JPH04316039A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material capable of being hardened efficiently by a small amount of hardener without impairing photographic performances and free from posthardening action by hardening a hydrophilic colloidal layer with a specified compound. CONSTITUTION:At least one of hydrophilic colloidal layers formed on a support is hardened with at least one of the compounds represented by formula I in which A is a group represented by formula II; each of X and Y is an O or S atom; R1 is alkyl, aryl, or aralkyl; B is a group represented by one of formulae III to V; Z1 is an atomic group necessary to form an N-containing hetero ring; Y1 is an O or S atom; Z2 is an atomic group necessary to form an N- containing hetero ring; each of R7-R11 is H or a substituent; l is 1, 2, or 3; m is 0, 1, or 2: and l+m=3.

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 material, and more particularly to a silver halide photographic material whose photographic constituent layers are hardened with a specific compound.

0002

BACKGROUND OF THE INVENTION In general, silver halide photographic materials (hereinafter referred to as "photosensitive materials") include, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, a subbing layer, an antihalation layer, and an ultraviolet absorbing layer. , an antistatic layer, a backing layer, and other various photographic constituent layers are formed on a support such as glass, paper, or synthetic resin film.

Since these photographic constituent layers are coated with an aqueous coating solution comprising a hydrophilic polymer and/or a water-dispersible polymer, their mechanical strength is weak as is. For example, gelatin films have low melting points and are excessively water-swellable. In addition, latex films have drawbacks such as extremely poor adhesion to the support and easy peeling.

For this reason, it is known to add a compound called a "hardening agent" to a photographic constituent layer to improve its mechanical strength. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732
, No. 303, No. 3,288,775, British Patent No. 974
, 723, 1,167,207, etc., ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl)urea, 2-hydroxy-4,6- dichloro-1
, 3,5-triazine, divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5
- Triazine, U.S. Pat. No. 3,232,763,
No. 635,718, compounds having reactive olefins described in British Patent No. 994,809, etc., U.S. Patent No. 3,53
No. 9,644, No. 3,642,486, Special Publication No. 1977-
No. 13563, No. 53-47271, No. 56-488
No. 60, JP-A-53-57257, JP-A No. 61-1282
No. 40, No. 62-4275, No. 63-53541,
Vinylsulfonyl compound described in 63-264572 etc., N-hydroxymethylphthalimide, U.S. Patent 2
, 732,316, 2,586,168, etc., and U.S. Pat. No. 3,103,437.
Isocyanates described in US Pat. No. 2,983, etc.
Aziridine compounds described in U.S. Pat. No. 611, U.S. Pat. No. 3,107,280, etc.;
Acid derivatives described in US Pat. No. 25,295, etc., U.S. Patent No. 3,1
Carbodiimide compounds described in US Pat. No. 00,704, etc., epoxy compounds described in US Pat. No. 3,091,537, etc., US Pat.
Organic hardeners such as isoxazole compounds described in No. 92, 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 hardening agent.

However, when these known hardening agents are used in photosensitive materials, they do not have sufficient hardening action.
There is a long-term change in the hardening effect called "post-hardening" caused by the slow hardening reaction to gelatin, which has a negative effect on the performance of light-sensitive materials (especially increased fog, decreased sensitivity or maximum density, and soft gradation). (e.g.), may lose its hardening effect due to coexisting photographic additives, or may be affected by other photographic additives (e.g., couplers in internal color emulsions).
All of them had some kind of drawback, such as those that reduced the effectiveness or caused contamination.

[0006] The hardening effect on gelatin is relatively fast;
As a hardening agent with less posterior dura mater, JP-A-50-3854
Compounds having a dihydroquinoline skeleton described in No. 0, 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, Japanese Patent Publication No. 1983
Compound containing two or more N-acyloxyimino groups in the molecule as described in No.-22089, JP-A-52-9347
Compounds having an N-sulfonyloxyimide group as described in No. 0, compounds having a phosphorus-halogen bond as described in JP-A-58-113929, JP-A-60-225148, JP-A-61-240236, JP-A-63- Chloroformamidinium compounds described in No. 41580 are known.

[0007] These hardeners have a fast curing action and are therefore characterized by less post-hardening. However, many of these hardeners affect the photographic properties, and the curing reaction of gelatin is fast, as well as the side reaction of decomposition by water. This technique has the disadvantage that the effective use efficiency of the hardening agent is extremely low, and that a large amount of hardening agent must be used in order to obtain a gelatin film with sufficient hardness.

[0008]

OBJECTS OF THE INVENTION Therefore, the first object of the present invention is to provide a photographic light-sensitive material hardened with a novel hardening agent that achieves sufficient hardness without any adverse effect on photographic properties. There is a particular thing. A second object of the present invention is to provide a photographic material hardened with a hardening agent that has rapid curing action and does not require post-hardening. A third object of the present invention is to provide a photographic material hardened with a hardening agent that reacts with high selectivity to reactive residues in gelatin and efficiently hardens gelatin.

[0009]

DESCRIPTION OF THE INVENTION The objects of the present invention are achieved by the following silver halide photographic material. (1) In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, at least one of the hydrophilic colloid layers contains at least one compound represented by the following general formula [I]. A silver halide photographic material characterized by being hardened with seeds. General formula [I]

0010

embedded image [In the formula, A represents a group selected from the groups represented by the following general formula [II]. General formula [II]

[0011]

(In the formula, X and Y each represent an oxygen atom or a sulfur atom, and R1 represents an alkyl group, an aryl group, or an aralkyl group.) B represents the following general formula [III], the general formula [IV
] and represents a group selected from the group represented by the general formula [V]. General formula [III]

0012

General formula [IV]

[0013]

[Chemical formula 12] (In the formula, Y1 represents an oxygen atom or a sulfur atom, and Z
2 represents an atomic group necessary to form a nitrogen-containing heterocycle. ) General formula [V]

[0014]

embedded image (In the formula, R7 to R11 each represent a hydrogen atom or a substituent.) l represents 1, 2 or 3, m is 0, 1 or 2
, and l+m=3. (2) The silver halide photographic material as described in item (1) above, wherein the compound represented by the general formula [I] is a compound represented by the following general formula [VI]. General formula [VI]

[0015]

[Formula 14] (In the formula, A represents a group selected from the groups represented by the general formula [II] described in item (1) above.) (3) The compound represented by the general formula [I] , the silver halide photographic material according to item (1) above, which is a compound represented by the following general formula [VII]. General formula [VII]

[0016]

embedded image (wherein A represents a group selected from the groups represented by the general formula [II] described in the above (1)), and C represents the group represented by the general formula [III] described in the above (1) or a group selected from the groups represented by the general formula [IV].) (4) The compound represented by the general formula [I] is a compound represented by the following general formula [VIII]. The silver halide photographic material according to item (1) above. General formula [VIII]

[0017]

[Formula 16] (wherein A represents a group selected from the groups represented by the general formula [II] described in the above item (1), and D represents the group represented by the general formula [V] described in the above item (1)) The present invention will be described in further detail.

In the general formula [II], R1 is
Preferably an alkyl group having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, 2
-ethylhexyl group, dodecyl group, etc.), carbon number 6-2
0 aryl group (for example, phenyl group, tolyl group, naphthyl group, etc.), and an aralkyl group having 7 to 21 carbon atoms (for example, benzyl group, phenethyl group, etc.).

The alkyl group, aryl group or aralkyl group represented by R1 may have a substituent, and examples of the substituent include a halogen atom (for example, a chlorine atom, a fluorine atom, a bromine atom, etc.), an alkoxy group ( For example, methoxy group,
ethoxy group, 1-propyloxy group, 2-propyloxy group, etc.), aryloxy group (e.g. phenoxy group,
tolyloxy group, naphthoxy group, etc.), acyl group (e.g. acetyl group, propionyl group, benzoyl group, etc.),
Examples include carbamoyl group, sulfamoyl group, sulfo group, sulfooxy group, and sulfamino group. The number and substitution positions of these substituents can be arbitrarily selected.

In the general formula [III] and the general formula [IV], Z1 and Z2 represent atomic groups necessary to form a nitrogen-containing heterocycle, but this nitrogen-containing heterocycle may be an aliphatic one. , may be aromatic.

[0021] Furthermore, it may be a monocyclic ring or a condensed ring.

Below, general formula [III] and general formula [
Preferred examples of the group represented by IV] are shown below, but the present invention is not limited thereto.

[0023]

[Chemical formula 17]

[0024]

[Chemical formula 18]

[0025]

[Chemical formula 19]

Here, R2 to R5 are hydrogen atoms, alkyl groups (eg, methyl, ethyl, propyl, butyl, etc.), aryl groups (eg, phenyl, tolyl, naphthyl, etc.), aralkyl groups (eg, benzyl), group, phenethyl group, etc.), or -CO2-, -CONH-, -
OCO-, -NHCO-, -SO2-, -SO2NH-
, -NHSO2-, -SO3-, -OSO2-. These may be further substituted.

Examples of substituents include halogen atoms (for example, chlorine atoms, fluorine atoms, etc.), hydroxyl groups, alkoxy groups (for example, methoxy groups, ethoxy groups, 1-propyloxy groups, 2-propyloxy groups, etc.), and aryloxy groups. (e.g., phenoxy group, tolyloxy group, naphthoxy group, etc.), carbamoyl group (e.g., N,N-dimethylcarbamoyl group, N-methylcarbamoyl group, etc.), sulfamoyl group (e.g., N,N-dimethylsulfamoyl group, N-methyl sulfamoyl group, etc.), sulfo group, sulfoamino group, sulfooxy group, etc.

In general formula [V], substituents represented by R7 to R11 include halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, -CO2
Mention may be made of the M group or the -SO3 M group.

[0029] Alkyl group, aryl group, alkoxy group,
The aryloxy group may be unsubstituted,
It may have a substituent.

Examples of the substituent include halogen atoms such as fluorine atoms and chlorine atoms, alkoxy groups such as methoxy groups and ethoxy groups, carboxyl groups, sulfo groups, sulfoamino groups, and sulfoxy groups.

Examples of the alkyl group include methyl group, ethyl group, propyl group, methoxyethyl group, chloromethyl group, chloroethyl group, sulfomethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, carboxymethyl group, and sulfaminoethyl group. and sulfooxyethyl group.

Examples of the aryl group include phenyl group, p-tolyl group, p-methoxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, 2,5-disulfophenyl group, p-sulfoxyphenyl group. The following groups can be mentioned.

M represents a hydrogen atom, an ammonium group, an alkali metal atom or an alkaline earth metal atom. Examples of the ammonium group include an ammonium group, a trimethylammonium group, a tetramethylammonium group, a tetraethylammonium group, a butyltrimethylammonium group, and the like.

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

[0035]

[C20]

[0036]

[C21]

[0037]

[C22]

[0038]

[C23]

[0039]

[C24]

[0040]

[C25]

[0041]

[C26]

[0042]

[C27]

[0043]

[C28]

[0044]

[C29]

[0045]

[C30]

[0046]

embedded image The compound of the present invention can be easily synthesized by a known method.

For example, when l=3 in the general formula [I], the compound represented by the following general formula [IX] and the phosphorus oxyhalide represented by the general formula [X] are combined in the presence of a base. It can be easily synthesized by reacting at a molar ratio of 3:1. Also, in general formula [I], l=1 or l
= 2, the compound represented by the following general formula [IX] and the phosphorus oxyhalide represented by the general formula [X],
After reacting in the presence of a base at a molar ratio of 1:1 or 2:1 to form a phosphoric acid amide dihalide represented by the general formula [XI] or a phosphoric acid diamide halide represented by the general formula [XII]. , can be easily synthesized by further reacting with a compound represented by general formula [XIII]. General formula [IX] H-A General formula [X]

[0048]

[C32] General formula [XI]

[0049]

[Chemical formula 33] General formula [XII]

[0050]

embedded image General formula [XIII] H-E [the above general formula [IX], general formula [XI] and general formula [
XII], A represents the same as A in general formula [I], and in general formula [XIII], E represents general formula [II].
I] represents a group represented by general formula [IV] or general formula [V]. X represents a halogen atom. ] Also, general formula [I
], when B is a group selected from the groups represented by the general formula [V], a phenol represented by the following general formula [XIV] and an oxyhalogen represented by the above general formula [X] Phosphate in the presence of a base at a molar ratio of 1:1 or 2.
: 1 to form a phosphoric acid phenol ester dihalide or phosphoric acid diphenol ester halide represented by the general formula [XV], and then further reacted with the compound represented by the general formula [IX] in the presence of a base. It can also be easily synthesized by reaction. General formula [XIV] H-F General formula [XV]

[0051]

embedded image [In the above general formula [XIV] and general formula [XV], F represents a group represented by general formula [V], and X represents a halogen atom. s and t represent 1 or 2, s+t
=3. ] Next, the above exemplary compounds 1, 15 and 2
The synthesis method will be specifically explained using No. 7 as an example. Synthesis of Exemplified Compound 1 15.0 g (0.15 mol) of 3-methyl-1,2,4-oxadiazol-5-one in 300 ml of methylene chloride
While cooling with water, 7.67 g (0.05 mol) of phosphorus oxychloride was added and dissolved in the solution. Then triethylamine 15.
A solution of 38 g (0.15 mol) in 50 ml of methylene chloride was added dropwise.

After stirring the reaction mixture at room temperature for 10 hours,
The resulting insoluble matter was filtered off, and the filtrate was concentrated to dryness.

The residue was recrystallized from acetonitrile to obtain 12.4 g (yield 72%) of colorless granular Exemplified Compound 1. Synthesis of Exemplary Compound 15 <Chlorophosphate N,N-bis[3-methyl-1,2,4
Synthesis of 3-methyl-1,2,4-oxadiazol-5-one 10.0 g (0.10 mol) of methylene chloride 250
ml solution was stirred vigorously and 7.ml of phosphorus oxychloride was added under cooling.
After adding 67 g (0.05 mol), a solution of 10.1 g (0.10 mol) of triethylamine in 50 ml of methylene chloride was added dropwise.

After stirring the reaction mixture at room temperature for 10 hours,
The resulting insoluble matter was filtered off, and the filtrate was concentrated to dryness.

The residue was recrystallized from acetonitrile to give colorless chlorophosphate N,N-bis[3-methyl-1,2,4-
Oxadiazol-5-one-1-yl]amide 10.
2 g (yield 73%) was obtained. <Synthesis of Exemplary Compound 15> Chlorophosphate N,N-bis[
A solution of 8.4 g (0.030 mol) of 3-methyl-1,2,4-oxadiazol-5-one-1-yl]amide in 30 ml of acetonitrile was added to an ice-cooled solution of 6-sulfo-1,
7.1 g (0.030 mol) of 2-benzisoxazol-3-ol sodium salt and 3.0 g of triethylamine
g (0.030 mol) in 50 ml of acetonitrile.

After stirring the reaction mixture at room temperature for 2 hours, the resulting insoluble matter was filtered off, and the filtrate was concentrated to dryness. The residue was recrystallized from acetonitrile to obtain 10.3 g (yield: 75%) of white crystals of Exemplified Compound 15. Synthesis of Exemplary Compound 27 (Synthesis of bis-4-methoxyphenyl chlorophosphate) 4
- A solution of 12.4 g (0.10 mol) of methoxyphenol in 250 ml of methylene chloride was vigorously stirred, and after adding 7.67 g (0.05 mol) of phosphorus oxychloride under water cooling,
A solution of 10.1 g (0.10 mol) of triethylamine in 50 ml of methylene chloride was added dropwise.

After stirring the reaction mixture at room temperature for 10 hours,
The resulting insoluble matter was filtered off, and the filtrate was concentrated to dryness. The residue was recrystallized from acetonitrile to obtain 11.5 g (yield: 70%) of colorless granular bis-4-methoxyphenyl chlorophosphate.

<Synthesis of Exemplary Compound 27> Bis-4-methoxyphenyl chlorophosphate 9.9 g (0.030 mol)
To 30 ml of acetonitrile solution was added 3.1 g of 3-methyl-1,2,4-oxadiazol-5-one (
0.031 mol) and then triethylamine 3.
A solution of 3 g (0.033 mol) in 20 ml of acetonitrile was added dropwise.

After stirring the reaction mixture at 0° C. for 1 hour, the resulting insoluble matter was filtered off, and the filtrate was concentrated to dryness. When the residue was recrystallized from ethyl acetate, colorless crystals of Exemplified Compound 27 were obtained.
．． 8g (yield 75%) was obtained.

[0060] Each of the above compounds was confirmed to be the desired product by NMR and IR.

Other compounds of the present invention can also be synthesized in good yields by similar methods.

[0062] The amount of hardening agent used when carrying out the present invention is as follows:
Although it varies depending on the type of photosensitive material to be applied and the type of hydrophilic binder, it is preferable that the dry weight of the binder is 0.
．． It ranges from 0.01 to 100% by weight, more preferably from 0.1 to 30% by weight.

The hydrophilic binder used in carrying out the present invention may be any commonly used gelatin, gelatin derivatives, or graft polymers of gelatin and other polymers.

[0064] As the water-dispersible polymer contained in the photographic constituent layer, a hydrophobic polymer obtained from a vinyl compound, an aqueous dispersion of a copolymer, an aqueous dispersion of a polycondensation polymer such as polyester can be used. .

Silver halide, chemical sensitizers, silver halide solvents, spectral sensitizing dyes, antifoggants, gelatin, etc. used in the silver halide emulsion layer or other layers of the light-sensitive material in carrying out the present invention There are no particular restrictions on hydrophilic protective colloids, ultraviolet absorbers, polymer latex, brighteners, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc.
e) Those described in Volume 176, pages 22-31 (December 1978) can be used.

[0066] In addition, supports for photosensitive materials, development processing methods,
Regarding the constituent layers of the photosensitive material, the description in the above-mentioned Research Disclosure magazine can be referred to.

[0067]

[Examples] The present invention will be further explained with reference to Examples below, but the present invention is not limited thereto. Example 1 In the following examples, the amount added in the silver halide photographic light-sensitive material is expressed in grams per m2 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

A multilayer color photographic material was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

First layer; antihalation layer (HC) black colloidal silver
0.15
Ultraviolet absorber (UV-1)
0.20 Colored cyan coupler (CC-1)
0.02 High boiling point solvent (O-1)
0
．． 20 High boiling point solvent (O-2)
0.20
gelatin
1.6
2nd layer; intermediate layer (IL-1) gelatin
1.
3 Third layer; low sensitivity red-sensitive emulsion layer (R-L) 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 D.I.
R compound (D-2)
0.01 High boiling point solvent (O
-1)
0.55 Additive (SC-1)

0.003 gelatin

1.0 4th layer; high sensitivity red-sensitive emulsion layer (R-
H) Silver iodobromide emulsion (Em-3)
0.9 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 DI
R compound (D-2)
0.02 High boiling point solvent (O
-1)
0.25 Additive (SC-1)

0.003 gelatin

1.0 5th layer; intermediate layer (IL-2) gelatin
0.
8 6th 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 point solvent (O-2)
0.70 Additive (SC-
1)
0.003 gelatin

1.0 7th 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)
0.1
3 Colored magenta coupler (CM-1)
0.04 DIR compound (
D-3)
0.004 High boiling point solvent (O-2)

0.35 Additive (SC-1)
0
．． 003 Gelatin

1.0 8th layer; yellow filter layer (YC)
yellow colloidal silver
0.1
Additive (HS-1)
0.07 Additive (HS-2)
0.07 Additive (SC
-2)
0.12 High boiling point solvent (O-2
)
0.15 gelatin

1.0 9th layer; low-speed blue-sensitive emulsion layer (B-
L) Silver iodobromide 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 D.I.
R compound (D-2)
0.006 High boiling point solvent (
O-2)
0.18 Additive (SC-1)

0.004 gelatin

1.3 10th layer; Highly sensitive 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 (O-2)
0.05
Additive (SC-1)
0.002 gelatin
1.0 11th layer;
First protective layer (PRO-1) Silver iodobromide emulsion (Em-5)
0.3 Ultraviolet absorber (UV-1)
0.07 Ultraviolet absorber (UV
-2)
0.1 Additive (HS-1)
0.
2 Additive (HS-2)
0.1
High boiling point solvent (O-1)
0.07 High boiling point solvent (O-3)
0.07 Gelatin

0.8 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2μ
m) 0.13 Polymethyl methacrylate (
Average particle size 3μm) 0.02 Slip agent (WAX-1)
0.04 Charge control agent (SU
-1)
0.004 Charge control agent (SU-2)

0.02 gelatin

0.5

Samples 1 to 18 were prepared by adding to each layer, in addition to the above, the hardener of the present invention or a comparative hardener as shown in Table 1. In addition, each layer contains a coating aid (SU-4), a dispersion aid (SU-3), and a stabilizer (ST-
1), preservative (DI-1), antifoggant (AF-1)
, (AF-2), and dyes (AI-1) and (AI-2) were added as appropriate.

The emulsions used in the above samples are as follows. Both are monodisperse emulsions with high internal iodine content. Em-1: Average silver iodide content 7.5 mol%, average grain size 0.55 μm, grain shape octahedral Em-2: Average silver iodide content 2.5 mol%, average grain size 0.36 μm, grain shape octahedral Em-3: Average silver iodide content 8.0 mol%, average grain size 0.84 μm, grain shape octahedral Em-4: Average silver iodide content 8.5 mol%, average grain size 1.02 μm, grain shape octahedral Em-5: Average silver iodide content 2.0 mol% Average grain size 0.08 μm

[0072]

[C36]

[0073]

[C37]

[0074]

[C38]

[0075]

[C39]

[0076]

[C40]

[0077]

[C41]

[0078]

[C42]

[0079]

[C43]

[0080]

[C44]

[0081]

[C45]

[0082] Each sample prepared is taken as a fresh sample,
A sample in which this sample was left at room temperature for 7 days, and a sample at 50°C.
Samples that were forced to deteriorate by being left at 50% RH for 2 days were prepared.

[0083] After these samples were wedge-exposed with white light, they were subjected to the following processing and the sensitivity and fog were measured.

Sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog + 0.5. Sample 1 was left at room temperature for 7 days after coating.
The relative sensitivity is shown with the sensitivity of 100 as 100.

[0085] The sample left at room temperature for 7 days was immersed in water at 30°C for 5 minutes, and a sapphire needle with a radius of 0.3 mm was brought into pressure contact with the sample surface, and a sapphire needle with a radius of 0.3 mm was pressed onto the membrane surface at a rate of 2 mm per second. The pressure load of the sapphire needle was continuously changed in the range of 0 to 200 g while the sample was moved in parallel, and the load at which damage occurred on the membrane surface of the sample was determined as the scratch resistance strength.

The results are also shown in Table 1 below.

Processing process Color development 38°C 3 minutes 15
Second bleaching 38℃ 6
Wash with water for 30 seconds at 38℃
Fixed for 3 minutes and 15 seconds at 38℃
Wash with water for 6 minutes and 30 seconds 3
Stabilized at 8℃ for 3 minutes and 15 seconds
Dry at 25℃ for 1 minute and 30 seconds.
45°C The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-N-(β-
Hydroxyethyl) Aniline Sulfate

4.75g anhydrous sodium sulfite

4.25g Hydroxylamine 1/2 sulfate 2.0
g Anhydrous potassium carbonate
37.5g
sodium bromide
1.3
g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g potassium hydroxide

Add 1.0g water to make 1 liter.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt
100g ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide

150.0g glacial acetic acid

Add 10.0 ml of water to make 1 liter, and adjust the pH to 6.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate
175.0g
anhydrous sodium sulfite
8.5g
sodium metasulfite
2.3g
Add water to make 1 liter and adjust to pH 6.0 using acetic acid.
Adjust to.

(Stabilizing liquid) Formalin (37% aqueous solution)
1.5ml
Konidax (manufactured by Konica Corporation)
Add 7.5ml water to make 1 liter.

[0092]

[C46]

[0093]

[Table 1]

As is clear from the results in Table 1 above, Samples 1 to 15 using the hardening agent according to the present invention all showed only a slight decrease in relative sensitivity compared to Comparative Samples 16 to 18. , no deterioration of fog was observed.

Further, even when forced deterioration is performed, samples 1 to 15 of the present invention show a slight decrease in sensitivity and only a slight increase in fog compared to comparative samples 16 to 18.

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

[0097] Also, from the results of scratch resistance, which indicates film strength,
Samples 1 to 5 of the present invention all exhibit higher film strength than Comparative Samples 6 to 7, which indicates that the hardener of the present invention hardens the film more efficiently than the comparative compounds. .

Example 2 Each layer having the composition shown below was sequentially formed on both sides of an undercoated polyethylene terephthalate support from the support side to obtain X-ray photosensitive material samples 19 to 30.

Additives other than silver halide are shown in amounts per mole of silver halide unless otherwise specified. 1st layer: Crossover cut layer Dye (I)

3mg/m2 Mordant (II)

0.12g/m2 gelatin

0.2g/m2 second layer:
Emulsion layer Emulsion consisting of AgBrI with an average grain size of 0.57 μm and containing 2 mol% of AgI
Coated silver amount
4.5mg/m2 Sensitizing dye (A)
450mg
Sensitizing dye (B)

20mg 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene


3.0g t-butyl-catechol

400mg polyvinylpyrrolidone (molecular weight 1
0,000) 1.0g
Styrene-maleic anhydride copolymer
2.5g trimethylolpropane
10g diethylene glycol
5g
p-Nitrophenyl-triphenylphosphonium chloride 50mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4g
Sodium 2-mercaptobenzimidazole-5-sulfonate 15mg Additive A

70mg Additive B

1g 1,1-dimethylol-1-bromo-
1-nitromethane 10mg gelatin
2g/
m2 3rd layer: Protective layer polymethyl methacrylate (average particle size 5 μm)
7mg/m2 Colloidal silica (average particle size 0.013μm)
70mg/m2 Additive C

10mg/m2 Additive D
2m
g/m2 Additive E

7mg/m2 Additive F

15mg/m2
gelatin

1 g/m2 Hardener (listed in Table 2) Preservative DI-1 was added to each sample.

[0100]

[C47]

[0101]

[C48]

[0102]

[C49]

Each sample was subjected to a storage test in the same manner as in Example 1, and then exposed to light and subjected to the following treatments, and photographic properties were measured in the same manner as in Example 1.

[0104] The sensitivity is the sensitivity of sample 19 7 days after application.
The relative sensitivity is expressed as 0.

The results are shown in Table 2.

(Processing process) Insertion
1.2 seconds development + transfer
35℃ 14.6 seconds
Establishment + migration 33℃
8.2 seconds Washing + Crossing
25℃ 7.2 seconds squeeze
40℃ 5.7
seconds dry 45
℃ 8.1 seconds (Developer) Hydroquinone
25.0g phenidone
1.2g potassium sulfite
55.0g boric acid

10.0g Sodium hydroxide
21.0
g triethylene glycol
17.5g 5-nitroimidazole
0.10g 5-nitrobenzimidazole
0.10g glutaraldehyde bisulfite
15.0g glacial acetic acid
16
．． 0g potassium bromide
4.0g
triethylenetetraminehexaacetic acid
Add 2.5g water to make 1 liter. (Fixer) Ammonium thiosulfate
130.9g Anhydrous sodium sulfite
7.3g boric acid

7.0g acetic acid (90wt%)
5.5g
Sodium acetate (trihydrate)
25.8g Aluminum sulfate (18 hydrate) 14.6g
Sulfuric acid (50wt%)
Add 6.77g water to make 1 liter.

[0107] While keeping the samples at 25°C and 50% RH humidity, a portion of each sample was taken out 2 hours, 1 day, and 7 days after coating, and swollen in water at 30°C for 5 minutes. Measure the film thickness of the sample, calculate the swelling degree V expressed by the following formula,
The change in hardening effect over time (postdurality) was observed.

The results are shown in Table 2 below.

[0109]

[Math 1] comparative compound

[0110]

[C50]

[0111]

[Table 2]

As is clear from the results in Table 2, X-ray photosensitive material samples 19 to 2 in which the hardening agent of the present invention was added to the protective layer
In sample No. 7, there was almost no change in photographic properties such as a decrease in sensitivity or an increase in fog, and furthermore, the change in degree of swelling was small and stable after one day or more after coating and drying, and compared to comparative samples 29 to 30, Durality is markedly improved. Moreover, when compared with sample 28, it can be seen that the dura mater was made efficiently.

[0113]

[Effects of the Invention] According to the present invention, the hardening effect can be efficiently achieved even with a small amount of hardening agent without impairing photographic performance.
It is possible to provide a silver halide photographic light-sensitive material containing a novel hardening agent that does not have a post-hardening effect.

Claims (4)

[Claims] Claim 1. A silver halide photographic material having at least one hydrophilic colloid layer on a support, comprising:
At least one of the hydrophilic colloid layers has the following general formula [
A silver halide photographic light-sensitive material, characterized in that it is hardened with at least one compound represented by [I]. General formula [I] [Formula, A represents a group selected from the groups represented by the following general formula [II]. General formula [II] [Formula 2] (In the formula, X and Y each represent an oxygen atom or a sulfur atom, and R1 represents an alkyl group, an aryl group, or an aralkyl group.) B is the following general formula [III], General formula [IV
] and represents a group selected from the group represented by the general formula [V]. General formula [III] [Chemical formula 3] (In the formula, Z1 represents an atomic group necessary to form a nitrogen-containing heterocycle.) General formula [IV] [Chemical formula 4] (In the formula, Y1 represents an oxygen atom or Represents a sulfur atom, Z
2 represents an atomic group necessary to form a nitrogen-containing heterocycle. ) General formula [V] (In the formula, R7 to R11 each represent a hydrogen atom or a substituent.) l represents 1, 2 or 3, m is 0, 1 or 2
, and l+m=3. ] 2. The silver halide photographic material according to claim 1, wherein the compound represented by the general formula [I] is a compound represented by the following general formula [VI]. General formula [VI] [Image Omitted] (wherein, A represents a group selected from the groups represented by general formula [II] according to claim 1.) 3. The silver halide photographic material according to claim 1, wherein the compound represented by the general formula [I] is a compound represented by the following general formula [VII]. General formula [VII] ] or a group selected from the group represented by the general formula [IV].) 4. The silver halide photographic material according to claim 1, wherein the compound represented by the general formula [I] is a compound represented by the following general formula [VIII]. General formula [VIII] ] Represents a group selected from the groups represented by.l' and m' represent 1 or 2, and l'+m'=3.)