JP3191191B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having a photographic layer hardened with a specific compound.

[0002]

2. Description of the Related Art In general, silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) include, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, an undercoat layer, an antihalation layer, and an ultraviolet absorbing layer. And various photographic constituent layers such as an antistatic layer and a backing layer on a support such as glass, paper or synthetic resin film.

Since these photographic constituent layers are provided with an aqueous coating solution comprising a hydrophilic polymer and / or a water-dispersible polymer, they have low mechanical strength as they are. For example, gelatin films have low melting points and are excessively water-swellable.
Further, the latex film has disadvantages such as extremely poor adhesion to the support and easy peeling.

[0004] For this reason, it is known that a compound called "hardener" is added to a photographic component layer to improve its mechanical strength. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732,303
Nos. 3,288,775 and 3,951,940, UK Patent 974,723
No. 1,167,207, etc., compounds having a reactive halogen atom, diacetyl, ketone compounds such as cyclopentadione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3 , 5-Triazine, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-
1,3,5-triazine, U.S. Pat.Nos. 3,232,763, 3,635,718
No., compounds having a reactive olefin described in British Patent No. 994,809, U.S. Pat.Nos. 3,539,644 and 3,642,486,
JP-B-49-13563, 53-47271, 56-48860, JP-A-53-57257, 61-128240, 62-4275, 63-535
41, vinyl sulfonyl compounds described in 63-264572 and the like, N-hydroxymethylphthalimide, U.S. Pat.
No. 316, N-methylol compounds described in 2,586,168 and the like,
Isocyanates described in U.S. Pat.No. 3,103,437, U.S. Pat.Nos. 2,983,611, Aziridine compounds described in 3,107,280, etc., U.S. Pat.No. 2,725,294, Acid derivatives described in 2,725,295, etc., described in U.S. Pat. Carbodiimide compounds, epoxy compounds described in U.S. Patent 3,091,537 and the like, U.S. Patents 3,321,313 and 3,543,2
No. 92 or the like, organic hardeners such as halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride It is a hardener.

[0005] However, these known hardeners, when used in photosensitive materials, do not have a sufficient curing action.
There is a long-term change in the hardening action called "post-hardening" caused by a slow hardening reaction to gelatin, which has an adverse effect on the performance of photosensitive materials (especially increase in fog, decrease in sensitivity or maximum density, soft gradation) Or other coexisting photographic additives, causing the curing action to be lost or other photographic additives (eg, couplers in internal color emulsions)
All of them have some disadvantages, such as those that reduce the effectiveness of or cause contamination.

The hardening action on gelatin is relatively fast,
As a hardening agent having a low post-hardening, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-5
9625, 62-262854, 62-264044, 63-184741
N-carbamoylpyridinium salts described in JP-B No.
Acylimidazoles described in JP-38655, JP-B-53-220
No. 89, a compound having two or more N-acyloxyimino groups in the molecule, JP-A-52-93470, a compound having an N-sulfonyloxyimide group, and JP-A-58-113929.
Compound having a phosphorus-halogen bond described in
The chloroformamidinium compounds described in 0-225148, 61-240236 and 63-41580 are known.

[0007] These hardeners are characterized in that they have a fast curing action and therefore have little post-hardening. However, many of these hardeners affect photographic properties, and the hardening reaction of gelatin is fast and the side reaction decomposed by water is also fast. Therefore, in a general method for producing a photographic light-sensitive material using an aqueous solution of gelatin, The effective use efficiency of the hardener was extremely low, and in order to obtain a gelatin film having a sufficient hardening degree, there was a disadvantage that a large amount of the hardener had to be used.

[0008]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to firstly provide a photographic light-sensitive material which is hardened by a novel hardener which achieves a sufficient degree of hardening without any adverse effect on photographic characteristics. It is to provide materials.

A second object of the present invention is to provide a photographic material which is hardened by a hardener having no post-hardening due to a rapid hardening action.

A third object of the present invention is to provide a photographic light-sensitive material hardened by a hardener which reacts with high selectivity to reactive residues in gelatin and hardens gelatin efficiently.

[0011]

An object of the present invention is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula: This is achieved by a silver halide photographic material characterized by being hardened with at least one compound represented by the formula [I], the formula [II] or the formula [III].

[0012]

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[0013]

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[0014]

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R ₁ and R ₄ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, an ethylhexyl group, etc.), and an aryl group having 6 to 20 carbon atoms (eg, a phenyl group) and naphthyl group), number 2-10 alkenyl group with a carbon (e.g. vinyl group, etc. propenyl _{group), R 7 O -, (} R 8) (R 9)> N -, (R 10) (R 11)> C = N-
Or R ₁₂ S-.

R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are preferably an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.), Aryl group (for example, phenyl group, naphthyl group, etc.), having 2 to 10 carbon atoms
An alkenyl group (for example, a vinyl group, a propenyl group, etc.). It is also preferable that R ₈ and R ₉ combine with each other to form a nitrogen-containing heterocyclic ring. Examples of such heterocycles include a pyrrolidine ring, a piperidine ring, a morpholine ring and the like. Examples of the ring in which R ₁₀ and R ₁₁ are bonded to each other to form a ring include a cyclohexane ring and a cyclopentane ring.

R ₁ and R ₄ may be further substituted. Examples of the substituent include an alkyl group (eg, a methyl group and an ethyl group), an aryl group (eg, a phenyl group,
A naphthyl group), an alkoxy group (for example, a methoxy group,
Ethoxy group, etc.), aryloxy group (eg, phenoxy group, naphthoxy group, etc.), acyl group (eg, acetyl group, propionyl group, etc.), N, N-disubstituted amino group, carbamoyl group, sulfamoyl group, sulfo group, etc. Can be Preferably, they are an alkoxy group and a sulfo group.

R ₂ , R ₅ and R ₁₇ preferably have 1 to 1 carbon atoms.
10 alkyl groups (eg, methyl group, ethyl group, propyl group, etc.), aryl groups having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group, etc.), and alkenyl groups having 2 to 10 carbon atoms (eg, vinyl group, propenyl group, etc.) ). R ₂ , R ₅ and R ₁₇ may be substituted. Examples of the substituent include R
_The same substituents as those described as ₁ can be mentioned.

R ₂ and R ₅ may combine to form a ring together with J ₁ , L ₁ , J ₂ and two nitrogen atoms. Also, R
₂ and J ₁ or R ₅ and J ₂ may combine to form a ring together with the nitrogen atom.

It is also preferred that R ₁ and R ₂ or R ₄ and R ₅ combine to form a nitrogen-containing heterocycle with a nitrogen atom. Preferred examples include a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, an oxazole ring, a benzoxazole ring, an oxazoline ring, an imidazole ring, a benzimidazole ring, an imidazoline ring, a thiazole ring, a benzothiazole ring, and a thiazoline ring. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring.

R ₃ , R ₆ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ ,
R ₁₈ , R ₁₉ and R ₂₀ each independently represent a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, etc.),
Alkyl group (methyl, ethyl, propyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (pyridyl, piperidyl, etc.), alkoxy group (methoxy, ethoxy, etc.), aryloxy group (phenoxy, naphthoxy, etc.), hydroxy Alkyl groups (hydroxymethyl, hydroxyethyl, etc.), acyl groups (acetyl, propionyl, benzoyl, etc.), unsubstituted amino groups, substituted amino groups (methylamino, ethylamino, etc.), N, N-disubstituted amino groups (dimethylamino, etc.) , Diethylamino and the like, and also includes cyclic amino groups such as pyridinopiperidino and morpholino), carbamoyl group, sulfamoyl group, sulfo group, -NH-SO
₃ ^- group, -O-SO ₃ ^- group, and the like. Also, R ₂₁ -CO ₂ -R ₂₂
−, R ₂₁ −OCO−R ₂₂ −, R ₂₁ −CON (R ₂₃ ) −R ₂₂ −, R ₂₁ −N
_{(R 23) CO-R 22} -, R 21 -SO 2 -R 22 -, R 21 -SO 2 N (R 23) -R
_{22 -, R 21 -N (R} 23) SO 2 -R 22 - group represented by may be mentioned as examples of the substituents. Here, R ₂₄ represents an alkyl group or an aryl group, and R ₂₂ represents a single bond, an alkylene group or an aralkylene group. R ₂₃ represents a hydrogen atom, an alkyl group or an aralkyl group.

These substituents may be further substituted. Examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an N, N-disubstituted amino group, a carbamoyl group, a sulfamoyl group, a sulfo group, and-
NH-SO ₃ ^- group, -O-SO ₃ ^- group, and the like. Also, R ₂₄ -CO
_{2 -, R 24 -OCO-, R} 24 -CON (R 25) -, R 24 -N (R 25) CO
−, R ₂₄ −SO ₂ −, R ₂₄ −SO ₂ N (R ₂₅ ) −, R ₂₄ −N (R ₂₅ ) SO ₂ −
The group represented by is also mentioned as an example of the substituent. Where R
₂₄ represents an alkyl group, and R ₂₅ represents a hydrogen atom or an alkyl group. This alkyl group may be substituted.

R ₃ , R ₆ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ ,
R _18, R ₁₉ and R ₂₀ are preferably an alkoxy group, a substituted amino group, N, N-disubstituted amino group, a sulfo group, -NH-SO ₃ ^-
Group, —O—SO ₃ ^— group and R ₂₆ —CO ₂ —, R ₂₆ —OCO—, R ₂₆ —CO
N (R ₂₇ ) −, R ₂₆ −N (R ₂₇ ) CO−, R ₂₆ −SO ₂ −, R ₂₆ −SO ₂ N (R
₂₇ )-and R ₂₆ -N (R ₂₇ ) SO _2- .

Alkyl groups, alkoxy groups and R ₂₆ having as substituents a group selected from an alkoxy group, an N, N-disubstituted amino group, a sulfo group, a —NH—SO ₃ ^— group and a —O—SO ₃ ^— group. −CO _{2
-, R 26 -OCO-, R 26} -CON (R 27) -, R 26 -N (R 27) CO-,
Groups represented by R ₂₆ —SO ₂ —, R ₂₆ —SO ₂ N (R ₂₇ ) —, and R ₂₆ —N (R ₂₇ ) SO ₂ — are also preferred. Here, R ₂₆ represents an alkyl group,
R ₂₇ represents a hydrogen atom or an alkyl group. More preferably, it is an alkyl group or an alkoxy group having a sulfo group, a —NH—SO ₃ ^— group, or a —O—SO ₃ ^— group as a substituent. The substituent is preferably substituted at the 3-, 4- or 5-position of the pyridine ring. l, m, p, q, r, s, v or w each independently represent 0, 1 or 2, and is preferably 1. u is 0,1,
Represents 2 or 3, preferably 0 or 1. l, m, p,
When g, r, s, t, u, v, and w are 2 or more, a plurality of substituents may be the same or different. Further, they may combine with each other to form a ring.

[0025] _{^{X 1 -, Y 1 -,}} X 2 -, Y 2 -, X 3 -, Y 3 -, X
_{^{4 -, Y 4 -, X}} 5 -, Y 5 - and X ₆ ^- represents an anion moiety or a free anion in the molecule. The anionic portion of the molecule, a sulfo group, -NH-SO ₃ ^- group or a -O-SO ₃ ^- group. The free anion, halide ions (Cl ^-, Br ^-, etc.), sulfonate ion, sulfate ion, Cl
^{_{O 4, BF 4 -, PF}} 6 - , and the like. Preferably Cl ^-, B
F ₄ ⁻ , PF ₆ ⁻ and sulfonate ions.

J ₁ , J ₂ , J ₃ and J ₄ are preferably an alkylene group having 1 to 10 carbon atoms (for example, methylene group, ethylene group, propylene group, etc.), an alkenylene group having 2 to 10 carbon atoms (for example, vinylene group) , A propenylene group, etc.).
J ₁ and J ₂ or J ₃ and J ₄ may be different or may be the same. J ₁ , J ₂ , J ₃ and J ₄ may be further substituted. Preferred substituents are hydroxy group, an alkoxy group, a sulfo group, -NH-SO ₃ ^- group, -O-SO ₃ ^- is a group.

L ₁ and L ₂ represent a single bond or a divalent organic group.

Examples of the divalent organic group include those having 1 to 10 carbon atoms.
Alkylene group, an arylene group having 6 to 20 carbon atoms (for example, o
-Phenylene group, m-phenylene group, p-phenylene group, 1,4
-Naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, etc.) and the following divalent heterocyclic groups.

[0029]

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Other examples of the divalent organic group include an alkylene group, an arylene group, a heterocyclic group and —OCO—, —CO ₂ —,
−N (R ₂₈ ) CO−, −CON (R ₂₈ ) −, −O−, −S−, −N (R ₂₈ )
_{-, - SO 2 -, -} N (R 28) SO 2 - or -SO ₂ N (R ₂₈₎ - groups which can by combining a linking group selected from the also exemplified. Here, R ₂₈ represents a hydrogen atom or an alkyl group.

Preferred as L ₁ and L ₂ are a single bond, an arylene group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms and —OCO—, —CO ₂
−, −N (R ₂₈ ) CO−, −CON (R ₂₈ ) −, −O−, −S−, −N
_{(R 28) -, - SO} 2 -, - N (R 28) SO 2 - or -SO ₂ N (R ₂₈₎ - is a group formed by combining a linking group selected from. Here, R ₂₈ represents a hydrogen atom or an alkyl group.

L ₁ and L ₂ may be further substituted. Preferred substituents are hydroxy group, an alkoxy group, a sulfo group, -NH-SO ₃ ^- is a group ^- or -O-SO _3.

N and t represent 0 or 1.

The compound represented by the general formula [I] or the general formula [II] releases a nitrogen-containing aromatic heterocyclic compound such as pyridine when hardening a photographic light-sensitive material. For the purpose, the pKa of the conjugate acid of these compounds
(Measured value at 25 ° C. in an aqueous solution, hereinafter the same meaning) is preferably in the range of 3 to 10. If the pKa of the conjugate acid of the heterocyclic compound is lower than this, synthesis of the compound becomes difficult, and the reactivity of the compound becomes too high, resulting in a problem that the stability when used as an aqueous solution is lowered. On the other hand, when the pKa of the conjugate acid of the heterocyclic compound is higher than this, the reactivity of the compound becomes too low, so that the desired rapid curing action does not occur.

More preferably, the heterocyclic compound has a pKa of the conjugate acid in the range of 5 to 8.

Examples of the compound represented by the general formula [I], the general formula [II] or the general formula [III] are shown below, but the present invention is not limited thereto.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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The compounds of the present invention can be easily synthesized by known methods.

For example, a compound represented by the following general formula [IV], [V] or [VI] is reacted with a compound represented by the general formula [VII], and each compound is represented by the general formula [I] ,
It can be a compound represented by the general formula [II] or the general formula [III]. Free anions in the molecule can be changed to any by anion exchange.

[0065]

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[Wherein R ₁ , R ₂ , R ₄ , R ₅ , J ₁ , J ₂ ,
L ₁ and n represent the same as those in the general formula [I]. X ₇ and X ₈ represent a leaving group such as a halogen atom or a sulfonyloxy group. Y ₇ ^- and Y ₈ ^- represents an anion moiety or a free anion in the molecule. ]

[0067]

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[Wherein R ₁₃ , R ₁₅ , J ₃ , J ₄ , L ₂ ,
p, r and t represent the same as those in the general formula [II]. X ₉ and X ₁₀ represent a leaving group such as a halogen atom and a sulfonyloxy group. Y ₉ ^- and Y ₁₀ ^- represents an anion moiety or a free anion in the molecule. ]

[0069]

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[Wherein R ₁₇ , R ₁₈ and u are represented by the general formula [II
I]. X ₁₁ and X ₁₂ represent a leaving group such as a halogen atom or a sulfonyloxy group.
Y ₁₁ ^- represents an anion moiety or a free anion in the molecule. ]

[0071]

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[Wherein, R represents a substituent, and x represents 0, 1 or 2. Examples of R ₂₉ and preferred are R ₃ ,
R ₆ . The same as R ₁₄ , R ₁₆ , R ₁₉ or R ₂₀ can be mentioned. Here, general formula [IV], general formula [V] or general formula [V
The compound represented by I] can be easily synthesized by a known method. For example, the compound represented by the general formula [IV] is obtained by halogenating or sulfonating a compound represented by the following general formula [VIII], or a compound represented by the following general formula [IX] by a general formula [X] Can be synthesized in good yield by reacting with the compound represented by Further, the compound represented by the general formula (V) is a compound represented by the following general formula (XI):
By reacting with the compound represented by I], the compound can be synthesized in good yield. Further, the compound represented by the general formula [VI] can be conveniently synthesized by reacting a compound represented by the following general formula [XIII] with a compound represented by the general formula [XIV].

[0073]

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[Wherein R ₁ , R ₂ , R ₄ , R ₅ , J ₁ , J ₂ ,
L ₁ and n represent the same as those in the general formula [I]. ]

[0075]

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[Wherein, R ₃₀ represents the same as R ₁ or R ₄ in formula [I], and R ₃₁ represents R _{1 in} formula [I].
It represents the same as ₂ or R _5. X ₁₃ represents a leaving group such as a halogen atom or a sulfonyloxy group. ]

[0077]

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[In the formula, J ₁ , J ₂ , L ₁ and n represent the same as those in the general formula [I]. X ₁₄ and X ₁₅ represent a leaving group such as a halogen atom or a sulfonyloxy group. ]

[0079]

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Wherein R ₃₂ represents R ₁₃ in the general formula [II]
Or the same meaning as R _15. x represents the same as p or r in the general formula [II]. X ₁₆ represents a leaving group such as a halogen atom and a sulfonyloxy group. ]

[0081]

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[Wherein J ₃ , J ₄ , L ₂ and t represent the general formula [I
I]. X ₁₆ and X ₁₇ represent a leaving group such as a halogen atom and a sulfonyloxy group. ]

[0083]

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Wherein R ₁₈ and n are the same as those in the general formula [III]. X ₁₈ and X ₁₉ represent a leaving group such as a halogen atom or a sulfonyloxy group. ]

[0085]

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[Wherein, R ₁₇ is the same as that in the general formula [III]. X ₂₀ represents a leaving group such as a halogen atom and a sulfonyloxy group. R ₁₇ and X ₂₀ may be bonded at two positions to form a cyclic molecule such as sultone. Next, the synthesis method will be specifically described with reference to Exemplified Compounds 76 and 106 of the present invention.

<Synthesis of Exemplified Compound 76> Tetramethylene bis (2-chloropyridinium) dibromide [2-chloropyridine and
Synthesized from 1,4-dibromobutane] 44.3 g (0.10 mol) was dissolved in a mixed solvent of 200 ml of acetone tolyl and 150 ml of DMF. In this, 37.4 g of 2- (4-pyridyl) ethanesulfonic acid
(0.20 mol) and a solution of 20.3 g (0.20 mol) of triethylamine in 200 ml of acetone tolyl were added at room temperature.
The mixture was stirred at room temperature for one day. The precipitated crystals were filtered, washed with acetone tolyl, and dried (yield: 55.8
g (85% yield)).

<Synthesis of Exemplified Compound 106> N-methyl iodide
29.0 g (0.10 mol) of 2,6-dichloropyridinium [synthesized from 2,6-dichloropyridine and methyl iodide] was dissolved in a mixed solvent of 200 ml of acetone tolyl and 100 ml of DMF. 37.4 g (0.20 mol) of 2- (4-pyridyl) ethanesulfonic acid in this
And a solution of 20.36 g (0.20 mol) of triethylamine in 200 ml of acetone tolyl was added at room temperature. As it is
Stirred overnight at room temperature. The precipitated crystals were filtered, washed with acetone tolyl and dried (yield 53.8 g (yield 91
%)).

The structure was confirmed by NMR and IR.

The other compounds of the present invention can be synthesized in good yield by the same method.

The amount of the hardener used in carrying out the present invention is as follows:
It varies depending on the type of photosensitive material applied, the type of hydrophilic binder, and the like, but is preferably 0.
The range is from 01 to 100% by weight, more preferably from 0.1 to 30% by weight.

The hydrophilic binder used in the practice of the present invention is arbitrary, such as generally used gelatin, gelatin derivatives, and graft polymers of gelatin and other polymers.

As the water-dispersible polymer contained in the photographic component layer, an aqueous dispersion of a hydrophobic polymer or copolymer obtained from a vinyl compound, or an aqueous dispersion of a condensation-polymerized polymer such as polyester can be used. .

In the practice of the present invention, silver halide, a chemical sensitizer, a silver halide solvent, a spectral sensitizing dye, an antifoggant, gelatin, etc., used in the silver halide emulsion layer or other layers of the light-sensitive material. A hydrophilic protective colloid,
The ultraviolet absorber, polymer latex, whitening agent, color coupler, anti-fading agent, dye, matting agent, surfactant and the like are not particularly limited. For example, Research Disclosure, Volume 176 (Dec. 1978)
Mon.), pp. 22-31.

For the support of the light-sensitive material, the developing method, the constituent layers of the light-sensitive material, etc., the description in the above-mentioned Research Disclosure Magazine can be referred to.

[0096]

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

Example 1 In the following examples, the amount added in the silver halide photographic light-sensitive material indicates grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye was represented by the number of moles per mole of silver.

On a triacetylcellulose film support, each layer having the following composition was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0.20 High boiling solvent (Oil- 2) 0.20 gelatin 1.6 Second layer: intermediate layer (IL-1) Gelatin 1.3 third layer: low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion ( Em-2) 0.3 sensitizing dye (S-1) 3.2 × 10 ^-4 sensitizing dye (S-2) 3.2 × 10 ^-4 sensitizing dye (S-3) 0.2 × 10 ^-4 cyan coupler (C-1) ) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 High boiling solvent (Oil-1) 0.55 Additive (SC-1) 0.003 gelatin 1.0 fourth layer: high-sensitivity red-sensitive emulsion layer (R-H) silver iodobromide emulsion (Em-3) 9 Sensitizing dye (S-1) 1.7 × 10 ^-4 Sensitizing dye (S-2) 1.6 × 10 ^-4 Sensitizing dye (S-3) 0.1 × 10 ^-4 Cyan coupler (C-2) 0.23 Colored cyan Coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling solvent (Oil-1) 0.25 Additive (SC-1) 0.003 Gelatin 1.0 Fifth layer: Intermediate layer (IL-2) Gelatin 0.8 Sixth layer : Low-sensitivity green-sensitive emulsion layer (GL) silver iodobromide emulsion (Em-1) 0.6 silver iodobromide emulsion (Em-2) 0.2 sensitizing dye (S-4) 6.7 × 10 ^-4 sensitizing dye (S-5) 0.8 × 10 ^-4 Magenta coupler (M-1) 0.17 Magenta coupler (M-2) 0.43 Colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 High boiling solvent (Oil-2) 0.70 Additive (SC-1) 0.003 Gelatin 1.0 Seventh layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S- 6) 1.1 × 10 ^-4 sensitizing dye (S-7) 2.0 × 10 ^-4 sensitizing dye (S-8) 0.3 × 10 ^-4 magenta coupler (M-1) 0.03 Magenta coupler (M-2) 0.13 colored Magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.004 High boiling solvent (Oil-2) 0.35 Additive (SC-1) 0.003 Gelatin 1.0 Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 added Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-2) 0.12 High boiling solvent (Oil-2) 0.15 Gelatin 1.0 Ninth layer: low-sensitivity blue-sensitive emulsion layer (BL) iodine Silver bromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-9) 5.8 × 10 ^-4 Yellow coupler (Y-1) 0.60 Yellow coupler (Y-2) 0.32 DIR compound (D-1) 0.003 DIR compound (D-2) 0.006 High boiling point solvent (Oil-2) 0.18 Additive ( C-1) 0.004 Gelatin 1.3 10th layer: high sensitivity blue-sensitive emulsion layer (B-H) silver iodobromide emulsion (Em-4) 0.5 Sensitizing dye (S-10) 3.0 × 10 -4 Sensitizing dye ( S-11) 1.2 × 10 ^-4 yellow coupler (Y-1) 0.18 yellow coupler (Y-2) 0.10 high boiling point solvent (Oil-2) 0.05 additive (SC-1) 0.002 gelatin 1.0 11th layer: 1st layer Protective layer (PRO-1) Silver iodobromide emulsion (Em-5) 0.3 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Gelatin 0.8 12th layer: 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size -2 μm) 0.13 Polymethyl methacrylate (average particle size: 3 μm) 0.02 Sliding agent (WAX-1) 0.04 Charge control agent (SU-1) 0.004 Charge control agent (S U-2) 0.02 Gelatin 0.5 Samples 1 to 20 were prepared by adding a hardener of the present invention or a comparative hardener to each layer as shown in Table 1 in addition to the above.

In each layer, a coating aid (SU-4), a dispersion aid (SU-3), a stabilizer (ST-1), and a preservative (D
I-1), antifoggants (AF-1), (AF-2),
Dyes (AI-1) and (AI-2) were appropriately added.

The emulsions used in the above samples are as follows. Each is an internal high iodine type monodisperse emulsion.

Em-1: average silver iodide content 7.5 mol%
Average grain size 0.55 μm Grain shape Octahedron Em-2: Average silver iodide content 2.5 mol% Average grain size 0.36
μm Grain shape Octahedron Em-3: Average silver iodide content 8.0 mol% Average particle size 0.84
μm Grain shape Octahedron Em-4: Average silver iodide content 8.5 mol% Average particle size 1.02
μm Grain shape Octahedron Em-5: Average silver iodide content 2.0 mol% Average particle size 0.88
μm

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Each prepared sample was used as a fresh sample,
A sample left at 25 ° C. and 50% RH for 7 days, and
The samples were left to stand at 50 ° C. and 50% RH or 50 ° C. and 80% RH for 2 days to prepare samples which were forcibly deteriorated, respectively.

After exposing these samples to wedges with white light, the following processing was performed to measure the sensitivity and fog.

The sensitivity is represented by the reciprocal of the amount of exposure that gives a density of fog + 0.5, and is expressed as a relative sensitivity, where the sensitivity of Sample 1 left at 25 ° C. and 50% RH for 7 days after coating is 100.

A sample left at 25 ° C. and 50% RH for 2 hours, 8 hours, 1 day and 7 days was immersed in water at 30 ° C. for 5 minutes.
A sapphire needle with a radius of 0.3 mm is pressed against the sample surface, and the sapphire needle pressure is changed continuously within the range of 0 to 200 g while moving in parallel on the film surface at a speed of 2 mm per second. The load when the surface was damaged was determined as the scratch resistance.

Table 1 also shows the results.

Processing Step Color development 38 ° C. 3 minutes 15 seconds Bleaching 38 ° C. 6 minutes 30 seconds Rinse 38 ° C. 3 minutes 15 seconds Fix 38 ° C. 6 minutes 30 seconds Rinse 38 ° C. 3 minutes 15 seconds Stabilize 25 ° C. 1 minute 30 seconds Drying 45 ° C The composition of the processing solution used in each processing step is as follows.

(Color developing solution) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1000 ml.

(Bleaching solution) Iron ammonium diaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Add water to make 1000 ml, and adjust the pH to 6.0 using aqueous ammonia.

(Fixing solution) Ammonium thiosulfate 175.0 g Sodium sulfite anhydrous 8.5 g Sodium metasulfite 2.3 g Water was added to make 1000 ml, and the pH was adjusted to 6.0 using acetic acid.

(Stabilizing Solution) Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Make up to 1000 ml with water.

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[Table 1]

As is clear from the results in Table 1 above, Samples 1 to 14 using the hardener according to the present invention showed only a slight decrease in relative sensitivity as compared with Comparative Samples 15 to 20. ,
No fog deterioration (increase) is observed.

Further, even when forcedly deteriorated, Samples 1 to 14 of the present invention show a slight decrease in sensitivity and little increase in fog compared to Comparative Samples 15 to 20.

Therefore, it can be seen that the hardener according to the present invention hardly inhibits the photographic properties.

Further, from the results of the scratch resistance indicating the film strength, each of the samples of the present invention 1 to 14 shows a higher film strength as compared with the comparative samples 15 to 20. Indicates that the film is hardened more efficiently than the comparative compound.
Further, when the change in scratch resistance is observed, all of the samples 1 to 14 of the present invention show no change after one day or more, indicating that there is almost no post-hardening property.

Example 2 Layers having the following compositions were sequentially formed on both sides of a subbed polyethylene terephthalate support from the support side to obtain photosensitive materials 21 to 40 for X-rays.

Additives other than silver halide are shown per mol of silver halide unless otherwise specified.

First layer: Crossover cut layer Dye (I) 3 mg / m ² mordant (II) 0.12 g / m ² Gelatin 0.2 g / m ² Second layer: Emulsion layer Average particle size 0.57 μm, AgI 2 mol% Emulsion consisting of AgBrI containing silver Coating amount of silver 4.5 g / m ² Sensitizing dye (A) 450 mg Sensitizing dye (B) 20 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3.0 mg t -Butyl-catechol 400mg Polyvinylpyrrolidone (Molecular weight 10,000) 1.0g Styrene-maleic anhydride copolymer 2.5g Trimethylolpropane 10g Diethylene glycol 5g p-Nitrophenyl-triphenylphosphonium chloride 50mg 1,3-Dihydroxybenzene-4-sulfonic acid Ammonium 4g 2-Mercaptobenzimidazole-5-sodium sulfonate 15mg Additive A 70mg Additive B 1g 1,1-Dimethylol-1-bromo-1-nitromethane 10mg Gelatin 2g / m ² Third layer: protective layer Polymethyl methacrylate (Average grain 7 mg / m ² Colloidal silica (average particle size 0.013 μm) 70 mg / m ² Additive C 10 mg / m ² Additive D 2 mg / m ² Additive E 7 mg / m ² Additive F 15 mg / m ² Gelatin 1 g / m ² hardener (described in Table 2) Preservative DI-1 was added to each sample.

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After a storage test was performed on each sample in the same manner as in Example 1, the sample was exposed to light and subjected to the following treatment, and the photographic characteristics were measured in the same manner as in Example 1.

The sensitivities were shown as relative sensitivities with the sensitivity of Sample 21 on the 7th day after application being taken as 100.

Table 2 shows the results.

(Processing step) Insertion 1.2 seconds Development + Crossover 35 ° C 14.6 seconds Fixing + Crossover 33 ° C 8.2 seconds Rinse + Crossover 25 ° C 7.2 seconds Squeeze 40 ° C 5.7 seconds Drying 45 ° C 8.1 seconds (Developer) Hydroquinone 25.0 g Phenidone 1.2 g Potassium sulfite 55.0 g Boric acid 10.0 g Sodium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Nitroimidazole 0.10 g 5-Nitrobenzimidazole 0.10 g Glutaraldehyde bisulfite 15.0 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylene Add 2.5g of tetramine hexaacetic acid water to make 1000ml. (Fixing solution) Ammonium thiosulfate 130.9 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Sodium acetate (trihydrate) 25.8 g Aluminum sulfate (18 hydrate) 14.6 g Sulfuric acid (50 wt%) 6.77 g Water To make 1000ml.

Further, while keeping the sample at 25 ° C. and a humidity of 50% RH, a part of each sample was taken out after 2 hours, 8 hours, 1 day and 7 days after application and swelled in water at 30 ° C. for 5 minutes. Then, the film thickness of each sample was measured, the degree of swelling V represented by the following equation was calculated, and the change over time (post-hardening property) of the curing action was observed.

The results are shown in Table 2 below.

V = film thickness increased by swelling / film thickness when dried

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[Table 2]

As is clear from the results shown in Table 2, in X-ray photosensitive material samples 21 to 34 in which the hardener of the present invention was added to the protective layer, fluctuations in photographic characteristics such as a decrease in sensitivity and an increase in fog were observed. Almost no. Moreover, the change in the degree of swelling is small and stable when more than one day after the application and drying, and the post-hardening property is remarkably improved. When the final degree of swelling is compared with Comparative Samples 35 to 40, it can be seen that the dura was efficiently formed.

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As described above, according to the present invention, a hardening action can be efficiently performed even with a small amount of a hardening agent without impairing photographic performance.
A silver halide photographic light-sensitive material hardened by a novel hardener without post-hardening action can be provided.

Claims (6)

(57) [Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers is formed of a compound represented by the following general formula [I]. A silver halide photographic material characterized by being hardened by at least one kind. Embedded image [Wherein R ₁ and R ₄ are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, R ₇ O—, (R ₈ ) (R ₉ )>
N -, represents an _{S- (R 10) (R 11} )> C = N- or R _12. These groups may be further substituted. R ₁ and R ₂ or R
₄ and R ₅ may combine to form a nitrogen-containing heterocyclic ring. This heterocyclic ring may be fused with another ring. R ₇ , R ₈ , R
_{9, R 10, R 11,} R 12 represents an alkyl group, an aryl group or an alkenyl group. R ₁₀ and R ₁₁ may be hydrogen atoms. R
₈ and R ₉ or R ₁₀ and R ₁₁ may be combined with each other to form a ring. R ₂ and R ₅ each independently represent an alkyl group, an aryl group or an alkenyl group. These groups may be further substituted. R ₃ and R ₆ each independently represent a substituent, and l and m each independently represent 0, 1 or 2. When 1 = 2 or m = 2, the two substituents may be the same or different from each other. Further, they may combine with each other to form a ring. J ₁ and J ₂ each independently represent an alkylene group or an alkenylene group. L ₁ represents a single bond or a divalent organic group. J ₁ and J ₂ may be further substituted. n represents 0 or 1. X ₁ ⁻ , Y ₁ ⁻ , X ₂ ⁻ , and Y ₂ ^— represent an anion portion in the molecule or a free anion. ] 2. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula [I
A silver halide photographic material, which is hardened with at least one compound represented by the formula (I). Embedded image Wherein R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each independently represent a substituent. p, q, r and s are each independently 0, 1
Or 2 is represented. p = 2 or q = 2 or r = 2 or s = 2
In the case, the two substituents may be the same or different from each other. Further, they may combine with each other to form a ring. J ₃ and J ₄ each independently represent an alkylene group or an alkenylene group. L ₂ represents a single bond or a divalent organic group. J ₃
And J ₄ may be further substituted. t is 0 or 1
Represents X ₃ ⁻ , Y ₃ ⁻ , X ₄ ⁻ , and Y ₄ ^— represent an anion portion in the molecule or a free anion. ] 3. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula [II]
A silver halide photographic material, which is hardened with at least one compound represented by the formula (I). Embedded image [In the formula, R ₁₇ represents an alkyl group, an aralkyl group or an alkenyl group. R ₁₈ , R ₁₉ and R ₂₀ each independently represent a substituent. u represents 0, 1, 2, or 3. u = 2 or u =
In the case of 3, a plurality of substituents may be the same or different. Further, they may combine with each other to form a ring. v, w
Each independently represents 0, 1 or 2. v = 2 or w =
In the case of 2, the two substitutions may be the same or different from each other. Further, they may combine with each other to form a ring. X ₅ ^-, X
₆ ^-, Y ₅ ^- represents an anion moiety or a free anion in the molecule. ] 4. An anionic group selected from the same number of sulfo groups (—SO ₃ ^— groups), —NH—SO ₃ ^— groups or —O—SO ₃ ^— groups as quaternary ammonium groups in the molecule. 4. The silver halide photographic material according to claim 1, wherein the silver halide photographic material has a betaine-type neutral molecule. 5. The pKa (measured at 25 ° C. in aqueous solution) of the conjugate acid of the nitrogen-containing aromatic heterocyclic compound released when the hydrophilic colloid layer is hardened by a curing reaction is in the range of 3 to 10. Claim 1, Claim 2, Claim 3 characterized by the above-mentioned.
Or a silver halide photographic material according to claim 4. 6. The pKa (measured at 25 ° C. in aqueous solution) of the conjugate acid of the nitrogen-containing aromatic heterocyclic compound released when the hydrophilic colloid layer is hardened by a curing reaction is in the range of 5 to 8. Claim 1, Claim 2, Claim 3 characterized by the above-mentioned.
Or a silver halide photographic material according to claim 4.