JPH04157454A - Silver halide photosensitive material for photograph - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material for photograph which achieves the sufficient film hardness and is film-hardened by a film-hardening agent free from after film hardening action by film-hardening at least one layer of the hydrophilic colloid layers by the specific compounds. CONSTITUTION:At least one layer of the hydrophilic colloid layers is film- hardened by at least one kind of the compounds represented by the formula I. In the formula I, A is a group selected from the group represented by the formula II, and B is a group selected from the group represented by the formulas III or IV. In the formulas II-IV, X is-CO-or-SO2-, Y is-O-or-S-, R1 is a substituted or nonsubstituted alkyl group, aryl group, etc., R2 is a hydrogen atom, substituted or nonsubstituted alkyl group, etc., and Z is an atomic group which is necessary for forming a penta or hexa heterocyclic ring, Y is-O-or-S-, and Z1, Z2 is an atomic group which is necessary for forming a nitrogen- containing heterocyclic ring Accordingly, the silver halide photosensitive material which contains a novel film hardening agent which performs film hardening action efficiently and is free from the after film hardening action can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material whose photographic constituent layers are hardened with a specific compound.

[Background of the Invention] Generally, 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 low as is. 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.

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. 2,732,303,
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-1,3,5-1-lyazine, U.S. Pat. No. 3,232.7+13, U.S. Pat. No. 3,1113
No. 5.718, compounds having reactive olefins described in British Patent No. 994.809, etc., U.S. Patent No. 3,539,
No. 11i44, No. 3,642.486, Special Publication No. 1977-
No. 13583, No. 53-47271, No. 5B-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., U.S. Patent No. 3,103,437
Isocyanates described in US Pat. No. 2,983.
aziridine compounds described in U.S. Pat. No. 2,725,294, U.S. Pat.
725.295, etc., U.S. Patent No. 3,
Carbodiimide compounds described in No. 100,704, etc.
Epoxy compounds described in U.S. Pat. No. 3,091,537, etc., U.S. Pat. No. 3,321,313, U.S. Pat. No. 3.543.
Organic hardeners such as isoxazole compounds described in No. 292, halokeracarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and chromium alum, zirconium sulfate, chromium trichloride, etc. It is an inorganic hardener.

However, when these known hardening agents are used in light-sensitive materials, they may not have sufficient hardening action, or there may be a long-term change in hardening action called "post-hardening" that occurs due to the slow hardening reaction to gelatin. materials, materials that adversely affect the performance of the photosensitive material (in particular, increased fog, decreased sensitivity or maximum density, softened gradation, etc.), loss of hardening effect due to coexisting photographic additives, and other photographic additives. All had some drawbacks, such as those that reduced the effectiveness of additives (such as couplers in internal color emulsions) or caused contamination.

As hardening agents that have a relatively fast hardening effect on gelatin and cause less post-hardening, there are compounds having a dihydroquinoline skeleton described in JP-A-50-38540, and JP-A-51-5.
No. 9625, No. 62-282854, No. 62-2E1
No. 4044, No. 63- [N-carbamoylpyridinium salts described in No. 14741, Japanese Patent Publication No. 1986-38655
Acylimidazoles described in the Japanese Patent Publication No. 53-220
The N-acyloxyimino group described in No. 89 is 2 in the molecule.
Compounds containing N-sulfonyloxyimide groups as described in JP-A-52-93470, compounds having a phosphorus-halogen bond as described in JP-A-58-113929, JP-A-6(1986) -225148 No. 6
Chloroformamidinium compounds described in No. 1-240236 and No. 63-41580 are known.

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. The method has the drawback 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.

[Object of the Invention] Therefore, the object of the present invention is, firstly, 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.

The second object is to provide a photographic light-sensitive material hardened with a hardening agent that has a rapid hardening effect and does not require a post-hardening film.

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.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support,
At least one of the hydrophilic colloid layers has the following formula [
This was achieved by hardening with at least one compound represented by [1].

In the general formula [I-P-BU, A represents a group selected from the groups represented by the following formula [II].

General formula [■ B represents a group selected from the groups represented by the following formula [m] and general formula [IV].

General formula [■Co゛・, -/' General formula [TV] y, J'--' (In the above formula [1], X is -CO- or -S
O, -, Y is 10-1-S-1-N- or -C
-N- is represented.

I 1R2 R1 represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R2 represents a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, or aralkyl group.

Z represents an atomic group necessary to form a 5- or 6-membered heterocycle.

In general formula [m] and -numerical formula [IV], Y.

represents -0- or -S-, and Z and Z2 represent an atomic group necessary to form a nitrogen-containing heterocycle. )] The present invention will be further explained in detail.

Preferred examples of the group represented by formula [11] are shown below, but the present invention is not limited thereto.

Below margin 0-N-8-N- L R4RiHt N→-
N-N- R2R2 R5Rs R4R6R7K
5 R, R.

I R+ R+R+
R.

Here, R1 represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R2 represents a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, or aralkyl group.

Further, R3, R4, R5, R6, R7 and R8 are substituted or unsubstituted alkyl groups, aralkyl groups, alkylaryl groups, aryl groups, or hydrogen atoms, or
-CO2-1-CONH-1-OCO-1-NHCO-
1-SO2-1-S02NH-1N HS O2-1-
It represents a straight chain, branched or cyclic hydrocarbon group containing at least one linking group selected from SO, -1-0502-.

Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group, a sulfo group, a sulfamino group, and a sulfoxy group.

In general formula [m] and general formula [IV], Z.

and Z2 represent an atomic group necessary to form a nitrogen-containing heterocycle, but this nitrogen-containing heterocycle may be aliphatic or
It may also be aromatic.

Further, it may be a monocyclic ring or a condensed ring.

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

R12R12 R9R,. R9R1゜R9
RIOR9Rt.

In the following margins, R9, R+o, R++ and R+2 are substituted or unsubstituted alkyl groups, aralkyl groups, alkylaryl groups, aryl groups, or hydrogen atoms, and t2 is -C
○2-1-CONH-1-OCO-1-NHCO-1-
SO, -1-502NH-1-NHSO2-1-SO,
Represents a straight chain, branched or cyclic hydrocarbon group containing at least one linking group selected from -1-0SO2-.

Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group, a sulfo group, a sulfamino group, and a sulfoquine group.

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

Margin below Compound example 1゜ CH3CH3 CB, CI (.

l 1 4゜CH2CToSOa CFlzCHzSOJ! C
Hi Cfb Ro UtN1 CH3CH.

CH3C113 1; CH2CToSOJ2 CtbCHzSO1N
a11°CH3CH.

12°13°OJ1 15°16° or less Margin The compound of the present invention can be easily synthesized by a known method. For example, a compound represented by the following general formula [V] and a phosphorus oxyhalide represented by the general formula [VI],
In the presence of a base, the reaction was carried out at a molar ratio of 2.1, and the general formula [■]
It can be easily synthesized by making the phosphoric acid diamide halide represented by the following formula and further reacting it with a compound represented by the general formula [■].

General formula [V] -A General formula [VI] -p-x General formula [■] -P-A General formula [■Co-B [Above general formula [■], General formula [■], General formula [■] In the general formula [■], A and B represent the same as in the general formula [1], and X represents a halogen atom. ] Next, the synthesis method will be specifically explained using the above Exemplified Compound 2 as an example.

Synthesis of Exemplary Compound 2 <Chlorophosphate N,N-bis[3,5-dioxo-4-
Synthesis of methyl-1,2,4-oxadiazolidinyl]amide 11.6i (0.10 mol) of 3.5-dioxo-4-methyl-1,2,4-oxadiazolidine in methylene chloride 250 ml The solution was stirred vigorously, and after adding 67 g (0.05 mol) of oxychloride phosphorus 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 give colorless chlorophosphate N,N-bis[3,5-dioxo-4-methyl-1,2
,4-oxadiazolidinyl]amide 1O, 9 g (yield 70%) was obtained.

Synthesis of Exemplified Compound 2> Chlorphosphate N,N-bis[3,5-dioxo-4-methyl-1,2,4-oxadiazolidinyl]amide9.
A solution of 4 g (0.03 mol) in 30 ml of acetonitrile was added with 7.1 g (0.03 mol) of 6-sulfo-1,2-benzisoxazol-3-ol sodium salt cooled on ice.
mol) and triethylamine 3.0g (0.03 mol)
into a 50 ml solution 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. When the residue was recrystallized from acetonitrile, 11.1 g of white crystals of Exemplified Compound 2 were obtained (
Yield: 72%).

The structure of this product was confirmed by NMR and IR.

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

The amount of hardening agent used when carrying out the present invention varies depending on the type of photosensitive material to be applied, the type of hydrophilic binder, etc., and is preferably 0.01 to 10% of the dry weight of the binder.
0% by weight, more preferably 01-30% by weight.

In addition, the hydrophilic binder used when carrying out the present invention is
Any commonly used gelatin, gelatin derivatives, or graft polymers of gelatin and other polymers may be used.

Further, 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, etc. can be used.

Hydrophilic properties of silver halide, chemical sensitizers, silver halide solvents, spectral sensitizing dyes, antifoggants, gelatin, etc. used in silver halide emulsion layers or other layers of light-sensitive materials when carrying out the present invention Protective colloid, UV absorber,
There are no particular restrictions on polymer latex, brighteners, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc., and for example, research disclosure (
Research Disclosure) 17
6, pp. 22-31 (December 1978) can be used.

Further, regarding the support of the photosensitive material, the development method, the constituent layers of the photosensitive material, etc., the descriptions in the above-mentioned Research Disclosure magazine can be referred to.

[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 to the silver halide photographic light-sensitive material indicates the number of grams per resist 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 each layer having the composition shown below on a triacetyl cellulose film support from the support side.

1st 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 (Oill-1) 0.20 High boiling point 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 (R-L) silver iodobromide emulsion (Em-1)
0.4 silver iodobromide emulsion (E m -2)
0.3 Sensitizing dye (S-1) 3
．． 2X 10-' sensitizing dye (S-2)
3.2x 10-' sensitizing dye (S-3) 0.2X t
o-'Cyan coupler (C-1) 0.5
0 cyan coupler (C-2) 0.13 colored cyan coupler (CC-1) 0.07DI
R compound (D-1) 0.006DIR
Compound (D-2) 0.01 high boiling point solvent (
Oin -1) 0.55 Additive (S C-
1) 0.003 gelatin
1.0 4th layer; Highly sensitive red-sensitive emulsion layer (
R-H) Silver iodobromide emulsion (E m -3) 0
．． 9 Sensitizing dye (S-1) 1.7xlO
-'Sensitizing dye (S-2) L, 6xlO-
'Sensitizing dye (S-3) 0. lX10-'
Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2>0.02 High boiling point solvent (Oill-1) 0.25 Additive (
S C-1) 0.003 gelatin
1,0 5th layer; middle layer (IL
-2) Gelatin 0.8 6th layer; low-sensitivity green-sensitive emulsion layer (GL) silver iodobromide emulsion (E m -
1) 0.8 silver iodobromide emulsion (E m -2)
0.2 sensitizing dye (S-4)
8.7xlO-'sensitizing dye (S-5)
0.8x 10-' Magenta Coupler (M-1)
0.17 magenta coupler (M-2) 0
．． 43 color magenta coupler (CM-1) 0.10DI
R compound (D-3) 0. (I2 high boiling point solvent (Oin -2) 0.70 additive (S
C-1) 0.003 gelatin
1.0 7th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (E m -3)
0.9 Sensitizing dye (S-6) 1. lX1
0-'sensitizing dye (S-7) 2.0xl
O-'sensitizing dye (S-8) 0.3xlO
-'Magenta coupler (M-1) 0.03 magenta coupler (M-2) 0.13 colored magenta coupler (CM-1) 0.04DI
R compound (D-3) 0.004 High boiling point solvent (Oil-2) 0.35 Additive (S
C-1) 0.003 gelatin
10 8th layer; Yellow filter layer (Y C) Yellow colloidal silver 0
．． 1 Additive (MS-1) 0.07 Additive (MS-2) 0.07 Additive (S C-2) 0.12 High boiling point solvent (Ofil-2) 0.15 Gelatin
1.0 9th layer; low-speed blue-sensitive emulsion layer (BL) silver iodobromide emulsion (E m -1)
0.25 silver iodobromide emulsion (E m -2)
0.25 sensitizing dye (S-9) 5.
8x 10~4 yellow coupler (Y-1)
0.60 YE echo coupler (Y-2) 0.
32DIR compound (D-1) 0.00
3DIR compound (D-2) 0.00
6 High boiling point solvent (OiN -2) 0.18 Additive (SC-1) 0.004 Gelatin l.3 10th layer: High sensitivity blue sensitive emulsion layer (B-H) Silver iodobromide emulsion (E m - 4)
0.5 sensitizing dye (S-10)
3. Ox 10-' sensitizing dye (S-11)
1.2xlo-' yellow coupler (Y-1)
0.18 yellow coupler (Y-2)
0.10 High boiling point solvent (OiN-2) 0.
05 Additive (S C-1) 0.00
2 Gelatin 1.0 11th layer: 1st protective layer (PRO-1) Silver iodobromide emulsion (E m -5) 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2 ) 0.1 additive (MS-1)
0.2 additive (HS-2)
0.1 high boiling point solvent (Oif -1)
0.07 high boiling point solvent (O1j7-3)
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 Slip agent (WAX-1) 0.04 Charge control agent (SU-1) 0.004 Charge control agent (SU-2) 0.02 Gelatin
Sample fish 1 to 8 were prepared by adding a hardening agent of the present invention or a comparative hardening agent to each layer as shown in Table 1 in addition to the above.

In addition, each layer contains a coating aid (SU-4) and a dispersion aid (
SU-3), stabilizer (ST-1), preservative (DI-
1), antifoggants (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 25 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 or less margin - I I I J C-1 M-1 D-3 H V-1 H V-2 C2H9 S-1 H7C-c=.

υ S-2 ■ U-1 NaOxS-CH-COOCH2 (CFzCF2) J Akebono CH2-C00CH2 (CF2CF2hHU-2 U-3 U-4 N!0zS-CH-COOCaL CHz-COOCHt7 C2H5 (CH2) 4303 (CH2) 3 SO3H (CHz)zsOtS-9 S-10 C-1 H C-2 mixture (2+ 3) 1f-1 2H5 2H5 Oi, Q-2 1R-3 I-1 I-2 T-1 (Component A) (Component B) (
Component C) (Component molar ratio Component A: Component B: Component C-5
0:4B:4) AF-1 AF-2 Each sample created with the following margins is a fresh sample, and this sample is a sample left at room temperature for 7 days, and a sample at 506°C and 50% RH.
Samples that were forced to deteriorate by being left for two days were prepared.

These samples were wedge-exposed to white light, then subjected to the following processing, and sensitivity and fog were measured.

The sensitivity is expressed as 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 No. 1, which was left under the chamber for 7 days after coating, as 100.

In addition, the sample that had been left at the above 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 degrees was pressed against the sample surface and moved in parallel on the membrane surface at a speed of 2 degrees per second. The pressure load of the sapphire needle was continuously changed from 0 to 200 g, 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℃ 3 minutes 15 seconds Bleaching
Wash at 38℃ for 6 minutes and 30 seconds.
Fixation at 38℃ for 3 minutes and 15 seconds 3
8℃ 6 minutes 30 seconds Wash with water 38℃
Stabilization for 3 minutes and 15 seconds at 25°C Drying for 1 minute and 30 seconds at 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 2.0g anhydrous Potassium carbonate 37.5g Sodium bromide
1°3g nitrilotriacetic acid 3
Sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1g.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide ゛150. Og glacial acetic acid
Add 10.0 ml of water to make 1 g, and adjust the pH to -8.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.52 Sodium metasulfite 2.3g Water was added to make Iff, and the pH was adjusted to -6.0 using acetic acid.

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

The following margins are Comparative Compound (1) (Compound described in JP-A No. 51-59625) Comparative Compound (n) I (Compound described in JP-A-58-113929) Comparative Compound (III) CTo□CH302CToCON) lCH2CHJHC
OCH2SOzCH=CH2 (JP-A-53-41221
As is clear from the results of Table 1 above, samples Nα1 to Nα5 using the hardening agent according to the present invention are all similar to comparative sample Nα.
Compared to α6 to α8, there is only a slight decrease in relative sensitivity, and no deterioration in fogging is observed.

In addition, even when forced deterioration was performed, the comparison sample had a
Compared to the sample kl~5 of the present invention, there is a slight decrease in sensitivity, and only a slight increase in fog is observed.

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

In addition, from the results of scratch resistance, which indicates film strength, the present invention sample N
Since α1 to α5 all exhibit higher film strength than comparative samples No. 6 to 7, it can be seen 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 a subbed polyethylene terephthalate support from the support side to obtain X-ray photosensitive material samples Nos. 9 to 14.

Additives other than silver halide are shown in amounts per mole of silver halide unless otherwise specified.

1st layer: Crossover cut layer Dye (■) 3■ / Mordant (II) O, 12sr / Gogelatin 0.2g / Go 2nd layer: Emulsion layer average grain size 0° 57 μm AgBr containing 2 mol% of SAgI
Emulsion coating amount consisting of 1 4.5 g/rrr Sensitizing dye (A) 450s+g Sensitizing dye (B) 20 mg 4-hydroxy-
6-Methyl-1,3,3a,7-chitrazaindene 3. Ogt-butyl-catechol 400■ Polyvinylpyrrolidone (molecular weight 10.000) 1.0g Styrene-maleic anhydride copolymer 2.5g Trimethylolpropane 10g Diethylene glycol
5gp-Nitrophenyl-triphenylphosphonium chloride 50g1.3-dihydroxybenzene = 4-ammonium sulfonate 4g 2-mercaptobenzimidazole-5-sodium sulfonate 15agR 1,1-dimethylol-1-promo-1- Nitromethane 10s+g gelatin
2tr/gojs 3 layers: Protective layer polymethyl methacrylate (average particle size 5μm) 7@g/gocolloidal silicone force (average particle size 0.013μm) 70mg/rn”CH
>Coo (CTo), cHy OJt Gelatin Lg/ni Hardener (Table-
2) Dye (I) Mordant (ff) H6Cz”CJ.

1/25O42e x:y-25 near 5 Note that the preservative DI-1 was appropriately added to each sample.

I-1 Decrease A) (Component B) (Component C) (Component molar ratio Component A: Component B: Component C-50
:46:4) After the storage test for each sample in the same manner as in Example 1, the samples were exposed to light and subjected to the following treatments, and the photographic properties were measured in the same manner as in Example 1.

The sensitivity was expressed as a relative sensitivity, with the sensitivity of sample seed 9 7 days after application being taken as 100.

The results are shown in Table-2.

(Processing process) Insert 1.2 seconds development + transition
35℃ 14.6 seconds fixation + transfer 3
3℃ 8.2 seconds water washing + crossing 25℃
7.2 seconds squeeze 40℃ 5.7 seconds drying 45℃ 8.1 seconds (developer) Hydroquinone 25.0g Phenidone 1.2g Potassium sulfite 55.0g Boric acid
10.0g sodium hydroxide
21.0g triethylene glycol 17.5
g5-nitroimidazole 0.10g5-nitropenzimidazole 0. lOg glutaraldehyde bisulfite 15.0g glacial acetic acid
16.0g potassium bromide
4.0g triethylenetetraminehexaacetic acid 2.
Add 5g of water to make it IN.

(Fixer) Ammonium thiosulfate 130.9g Anhydrous sodium sulfite 7.3g Boric acid
7.0g acetic acid (9wt%)
5.5g Sodium acetate (trihydrate)
25.8g aluminum sulfate (18 hydrate)
14.6g sulfuric acid (50νt%)
Add 6.77g water to make 1fI.

In addition, while maintaining the sample 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 allowed to swell in water at 30°C for 5 minutes. The thickness was measured, the swelling degree V expressed by the following formula was calculated, and the change over time in the curing effect (post-curability) was observed.

The results are shown in Table 2 below.

Comparative Compound (IV) HCHO (V) CHO HO As is clear from the results in Table 2, in X-ray photosensitive material samples 9 to 11 in which the hardening agent of the present invention was added to the protective layer,
There is almost no change in photographic properties such as a decrease in sensitivity or an increase in fog, and the change in swelling degree is small and stable after one day or more after coating and drying. performance has been significantly improved. Moreover, when compared with Sample 12, it can be seen that the dura mater was made efficiently.

[Effects of the Invention] According to the present invention, a silver halide containing a novel hardening agent that efficiently hardens even with a small amount of hardener without impairing photographic performance and has no post-hardening effect. A photographic material can be provided.

Applicant Co., Ltd.

Claims (1)

[Scope of Claims] 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 is a compound represented by the following general formula [I]. A silver halide photographic material characterized by being hardened with at least one of the following. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A represents a group selected from the groups represented by the following general formula [II]. General formula [II] ▲There are numerical formulas, chemical formulas, tables, etc.▼ B represents a group selected from the groups represented by the following general formula [III] and general formula [IV]. General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above general formula [II], X is -CO- or -S
Represents O_2-, and Y represents -O-, -S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_1 represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group. R_2 represents a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. Z represents an atomic group necessary to form a 5- or 6-membered heterocycle. In general formula [III] and general formula [IV], Y_1 is −
It represents O- or -S-, and Z_1 and Z_2 represent an atomic group necessary to form a nitrogen-containing heterocycle. )]