye (SD-8) 0.9 3 × 10 ^-4 Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0.133 Colored magenta coupler (CM-1) 0.014 High boiling solvent (Oil-1) 0.15 High boiling solvent (Oil-2) 0.42 Gelatin 1.08 Eleventh layer: Yellow filter layer Yellow colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 Formalin scavenger (HS-1) 0.14 High boiling point solvent (Oil-2) 0.21 Gelatin 0.73 12th layer: Intermediate layer Formalin scavenger (HS-1) 0.18 Gelatin 0.60 13th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size) 0.59 μm, silver iodide content 8.0 mol%) 0.073 silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 3.0 mol%) 0.16 silver iodobromide emulsion (Average particle size .27Myuemu, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-9) 2.1 × 10 -4 Sensitizing dye (SD-10) 2.8 × 10 -4 Yellow coupler ( Y-1) 0.89 DIR compound (D-4) 0.008 High boiling solvent (Oil-2) 0.37 Gelatin 1.51 14th layer: Highly sensitive blue-sensitive layer Silver iodobromide emulsion (Average particle size) 1.00 μm, silver iodide content 8.0 mol%) 0.95 sensitizing dye (SD-9) 7.3 × 10 ^-4 sensitizing dye (SD-10) 2.8 × 10 ^-4 yellow coupler (Y-1) 0.16 High boiling point solvent (Oil-2) 0.093 Gelatin 0.80 15th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.05 μm, silver iodide content 3 0.00 mol%) 0.30 UV absorber (UV-1) 0.094 UV absorber (UV-2) 0.10 Formalin scuba Janger (HS-1) 0.38 High boiling point solvent (Oil-1) 0.10 Gelatin 1.44 16th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.55 In addition to the above composition, coating aid SU-1, dispersing aid SU-2, viscosity modifier, stability Agent ST-1, Dye AI-
1, AI-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 100,000
Of polyvinylpyrrolidone (AF-2) and the preservative DI-1 were added. The amount of DI-1 added is 9.4 mg.
/ M ² .

The hardener of the present invention and the hardener of the comparative example were added to the second protective layer immediately before coating. The hardener is the total amount of gelatin (total of gelatin used in the first to 16th layers)
Was added in the amounts shown in Table 2.

The structure of the compound used in the above sample is shown below.

[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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<< Evaluation of Photographic Performance >> Each prepared sample was used as a fresh sample, and this sample was treated at 50 ° C. and 50% RH for 3 hours.
Samples left for a day were prepared. After wedge exposure of these samples with white light, the following processing was performed, and the sensitivity and fog were measured. The sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog + 0.5, and is expressed as a relative sensitivity with the sensitivity of Sample 1-1 left at 50 ° C. and 50% RH for 3 days after coating as 100.

<< Evaluation of Hardening Performance >> A sample left at 25 ° C. and 50% RH for 3 hours, 2 days and 5 days was immersed in water at 30 ° C. for 5 minutes, and a sapphire needle having a radius of 0.3 mm was placed on the sample surface. The sapphire needle is continuously pressed and changed in the range of 0 to 200 g while being parallel-translated on the membrane surface at a speed of 2 mm per second during the pressure contact, and the load when the membrane surface of the sample is damaged is scratch-resistant. The strength was determined.

<< Evaluation of Residual Color >> The unexposed sample was developed under the following conditions, and the residual color level when five sheets were superimposed was visually evaluated on a five-point scale. Rank 5 is the best level, Rank 3
The above is a practically usable level.

(Processing step) Step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

<Preparation of Processing Agent> (Composition of Color Developing Solution) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Work up to 1.0 l and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Finished to 1.0 liter by adding water, and adjusted to pH 1 with potassium hydroxide or 20% sulfuric acid. Adjust to 0.18.

(Composition of bleaching solution) Water 700 ml 1,3-Diaminopropanetetraacetate iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Alternatively, adjust the pH to 4.4 using glacial acetic acid.

(Bleach replenisher composition) Water 700 ml 1,3-Diaminopropanetetraacetate ammonium iron (III) 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 with water or glacial acetic acid.

(Fixing solution formulation) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water is added to make up to 1.0 liter, and the pH is adjusted to 6.2 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 with aqueous ammonia or glacial acetic acid.

(Formulation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Water was added to make up to 1.0 liter, and the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

The results obtained are shown in Table 2 below.

[0144]

[Table 2]

As is evident from the results in Table 2, Samples 1-1 to 1-15 using the hardener of the present invention show a decrease in relative sensitivity and a small increase in fog even under forced deterioration conditions. Therefore, it can be seen that the hardener of the present invention hardly inhibits the photographic properties.

Further, from the time-dependent changes in the strength against damage indicating the film strength, all of the samples 1-1 to 1-15 of the present invention were compared with the comparative samples 1-16 and 1-17 more than two days after application. Since no change occurs after passing, it is understood that there is almost no post-hardening property.

Example 2 <Preparation of seed emulsion-I> Seed emulsion-I was prepared as follows.

A1 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 bromide 841 g of potassium 2825 ml of water D1 1.75 N aqueous solution of potassium bromide The following silver potential control amount: 42 ° C, JP-B-58-58288, 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. in 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again added. B1 and the solution C1 were each mixed by the simultaneous mixing method.
It was added at a flow rate of 4 ml / min for 42 minutes.

The temperature was raised from 42 ° C. to 60 ° C.
1. During the re-simultaneous mixing by C1, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to +8 mV and +16 mV, respectively, using the solution D1. After the addition was completed, the pH was adjusted to 6 with 3% KOH
, And immediately desalted and washed with water. The resulting seed emulsion is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 in at least 90% of the total projected area of the silver halide grains. The average thickness of the hexagonal tabular grains is 0.064 μm. It was confirmed by an electron microscope that the average particle size (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

<Preparation of Em-1> A tabular pure silver bromide emulsion Em-1 was prepared using the above seed emulsion-1 and the following three kinds of solutions.
Was prepared.

A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous solution of ethanol) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3150 ml with water B2 1747 g potassium bromide 3669 ml with water C2 Silver nitrate 2493 g Finished to 4193 ml with water While maintaining the solution A2 at 60 ° C. in a reaction vessel, the solution A2 was vigorously stirred, and the total amount of the solution B2 and the solution C2 was added thereto over 100 minutes by a simultaneous mixing method. During this time, the pH was adjusted to 5.8 and p
Ag was kept at 8.8 throughout. Here, solution B2 and solution C2
The addition rate was varied as a function of time to match the critical growth rate. That is, they were added at an appropriate addition rate so as to prevent generation of small particles other than the growing seed particles and to prevent polydispersion by Ostwald ripening.

After the addition was completed, the emulsion was cooled to 40 ° C.
As an aggregating polymer agent, 1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate 90%) was added and stirred for 3 minutes. afterwards,
A 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.6, and the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 4
After adding 9.0 l of distilled water at 0 ° C. and stirring and standing, the supernatant was drained, and 11.25 l of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% (by weight) aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse.

After redispersion, the pH was adjusted to 5.80 and the pA at 40 ° C.
g was adjusted to 8.06. When the obtained silver halide emulsion was observed with an electron microscope, a tabular halogen having an average particle size of 1.11 μm, an average thickness of 0.25 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% was obtained. It was silver halide particles. The average of the twin plane distance (a) is 0.020 μm.
m, the coefficient of variation of (a) was 32%.

After the emulsion was heated to 60 ° C., a predetermined amount of spectral sensitizing dye was added as a dispersion in the form of solid fine particles, and then adenine, ammonium thiocyanate and a sensitizer were added.
After 0 minute, a silver iodide fine grain emulsion was added and subjected to chemical ripening for a total of 2 hours.

At the end of the chemical ripening, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above additives and their amounts (per mole of AgX) are shown below.

Spectral sensitizing dye (SD-11) 2.0 mg Spectral sensitizing dye (SD-12) 120 mg Adenine 15 mg Ammonium thiocyanate 95 mg Sensitizer Water-soluble gold compound (HAuCl ₄ .4H ₂ O) 6.5 × 10 ⁻⁶ mol / mol silver Unstable sulfur compound (Na ₂ S ₂ O ₃ .5H ₂ O) 8.1 × 10 ⁻⁶ mol / mol silver Selenium compound (Ph ₃ P = Se) 8.1 × 10 ⁻⁶ Mol / mole silver iodide fine particles 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg

[0159]

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A dispersion of the solid fine particles of the spectral sensitizing dye was prepared according to the method described in Japanese Patent Application No. 4-99437.
That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been adjusted to 27 ° C. in advance, and the mixture is mixed with a high-speed stirrer (dissolver) at 3.500 rpm.
By stirring at for 30-120 minutes.

The average iodine content of the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-1) by the addition of the silver iodide fine grains was about 4 mol%.

Additives described below were added to the emulsion thus sensitized to prepare an emulsion layer coating solution, and at the same time, a protective layer coating solution was prepared.

The support had a thickness of 175 μm and a concentration of 0.1 μm.
On both sides of a polyethylene terephthalate film base for X-rays colored 15 in blue, diluted so that the concentration of a copolymer composed of three monomers of 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate and 40 wt% of butyl methacrylate would be 10 wt%. The resulting aqueous dispersion of the copolymer was dispersed and used as an undercoat liquid.

The following dye layers were coated on both sides of the support,
Next, the emulsion layer coating solution and the protective layer coating solution were simultaneously coated on both sides using two slide hopper type coaters so that the following coating amounts were obtained, dried, and dried to obtain a sample (No. I).
-F to IJ, II-F to II-J, III-F to III-J, IV
-B).

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (F-3) 180 mg / m ² Gelatin 0.2 g / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Latex (L-1) 0.2 g / m ² colloidal silica (average particle size: 0.014 μm) 10 mg / m ² Second layer (emulsion layer) The following various additives were added to Em-1 obtained above.

Compound (ST-2) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinyl Pyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium Chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (HS-2) 0.5 mg / m ² n- C ₄ H ₉ OCH ₂ CH (OH ) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (ST-3) 5 mg / m ² compound (ST-4) 0.2 mg / m ² compound (ST-5) 5 mg / m ² compound (ST- 6) 0.2 mg / m ² colloidal silica (particle size 0.3 μm or less) 0.5 g / m ² latex (L-1) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² 5- Methylbenzotriazole 0.7 mg / m ² However, it was adjusted to 1.0 g / m ² as gelatin.

Third layer (protective layer) Gelatin 0.8 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 20 mg / m ² Matting agent composed of polymethyl methacrylate 50 mg / m ² (area average particle size 7.0 μm) Latex (L-1) 0.2 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (HS-3) 20 mg / m ² compound (SA-1) 12 mg / m ² compound (SA-2) 2 mg / m ² compound (SA-3) 7 mg / m ² compound (HS-4) 15 mg / m ² compound (SA-4) 50 mg / m ² compound (SA-5) 5mg / m 2 C 9 F 19 -O- (CH 2 CH 2 O) 11 -H 3mg / m 2 (C 8 F 17 SO 2) (C 3 H 7) N - (CH ₂ CH ₂ O ^{_{15 -H 2mg / m 2 (C}} 8 F 17 SO 2) (C 3 H 7) N- (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2

[0168]

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[0169]

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[0170]

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The preservative DI-1 used in Example 1 was added to each sample. The hardener of the present invention and the comparative hardener were added to the protective layer immediately before application. The hardener was added in the amount shown in Table 2 with respect to the total amount of gelatin (total of gelatin used in the first to third layers).
The amount of the material applied was one side, and the amount of silver applied was adjusted to 1.6 g / m ² as one side.

Then, each of the prepared samples was used as a fresh sample, and the samples were left at 50 ° C. and 50% RH for 3 days to prepare samples.

The evaluation method was as follows. First, a sample was placed on two intensifying screens KO.
-250 (manufactured by Konica Corporation), tube voltage 80 kVp, tube current 100 mA, 0.05 through aluminum wedge
It was exposed to X-rays for 2 seconds. Next, automatic developing machine SRX
Using -502 (manufactured by Konica Corporation), the mixture was treated with a developer and a fixer having the following formulation.

Developer Formulation Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-methylbenzotriazole 1.2 g 1-phenyl-5 -Mercaptotetrazole 0.2 g Hydroquinone 340 g Water is added to make up to 5000 ml.

Part-B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1.0 L .

Fixer Formulation Part-A (for finishing 18 liters) Ammonium thiosulfate (70 wt / vol%) 6000 g sodium sulfite 110 g sodium acetate trihydrate 450 g sodium citrate 50 g gluconic acid 70 g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18 g Part-B 800 g of aluminum sulfate To prepare a developer, add Part A and Part B simultaneously to about 5 l of water, add water while stirring and dissolving, and add 12 l to make the pH to 10.40 with glacial acetic acid. It was adjusted. This is used as a developer.

20 ml / l of the above-mentioned starter was added to 1 liter of the developer to adjust the pH to 10.26 to obtain a working solution.

The fixing solution was prepared by adding Part A, P
artB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is used as a fixing replenisher.

The processing temperature was 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for washing, 50 ° C. for drying, and the processing time was dry.
45 seconds for to dry.

<< Evaluation of Photographic Performance >> After the treatment, the sensitivity was measured. The sensitivity in the table is represented by the reciprocal of the amount of exposure that gives a density of fog +0.5. The relative sensitivity was expressed by setting the sensitivity of 2-1 to 100.

<< Evaluation of Hardening Property >> 3 at 25 ° C. and 50% RH
Time, 2 days, 5 days
Sapphire needle with a radius of 0.3 mm is pressed against the sample surface, and the pressure load of the sapphire needle is continuously changed in the range of 0 to 200 g while moving parallel to the film surface at a speed of 2 mm per second. Then, the load when the film surface of the sample was damaged was determined as the scratch resistance.

<< Evaluation of Residual Color >> The unexposed sample was developed under the above-mentioned conditions, and the residual color level when five sheets were superimposed was visually evaluated in five steps. Rank 5 is the best level, Rank 3
The above is a practically usable level.

Table 3 shows the obtained results.

[0184]

[Table 3]

As is evident from the results in Table 3 above, Samples 2-1 to 2-15 using the hardener of the present invention showed little decrease in relative sensitivity and little increase in fog even under forced deterioration conditions.
Therefore, it can be seen that the hardener of the present invention hardly inhibits the photographic properties.

Example 3 A film sample containing the general formula (T) was prepared as follows.

Monodisperse, cubic silver chlorobromide particles having an average particle size of 0.15 μm and having a silver chloride content of 98 mol% and a silver bromide content of 2 mol% were prepared by a double jet method. K ₃ Rh (H ₂ O) during mixing
7 × 10 ⁻⁵ mol of Br ₅ was added per mol of silver. Before the desalting step of removing soluble salts by a conventional method, 0.6 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added per mol of silver (hereinafter, referred to as “the salt”). Unless otherwise specified, the amount is based on 1 mol of silver).

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

Next, additives were added so as to be in the following amounts per m ² to prepare a coating solution.

<Emulsion coating solution> Gelatin 10% solution 5.26 ml / m ² NaOH 0.5N solution 4.39 ml / m ² Compound B 6.53 mg / m ² Tetrazolium compound (T-1) 50 mg / m ² Killayasaponin 107 mg / m ² compound Q 18.5 mg / m ² compound I 9.8 mg / m ² compound table 4 described according to gelatin latex 480 mg / m ² of polystyrene sulphonic acid Na 52.2 mg / m ² table 4 <protective layer underlying solution preparation > gelatin 0.5 g / m ² compound F-6 62.0mg / m ² citric acid 4.1 mg / m ² compound G 1.7 mg / m ² of polystyrene sulphonic acid Na 11.0mg / m ² <upper protective layer> gelatin 0.3 g / m ² compound SA-5 18.0mg / m ² compound F-6 48.4mg / m ² compound Y 105.0 mg / m ² compound SA-6 .25mg / m ² amorphous silica (average particle 1.63 micron) 15.0 mg / m ² amorphous silica (average particle size 3.5 microns) 21.0 mg / m ² Citric acid 4.5 mg / m ² of polystyrene sulphonic Sodium acid 11.0 mg / m ^{2 In-} line addition of Compound G Treatment water content 6.0 g / m ² <Backing coating solution> Compound F-1 170 mg / m ² Compound F-6 30 mg / m ² Compound F-5 45 mg / m ² compound J 10 mg / m ² Quillaja saponin 111 mg / m ² compound L-3 200mg / m ² colloidal silica 200 mg / m ² compound U 35 mg / m ² compound R 31 mg / m ² compound V 3.1 mg / m ² Porimechirumeta Acrylic acid polymer (average particle size 5.6 microns) 28.9 mg / m ² glyoxal 10.1 mg / m ² Citric acid 9.3 mg / m ² polystyrene sulfonate Na 71.1 mg / m additive compound the following ^2-line AA 81 mg / m ² Compound BB 88.2mg / m ² of calcium acetate 3.0 mg / m ² Compound G treatment water content 6.0 g / m ²

[0191]

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[0192]

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The above-mentioned coating solution was applied by adding the addition amount shown in Table 4 to the total amount of gelatin. The coating amount was uniform so that the silver amount of the emulsion layer was 2.0 g / m ² and the gelatin amount of the backing layer was 2.1 g / m ² .

<Per liter of developer composition> Diethylenetriaminepentaacetic acid / 5 sodium salt 1.0 g Sodium sulfite 42.5 g Potassium sulfite 17.5 g Potassium carbonate 55.0 g Hydroquinone 20.0 g 1-phenyl-5-mercaptotetrazole 03 g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.85 g potassium bromide 4.0 g benzotriazole 0.21 g boric acid 8.0 g diethylene glycol 40.0 g 8-mercaptoadenine 0.07 g water and hydroxylated Add potassium to make up to 1 liter and pH
10.4

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

<< Evaluation of Photographic Performance >> Each prepared sample was used as a fresh sample, and this sample was treated at 50 ° C. and 50% RH for 3 hours.
Samples left for a day were prepared. After wedge exposure of these samples with white light, the following processing was performed, and the sensitivity and fog were measured. The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 0.5, and the sample No. was left at 50 ° C. and 50% RH for 3 days after coating. The relative sensitivity was expressed by setting the sensitivity of 3-1 to 100.

<< Evaluation of Hardening Performance >> A sample left at 25 ° C. and 50% RH for 3 hours, 2 days and 5 days was immersed in water at 30 ° C. for 5 minutes, and a sapphire needle having a radius of 0.3 mm was placed on the sample surface. The sapphire needle is continuously pressed and changed in the range of 0 to 200 g while being parallel-translated on the membrane surface at a speed of 2 mm per second during the pressure contact, and the load when the membrane surface of the sample is damaged is scratch-resistant. The strength was determined.

<< Evaluation of Residual Color >> The unexposed sample was developed under the following conditions, and the residual color level when five sheets were superimposed was visually evaluated on a five-point scale. Rank 5 is the best level, Rank 3
The above is a practically usable level.

The results obtained are shown in Table 4 below.

[0201]

[Table 4]

As is clear from the results, the samples 3-1 to 3-16 of the present invention show that there is little decrease in relative sensitivity and little rise in fog even under forced deterioration conditions, and there is no deterioration in photographic performance. I have. Also, regarding the scratch resistance indicating the film strength, any of Samples 3-1 to 3-16 of the present invention does not change after 2 days or more after application compared to the comparative sample, so that almost no post-hardening property is recognized. I couldn't.

Example 4 (Preparation of Silver Halide Emulsion A-1) The following aqueous silver nitrate solution A and a water-soluble halide solution B comprising NaCl and KBr
Was added to the C solution at a silver potential (EAg) of 120 mV, pH 3.0, 35 ° C. for 7 minutes by a double jet method to form a nucleus of 0.09 μm of 70 mol% of AgCl and 30 mol% of Br. Then, the silver potential was adjusted to 100 mV with NaCl, an aqueous silver nitrate solution D and a water-soluble halide solution E were added again for 15 minutes, and AgCl 7 having a particle size of 0.20 μm (coefficient of variation 15%) was added.
An emulsion consisting of 0 mol% and 30 mol% of Br was obtained. Thereafter, the pH was adjusted to 5.6 with a 1N-NaOH aqueous solution, and sensitizing dye S-1 described below was added at 2 × 10 ^-4 mol per mol of silver, followed by ripening at 50 ° C. for 10 minutes.

Next, denatured gelatin treated with phenyl isocyanate was added, and the floc was washed with water at pH 4.2. After washing with water, 15 g of gelatin per mole of silver was added to adjust the pH to 5.7, and dispersed at 55 ° C. for 30 minutes. did. After dispersion
Chloramine T was added in an amount of 4.times.10.sup.- ⁴ mol per mol of silver. The silver potential of the resulting emulsion is 190 mV (40 ° C.)
Met.

A: silver nitrate 16 g nitric acid 5% 5.3 ml ion-exchanged water 48 ml B: NaCl 3.8 g KBr 3.5 g ossein gelatin 1.7 g ion-exchanged water 48 ml C: NaCl 1.4 g ossein gelatin 7 g nitric acid 5% _{6.5ml K 2 RhCl 5 (H 2} O) 0.06mg ion exchanged water 700 ml D: Silver nitrate 154g nitric acid 5% 4.5 ml ion-exchanged water 200ml E: NaCl 37g KBr 33g ossein gelatin 6g K ₂ RhCl ₅ (H ₂ O) 0.04 mg ion-exchanged water 200 ml 4-hydroxy-6
Methyl-1,3,3a, 7-tetrazaindene (TA
I) was 1.5 × 10 ⁻³ mol, and potassium bromide was 8.5 × 1.
The pH was adjusted to 5.6 and the EAg to 123 mV by adding 0 ^-4 mol.

Next, 2 × 10 ⁻⁵ mol of sulfur flower dispersed as fine particles as sulfur atom and 1.5 × 10 ⁻⁵ mol of chloroauric acid were added.
^-5 mol, and a chemical ripening at a temperature of 60 ° C. for 80 minutes was carried out. Then, 2 × 10 ^-3 mol of TAI, 3 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and 1 × 10 ^-4 mol of iodine per mol of silver were added. 1.5 × 10 ^-3 mol of potassium iodide was added.

Then, after the temperature was lowered to 40 ° C., 2 × 10 ^-4 mol of sensitizing dye S-2 described below was added per mol of silver.

(Preparation of Silver Halide Emulsion A-2)
In the emulsion formulation of 1 Solution C K ₂ RhCl ₅ (H
The ₂ O) and 0.10 mg, the mixing temperature except for the 40 ° C., the particle size 0.25μm was prepared exactly as Emulsion A-1
(Coefficient of variation: 15%) An emulsion composed of 70 mol% of AgCl and 30 mol% of Br was obtained. Thereafter, chemical sensitization and spectral sensitization were performed in the same manner as in Emulsion A-1.

Next, a redox compound layer, a solid disperse dye layer, a silver halide emulsion layer, and an emulsion protective layer each having the following composition were coated simultaneously on the undercoated polyethylene terephthalate base support from the support side. After the cooling setting, a backing layer and a backing protective layer were simultaneously applied on the undercoating layer on the opposite side from the support side, and cooled and set at -1 ° C., and both sides were simultaneously dried.

Preparation of Coating Solution Redox Compound Layer Silver Halide Emulsion A-2 Ag amount 0.3 g / m ² Gelatin 0.3 g / m ² Saponin 60 mg / m ² DIR-2 50 mg / m ² Solid disperse dye layer Gelatin 1 0.0 g / m ² AD-11 15 mg / m ² AI-2 5 mg / m ² L-2 (particle size 0.25 μm) 0.3 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Silver halide emulsion layer Halogen Silver halide emulsion A-1 Ag amount 3.3 g / m ² Gelatin 1.5 g / m ² Hydrazine compound H-34 10 mg / m ² Latex (L-1) (particle size 0.10 μm) 0.5 g / m ² colloid Suspension polymer of 75% by weight of silica and 12.5% by weight of vinyl acetate and 12.5% by weight of vinyl pivalinate 1.0 g / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxypropyl Phosphorus 2 mg / m ² Ascorbic acid 20 mg / m ² EDTA · 2Na 25 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500,000) 15 mg / m ² Compound listed in Table 5 Table 5 Coating solution pH was 5.2 .

Intermediate layer Gelatin 0.32 g / m ² Nucleation promoter: N-1 12.9 mg / m ² Latex (L-1) 0.3 g / m ² Sodium polystyrene sulfonate (average molecular weight 500,000) 10 mg / m ² protective layer gelatin 0.48 g / m ² dye: F-2 50 mg / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 12 mg / m ² compound SA-3 0.6 mg / m ² matting agent: mean Particle size 3 μm irregular silica 22.5 mg / m ² Garlic acid propyl ester 90 mg / m ² Dimethylsiloxane (average molecular weight 100,000) dispersion (average particle size 0.2 μm) 12 mg / m ² Hardener K-12 30 mg / m ² sodium polystyrenesulfonate 10 mg / m ² fungicide Z 0.5 mg / m ² backing layer gelatin 3.0 g / m ² sodium - iso - amyl -n Decyl sulfosuccinate 5 mg / m ² Compound D 50 mg / m ² Compound L-3 0.3g / m ² Colloidal silica (average particle size 0.05μm) 0.5g / m ² Sodium polystyrenesulfonate 10 mg / m ² F- 1 120 mg / m ² F-4 15 mg / m ² F-5 37 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² Compound: D 50 mg / m ² Hardener K-11 100 mg / m ² Backing protection Layer Gelatin 1.1 g / m ² Matting agent: monodispersed polymethyl methacrylate having an average particle size of 3 μm 45 mg / m ² sodium-di (2-ethylhexyl) sulfosuccinate 10 mg / m ²

[0212]

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[0213]

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Composition of used developer (per liter of used solution) Pure water 224 ml DTPA · 5Na 1.0 g Potassium sulfite 12.54 g Sodium sulfite 42.58 g KBr 4 g H ₃ BO ₃ 8 g Potassium carbonate 55 g Diethylene glycol 40 g 5-methylbenzotriazole 0.21 g 1-phenyl-5-mercaptotetrazole 0.03 g Dimezone S 0.85 g Hydroquinone 20 g KOH 18 g Dissolved according to the above-mentioned formula to finish to 400 ml. When used, 600 ml of pure water was mixed to make 1 liter. The pH of the working solution was 10.40.

Fixer composition (per liter of working solution) Pure water 216 ml Ammonium thiosulfate 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 37.8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate 18 hydrate 18 g According to the above-mentioned formula, it melt | dissolved and completed it to 400 cc with pure water. When used, 600 ml of pure water and the above-mentioned concentrated liquid are mixed and used. The pH of the working solution was 4.83.

(Processing Conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / Dry 45 ° C. 30 seconds Total 100 seconds Each prepared sample is used as a fresh sample. This sample is
Leave at 0 ° C. and 50% RH for 3 days to obtain a forcibly deteriorated sample, for example. These samples were irradiated with 3200 ° K tungsten light.
Exposure for 2 seconds, automatic developing machine GR-27 (manufactured by Konica Corporation)
Was processed under the above conditions with the developing solution and the fixing solution having the above formulation.

<< Evaluation of Photographic Performance >> The sensitivity in the table is +0.5.
Is expressed as the reciprocal of the exposure amount that gives the density of
Sample No. was left at 0% RH for 3 days. 4-1 sensitivity is 1
The relative sensitivity when the value was set to 00 was shown.

<< Evaluation of Hardening Performance >> A sample left at 25 ° C. and 50% RH for 3 hours, 2 days and 5 days was placed at 30 ° C.
Immersed in water for 5 minutes, a sapphire needle having a radius of 0.3 mm was pressed against the sample surface, and the sapphire needle was pressed against the surface of the sample within a range of 0 to 200 g while moving in parallel at a speed of 2 mm per second. The load when the film surface of the sample was damaged by continuous change was determined as the scratch resistance.

<< Evaluation of Residual Color >> The unexposed sample was developed under the above conditions, and the residual color level when five sheets were superimposed was visually observed.
It was evaluated on a scale. Rank 5 is the best level, and rank 3 or higher is a level that can withstand practical use.

Table 5 shows the obtained results.

[0221]

[Table 5]

As is clear from the results shown in Table 5, Samples 4-1 to 4-14 of the present invention showed little decrease in relative sensitivity and little fog even under forced deterioration conditions, and did not deteriorate photographic performance. . In addition, the samples 4-1 to 4-14 of the present invention show no change after 2 days or more after the application compared with the comparative samples 4-15 and 4-16 from the temporal change of the scratch resistance indicating the film strength. This shows that there is no post-hardening property.

Example 5 (Preparation of Silver Halide Emulsion B) The silver chloride emulsion 100 was prepared by controlling the potential to 90 mV using a double jet method.
Silver chloride core particles having an average particle size of 0.12 μm consisting of mol% were prepared. At the time of mixing the core particles, 5 × 10 ⁻⁵ mol of K ₂ OsCl ₅ (NO) was added per mol of silver.

By controlling the electric potential to 90 mV by using a double-mixing method, silver chloride 100
A shell consisting of mol% was attached. At that time, K ₂ OsCl
₅ (NO) was added in an amount of 7.5 × 10 ⁻⁵ mol per mol of silver.

The obtained emulsion was a core / shell type monodispersed (coefficient of variation: 10%) silver chloride emulsion having an average particle size of 0.15 μm. Then, a modified gelatin described in JP-A-2-280139 (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139).
(3), and then desalted. Further, before the desalting step, 1 × 10 ⁻³ mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver. (Hereinafter, unless otherwise specified, the amount is per mol of silver). The EAg after desalting was 190 mV at 50 ° C.

To the obtained emulsion, 1 × 10 −3 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per 1 mol of silver, and potassium bromide and citric acid were further added. to pH 5.6, and adjusted to EAg123mV, 3 × 10 ^-6 mol of inorganic sulfur after chloroauric acid were added 1 × 10 ^-5 mol, diphenyl pentafluorophenyl selenide 2 × 10 ^-6 mol added Aging at 60 ° C. for 60 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, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻⁴ mol, and gelatin was added. The emulsion was set at a reduced temperature.

Next, the first emulsion layer, the second emulsion layer, the lower protective layer, and the upper protective layer were successively coated on one undercoat layer of the following support so that the following amounts per m ² were obtained. Minute 2
Simultaneous multilayer coating was performed at 50 m by a curtain coating method.

After forming an antistatic layer of the following composition on the undercoat layer on the opposite side, a backing layer, a hydrophobic polymer layer and a backing protective layer were simultaneously formed so that the following amounts per unit m ² were obtained. Multi-layer coating was performed.

<Support> A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) is provided with 30 W /
After a corona discharge of (m ² · min), an undercoat layer having the following composition was applied on both sides and dried at 100 ° C. for 1 minute.

(Undercoat layer) Copolymer of 2-hydroxyethyl methacrylate (25) -butyl acrylate (30) -t-butyl acrylate (25) -styrene (20) (numbers are weight ratio) 1.5 g / m ² surfactant SA-1 10 mg / m ² hexamethylene-1,6-bis (ethyleneurea) 15 mg / m ² 10 W a polyethylene terephthalate support subjected to (antistatic layer) subbing layer / (m ² · min), a coating solution for an antistatic layer having the following composition was applied on one side to 70 m / min.
min using a roll-fit coating pan and an air knife, drying at 90 ° C for 2 minutes,
Heat treatment was performed at 140 ° C. for 90 seconds.

Coating solution for antistatic layer Water-soluble conductive polymer L-4 0.6 g / m ² Hydrophobic polymer particle L-5 0.4 g / m ² Polyethylene oxide compound X 0.1 g / m ² Hardener K -12 0.2 g / m ² First emulsion layer composition Emulsion B coated silver amount 1.5 g / m ² Gelatin 0.3 g / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² Compound Y 10 mg / m ² hydrazine compound H-29 50mg / m ² nucleation accelerator P-1 20mg / m ² nucleation accelerator N-1 20mg / m ² chloroauric acid 0.1 mg / m ² of polystyrene sulphonic acid Na 50 mg / m ² styrene - the hydrophilic polymer 20 mg / m ² Sodium maleic acid copolymer - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² 5-methylbenzotriazole 10 mg / m ² Shikurodekisu Phosphorus (hydrophilic polymer) 0.5 g / m ² Table 6 Compound Table 6 wherein the second emulsion layer composition emulsion described B coated silver amount 1 g / m ² Gelatin 0.9 mg / m ² N-oleyl -N- methyl taurine sodium Salt 35 mg / m ² Nucleation enhancer N-1 20 mg / m ² Compound I 10 mg / m ² Adenine 20 mg / m ² Compound D 10 mg / m ² Latex L-2 1 g / m ² Colloidal silica (mean particle size 0.05 μm ) 100 mg / m ² of polystyrene sulphonic acid Na 20 mg / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² protective layer underlayer composition gelatin 0.8 g / m ² dye solid fine particle AD-11 60mg / m ² hydroquinone 50 mg / m ² latex L-2 1 g / m ² colloidal silica (average particle size 0.05 .mu.m) 100 mg / m ² of polystyrene Sulfonic acid Na 11 mg / m ² Styrene - hydrophilic polymer 20 mg / m ² Sodium maleic acid copolymer - iso - amyl -n- decyl sulfosuccinate 12 mg / m ² upper protective layer composition Gelatin 0.8 g / m ² Compound F-6 30 mg / m ² matting agent: amorphous silica (average particle size 1.63 μm) 15.0 mg / m ² matting agent: amorphous silica (average particle size shown in Table 2) 21.0 mg / m ² citric acid 4.5 mg / m ² of polystyrene sulphonic acid Na 11.0 mg / m ² hardener K-12 5 mg / all layers of gelatin 1g around surfactant SA-3 1mg / m ² Sodium - iso - amyl -n- decyl sulfosuccinate Nate 12 mg / m ² Backing layer composition Gelatin 0.8 g / m ² Sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² Latex L-2 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Hardener K-12 10 mg / m ² Hydrophobic polymer layer composition Latex (methyl methacrylate: acrylic acid) = 97: 3) 1.0 g / m ² Hardener K-11 6 mg / m ² Backing protective layer composition Gelatin 0.5 g / m ² F-1 160 mg / m ² F-5 30 mg / m ² Styrene-maleic acid Copolymer hydrophilic polymer 20 mg / m ² Matting agent Monodisperse polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant SA-3 50 mg / m ² HO (CH ₂ CH ₂ O) ₆₈ H 50 mg / m ² Hardener K-12 20 mg / m ²

[0233]

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The surface resistivity of the backing layer after coating and drying was 6 × 10 ¹¹ at 23 ° C. and 20% RH, and the pH of the emulsion side surface was 5.5.

(Preparation of solid fine particle dispersion) In the examples of the present invention, solid fine particle dyes prepared according to the following method were used.

In a 60 ml screw cap container, 21.7 ml of water and Triton X- as a surfactant were added.
6.7% solution 30 of 200 (Rohm & Haas)
of the dye powdered in a mortar into this container.
0 g and a surfactant were added, and 40 ml of zirconium oxide beads (2 mm diameter) were added. Close the cap, place in a ball mill, disperse at room temperature until the desired particle size is achieved, add 8.0 g of a 12.5% gelatin aqueous solution, mix well, filter out zirconium oxide beads, and remove solid fine particle dispersion. Obtained.

(Composition of processing solution used in this example) Development start solution (HAD-S) (per liter of used solution) Diethylenetriaminepentasodium pentasodium 10.9 g Potassium sulfite 31.8 g Sodium sulfite 42.6 g KBr 4 g H ₃ BO ₃ 8 g Potassium carbonate 112.2 g 2-mercaptoadenine 0.07 g Diethylene glycol 40 g 5-methylbenzotriazole 0.21 g 1-phenyl-5-mercaptotetrazole 0.03 g Dimezone S (1-phenyl-4-hydroxymethyl-4 -Methylpyrazolidone) 0.85 g Hydroquinone 20 g Compound E 5.5 g Pure water and KOH are added to make 1000 ml and the pH is adjusted to 10.40.

Preparation of Development Replenishing Granules (KR) <Preparation of Granulation A Parts> (for 1 liter of liquid used) Diethylenetriaminepentasodium pentasodium 1.45 g Sodium carbonate (monohydrate) 76.27 g D-mannitol (product) 6.94 g Sorbitol 2.93 g LiOH 10 g The above materials were mixed in a commercially available bandal mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. It was dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain a granulated A part having an average particle diameter of 3000 μm and a repose angle of 33 °.

<Preparation of Granulation B Parts> (for 1 liter of liquid used) Sodium sulfite 56.58 g KBr 2 g H ₃ BO ₃ 4 g 2-mercaptoadenine 0.25 g 5-methylbenzotriazole 0.26 g 1-phenyl-5 -Mercaptotetrazole 0.06 g Dimezone S 1.25 g Hydroquinone 20 g Compound E 5.5 g D-mannitol (trade name: manufactured by Kao Corporation) 4.77 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and then further commercially available under stirring. After granulating at room temperature for 10 minutes with a granulator, the granulated product was dried in a fluidized-bed dryer at 40 ° C. for 2 hours to obtain a granulated product B part having an average particle size of 4000 μm and a repose angle of 30 °.

The above parts A and B were thoroughly mixed to obtain a replenisher for granule development HAD-KR.

[0241] At the time of use, it was dissolved in water to make 1 liter. The pH of the working solution was 10.70.

1 liter of fixing start solution (HAF-S) used solution 1 liter pure water 116 ml ammonium thiosulfate 140 g sodium sulfite 22 g boric acid 9.8 g tartaric acid 3 g sodium acetate trihydrate 34 g acetic acid (90% aqueous solution) 14.5 g aluminum sulfate 18-hydrate salt 18 g Finished to 400 ml with pure water. When using, mix 600 ml of pure water with the above-mentioned concentrated liquid. The pH of the working solution was 4.90.

Preparation of Fixation Replenishing Granules (HAF-KR) <Preparation of Granulation A Parts> (for 1 liter of liquid used) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium metabisulfite 7.5 g Acetic acid Sodium 40g Pine flow (trade name: manufactured by Matsutani Chemical Co., Ltd.) 11.8g The above materials were mixed in a commercially available vandal mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator.
The granulated product was dried in a fluidized-bed dryer at 40 ° C. for 2 hours to obtain a granulated product A part having an average particle size of 4000 μm and a repose angle of 40 °.

<Preparation of Granulation B Parts> (for 1 liter of liquid used) 10 g of boric acid 3 g of tartaric acid 26.5 g of sodium hydrogen sulfate 15.8 g of aluminum sulfate / 18-hydrate D-mannitol (trade name: manufactured by Kao Corporation) 4 g N-lauroyl taurine (trade name: manufactured by Nikko Chemicals) 2 g Demol N (trade name: manufactured by Kao Corporation) 5 g The above materials were mixed in a commercially available vandal mill for 30 minutes, and further mixed with a commercially available stirring granulator at room temperature. After granulating for 10 minutes, the granulated product was dried in a fluidized-bed dryer at 40 ° C. for 2 hours to obtain a granulated product B part having an average particle diameter of 3300 μm and a repose angle of 28 °.

The parts A and B were completely mixed to obtain a fixing granule replenisher HAF-KR. When used, it was used by dissolving it in water so that the volume became 1 liter. The pH of the working solution was 4.20.

As an automatic developing machine (GR- manufactured by Konica Corporation)
26SR). The drying zone of this automatic processor has a far-infrared heater and a cover that covers the entire surface of the processing tank so that the processing liquid is not easily evaporated.

[0247] The fixing waste liquid is processed while returning the processing liquid after silver recovery using the silver recovery apparatus described in Example 1 of JP-A-6-27623 to the fixing tank again. The treatment was carried out using a descaling device (water clean).

Each prepared sample was used as a fresh sample.
This sample was left at 50 ° C. and 50% RH for 3 days to prepare a forced deterioration sample. The obtained sample is sent to a light room printer P6.
Exposure was performed using 27FM (manufactured by Konica Corporation) using a step wedge, and the film was processed under the above processing conditions using the above automatic developing machine.

<Evaluation of photographic performance> Sensitivity is represented by the reciprocal of the exposure amount giving a density of +0.5.
H for 3 days. The relative sensitivity is shown with the sensitivity of 5-1 taken as 100. <Evaluation of Hardening Characteristics> A sample left at 25 ° C. and 50% RH for 3 hours, 2 days, and 5 days was immersed in water at 30 ° C. for 5 minutes, and a sapphire needle having a radius of 0.3 mm was pressed against the sample surface. The load at the time when the film surface of the sample is damaged is determined as the scratch resistance by continuously changing the pressure contact load of the sapphire needle within the range of 0 to 200 g while moving in parallel on the film surface at a speed of 2 mm per second. Was.

<Evaluation of Residual Color> The unexposed sample was developed under the above conditions, and the residual color level when five sheets were superimposed was visually observed.
It was evaluated on a scale. Rank 5 is the best level, and rank 3 or higher is a level that can withstand practical use.

The obtained results are shown below.

[0252]

[Table 6]

As is clear from the results shown in Table 6, Samples 5-1 to 5-16 of the present invention showed little decrease in relative sensitivity and little fog even under forced deterioration conditions, and showed little impairment of photographic performance. I understand. In addition, from the change with time of the scratch resistance indicating the film strength, all of the samples 5-1 to 5-16 of the present invention disappear after 2 days or more after application compared with the comparative samples 5-17 and 5-18. This shows that there is no post-hardening property.

Example 6 (Preparation of Silver Halide Emulsion C-1) Using a double jet method, 70 mol% of silver chloride was used, and the balance was made of silver bromide.
09 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 7 × 10 ⁻⁸ mol per mol of silver per mol of silver, and K ₃ O was used.
In the presence of 8 × 10 ^-6 mol of sCl ₆ , 40 ° C., p
While maintaining H3.0 and the silver potential (EAg) at 165 mV, an aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed.

EAg was added to the core particles with sodium chloride at 125 mV.
And a shell was attached by the simultaneous mixing method. At this time, K ₂ IrCl ₆ was added to the halide solution in an amount of 3 × 10 ⁻⁷ mol per mol of silver,
9 × 10 ⁻⁸ mol of K ₃ RhCl ₆ was added. Further, KI conversion was performed using silver iodide fine grains. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide having an average diameter of 0.15 μm (silver chloride: 70 mol%,
(A silver iodobromide 0.2 mol%, the balance being silver bromide).

Then, the modified gelatin described in JP-A-2-280139 (example 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) is used. Use desalted.
The EAg after desalting was 190 mV at 50 ° C.

The resulting emulsion was mixed with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at 1.5 × 10 ^-3 mol per mol of silver and potassium bromide at 8.5 × 10 ³ mol.
PH 5.6, EAg12 with addition of ^-4 mol and citric acid
After adjusting the pressure to 3 mV and adding 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) to cause a reaction, the inorganic sulfur (S) dispersed in the solid was added.
8) The compound was dispersed in a mean particle size of 0.5 μm by adding saponin using PM-1200 manufactured by Seishin Enterprise Co., Ltd., and 1.5 × 10 ⁻⁵ mol of chloroauric acid was added thereto and the temperature was increased. After chemical ripening at 55 ° C until maximum sensitivity is obtained, 5
At 0 ° C., 100 mg of sensitizing dye d-1 and 5 mg of trihexylamine were added, and the temperature was further lowered to 40 ° C., and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to 1 mol of silver. After adding 2 × 10 ^-3 mol, 3 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and 5 × 10 ^-3 mol of potassium iodide, the pH was adjusted to 5.1 with citric acid. (Preparation of silver halide emulsion C-2) The reaction temperature was 50
℃ to make the particle size 0.19μm, K ₃ R
A silver halide emulsion C-2 was prepared in exactly the same manner as in C-1, except that the amount of hCl ₆ was changed to 6 × 10 ⁻⁸ mol.

When the same chemical sensitization as in C-1 was performed, C
The emulsion of -2 was 40% more sensitive than the emulsion of C-1.

Next, a gelatin subbing layer of the following formula 1 was placed on a support so that the amount of gelatin was 0.45 g / m ² .
The silver halide emulsion layer 1 of the formula 2 was overlaid thereon with a silver amount of 1.5.
g / m ² , and the amount of gelatin is 0.65 g / m ² .
Further, the silver halide emulsion layer 2 of formula 3 was further overlaid thereon with a protective layer coating solution of formula 4 below so that the amount of silver was 1.5 g / m ² and the amount of gelatin was 0.65 g / m ^2. Simultaneous multi-layer coating was performed so as to obtain 0.7 g / m ² .

On the other side of the undercoat layer, a backing layer of the following formulation 5 was provided so that the amount of gelatin was 1.5 g / m ^2, and a backing protective layer of the following formulation 6 was provided thereon with a gelatin amount of 0.1 g / m ² . The emulsion layer side and the emulsion layer side were simultaneously layer-coated at a speed of 200 m / min by a curtain coating method so that the emulsion layer side became 8 g / m ² , and cooled and set. It was cooled and set, and both sides were dried at the same time.

Formulation 1 (Gelatin undercoat layer composition) Gelatin 0.45 g / m ² saponin 56.5 mg / m ² Redox compound DIR-2 (dissolved in ethyl acetate and dispersed in a gelatin solution, then ethyl acetate was removed under reduced pressure 25 mg / m ² Solid disperse dye AD-11 50 mg / m ² Sodium polystyrene sulfonate (average molecular weight: 50,000) 15 mg / m ² Disinfectant z 0.5 mg / m ² Prescription 2 (Composition of Silver Halide Emulsion Layer 1) Silver Halide Emulsion C-1 Silver equivalent of 1.5 g / m ² equivalent Sensitizing dye S-3 150 mg / Ag 1 mol Hydrazine compound H-26 2 × 10 ^-3 mol / Ag 1 Molar amino compound N-1 7 mg / m ² Compound J 100 mg / m ² 2-pyridinol 1 mg / m ² Latex L-2 (particle size 0.25 μm) 0.25 g / m ² Compound described in 7 Table 7 shows sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² sodium naphthalenesulfonate 8 mg / m ² saponin 20 mg / m ² hydroquinone 20 mg / m ² 2-mercapto-6 Hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 150 mg / m ² Ascorbic acid 20 mg / m ² EDTA 25 mg / m ² Sodium polystyrene sulfonate 15 mg / m ² Coating solution pH Was 5.2.

Formulation 3 (Composition of Silver Halide Emulsion Layer 2) Silver Halide Emulsion C-2 Amount of silver 1.5 g / m ² equivalent Sensitizing dye S-4 100 mg / Ag 1 mol Hydrazine compound H-274 4 × 10 ^-3 mol / Ag 1 mol Amino compound N-1 7 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Nicotinamide 1 mg / m ² Gallic acid n-propyl ester 50 mg / m ² Mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² Latex L-6 (JP-A-5-66512) Example 3 Type Lx-3 Composition (9)) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² gelatin Was a phthalated gelatin, and the coating solution pH was 4.8.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² amino compound N-1 14 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: average particle size 3 0.5 μm spherical polymethyl methacrylate 25 mg / m ² Average particle size 8 μm amorphous silica 12.5 mg / m ² Surfactant SA-3 26.5 mg / m ² Slip agent (silicone oil) 4 mg / m ² Compound J 50 mg / m ² latex L-3 (particle size 0.10 μm) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 500 mg / m ² F-6 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² hardener K-11 30mg / m ² of sodium polystyrenesulfonate 10 mg / m ² fungicide Z 0.5 mg / m ² formulation 5 (aeration Grayed layer composition) Gelatin 0.6 g / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² Latex L-3 0.3g / m ² Colloidal silica (average particle size 0.05 .mu.m) 100 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² F-6 65 mg / m ² F-4 15 mg / m ² F-7 100 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² Hardener K-12 100 mg / m m ² zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² prescription 6 (backing protective layer) gelatin 0.4 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 system silica 12.5 mg / m ² Sodium - di-2-ethylhexyl - sulfosuccinate 10 mg / m ² surfactant SA ^{3 1mg / m 2 F-6} 65mg / m 2 F-4 15mg / m 2 F-7 100mg / m 2 Dye AD-11 (solid dispersion) 2
0 mg / m ² Compound J 50 mg / m ² Hardener K-12 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ²

[0264]

Embedded image

(Composition of developer) 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 in an amount such 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 sulfuric acid was used to adjust the pH of the working solution to 4.9.

(Processing conditions) (Step) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / dry 50 ° C. 30 seconds 100 seconds in total The obtained sample was used as a fresh sample. 50 samples
Samples left for 3 days at 50 ° C. and 50% RH were prepared. These samples were exposed using a laser sensitivity meter using a 633 nm He-Ne laser at 1.5 × 10 ⁻⁷ seconds using a step wedge, and the above formulation was applied using an automatic developing machine GR-27 (manufactured by Konica Corporation). With a developer and a fixer.

<Evaluation of photographic performance> Sensitivity is represented by the reciprocal of the exposure amount giving a density of +0.5.
H for 3 days. The relative sensitivity was defined assuming that the sensitivity of 6-1 was 100.

<Evaluation of Hardening Characteristics> A sample left at 25 ° C. and 50% RH for 3 hours, 2 days and 5 days was immersed in water at 30 ° C. for 5 minutes, and a sapphire needle having a radius of 0.3 mm was placed on the sample surface. The sapphire needle is continuously pressed and changed in the range of 0 to 200 g while being parallel-translated on the membrane surface at a speed of 2 mm per second during the pressure contact, and the load when the membrane surface of the sample is damaged is scratch-resistant. The strength was determined.

<Evaluation of Residual Color> The unexposed sample was developed under the above conditions, and the residual color level when five sheets were superimposed was visually evaluated in five steps. Rank 5 is the best level, Rank 3
The above is the level that can withstand practical use. The results obtained are shown in the table below.

[0271]

[Table 7]

As is clear from the results shown in Table 7, the samples 6-1 to 6-16 of the present invention have less decrease in relative sensitivity and less fog as compared with the comparative sample even when forcibly deteriorated. . Further, in the case of the film strength, Comparative Samples 6-17,
No change was observed after 2 days or more after application compared to 6-18, indicating that there was almost no post-hardening property. Further, residual color contamination by the hardener was slight in the sample of the present invention, and there was no problem in practical use.

[0273]

As demonstrated in the examples, according to the present invention, a compound having a fast hardening action on gelatin and having no post-hardening property was obtained. Furthermore, according to the silver halide photographic light-sensitive material of the present invention, a silver halide photographic light-sensitive material free from residual color contamination and having no deterioration in photographic performance after processing with a low pH developing solution could be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 213/32 C07D 213/32 C09B 67/10 C09B 67/10 G03C 1/06 501 G03C 1/06 501 1/30 1/30 5/29 501 5/29 501

Claims (7)

[Claims] 1. A compound represented by the following general formula [I]. Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a monovalent organic group. A and A ′ represent —CONR ₅ —, —O—, and —S
(O) _m- , -NR _6- , -NR ₇ CO-, -SO ₂ NR ₈
—, —NR ₉ CONR ₁₀ —, wherein R ₅ , R ₆ , R ₇ ,
R ₈ , R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group or an aryl group, and m represents an integer of 0 to 2. J represents an alkylene group or an arylene group having at least one hydroxyl group, carboxyl group, sulfo group, mercapto group, or quaternary ammonium group as a substituent. However, A, A 'are both -CONR ₅ - when the, J never have as a substituent a hydroxyl group. 2. A compound represented by the following general formula [Ia]. Embedded image In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ represent R ₁ ,
It has the same meaning as R ₂ , R ₃ , R ₄ and R ₅ . J represents an alkylene group or an arylene group having at least one carboxyl group, sulfo group, mercapto group or quaternary ammonium group as a substituent. 3. A silver halide photographic material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, wherein at least one of the hydrophilic colloid layers has the general formula [ A silver halide photographic material, which is hardened with the compound represented by formula (I). 4. A silver halide photographic light-sensitive material having a hydrophilic colloid layer including a silver halide emulsion layer, wherein said silver halide emulsion layer and / or hydrophilic colloid layer contains at least one tetrazolium compound. 4. The silver halide photographic light-sensitive material according to claim 3, wherein: 5. A silver halide photographic material having a hydrophilic colloid layer including a silver halide emulsion layer, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer contains at least one hydrazine derivative. 4. The silver halide photographic light-sensitive material according to claim 3, wherein: 6. The silver halide photographic material according to claim 3, wherein at least one of a carboxyl group-activating hardener is contained in a hydrophilic colloid layer including the silver halide emulsion layer. A silver halide photographic light-sensitive material characterized by containing one kind. 7. The silver halide photographic light-sensitive material according to claim 3, wherein the pH is 7.5 to 10.
5. A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed using the developer of 5.