JPH03259241A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To attain a sufficiently high hardening degree without adversely affecting photographic characteristics by hardening at least one of hydrophilic colloidal layers with at least one of specified compounds. CONSTITUTION:At least one of the hydrophilic colloidal layers of the photographic sensitive material 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, III, or the like; each of R1-R6 is H, halogen, aryl, alkoxy, aryloxy, -CO2M, or -SO3M, thus permitting the obtained silver halide photographic sensitive material to be hardened efficiently with a small amount of hardener without impairing and photographic performance and to contain a novel hardener freed of after-hardening action.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] 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.

[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 consisting of a hydrophilic polymer and/or a water-dispersible polymer, their mechanical strength is weak as is. It is swellable. In addition, latex films have drawbacks such as extremely poor adhesion to the support and easy peeling.

For this reason, it is known that compounds called "hardeners" are added to photographic constituent layers to improve their mechanical strength.1 For example, aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732,303 issue,
No. 3,288,775, British Patent No. 974.723,
1,167.207, getone compounds such as diacetyl and cyclobentanedione, bis(2-chloroethyl)urea, 2-hydroxy-4°6-dichloro-1, 3,5-)
-Ryazine, divinylsulfone, 5-acetyl-1,3
-Diacryloylhexahydro-1,3,5-)riazine, U.S. Pat. No. 3,232,763, U.S. Pat.
No. 18, compounds having reactive olefins described in British Patent No. 994.809, etc., U.S. Patent No. 3,539,644
No. 3,642,486, Special Publication No. 49-13563
No. 53-47271, No. 56-48860, JP-A No. 53-57257, No. 61-128240, No. 62-4275, No. 63-53541, No. 63-2
Vinylsulfonyl compounds described in No. 64572 etc., N-
Hydroxymethylphthalimide, U.S. Pat. No. 2,732,
N-methylol compounds described in No. 316, No. 2,586,168, etc., isocyanates described in U.S. Pat. No. 3,103,437, etc., U.S. Pat. No. 2,983,611,
Aziridine compounds described in U.S. Patent No. 3,107,280, etc., U.S. Pat.
Acid derivatives described in No. 5, etc., U.S. Patent No. 3.100.70
Carbodiimide compounds described in No. 4, etc., U.S. Patent No. 3,
Epoxy compounds described in US Pat. No. 091,537, isoxazole compounds described in US Pat. No. 3,321,313, US Pat. These include organic hardeners such as dioxane derivatives such as dichlorodioxane, and inorganic hardeners such as chromium alum, Kn zirconium, and chromium trichloride.

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. 62-262854, No. 62-264
N-carbamoylvinidinium salts described in No. 044 and No. 63-184741, compounds containing two or more N-acino) oximino groups in the molecule as described in Japanese Patent Publication No. 53-22089, Compounds having an ON-sulfonino 1 oximide group described in JP-A No. 52-93470, compounds having a phosphorus-halogen bond described in JP-A-58-113929, JP-A-60-225148 and JP-A-61
~ No. 240236, No. 63-4i580
v, Vphor b7midinium compounds, etc. are known.

1) Hardeners have the characteristics of fast curing action and, therefore, less hardening. However, these hardeners have a lot of L/X stiffness that affects photographic properties, hardening reaction of gelatin is fast, and 1,
Since the side reactions caused by H are also fast, the general manufacturing method of photographic light-sensitive materials using an aqueous solution of gelatin has extremely low efficiency of effective use of the hardening agent, and it is difficult to obtain a gelatin film with sufficient hardness. To do this, use a large amount of hardening agent.]
, it had the disadvantage of not having to be used.

[Object of the Invention] Therefore, the object of the present invention is, firstly, to improve the hardness of the material by using a novel hardening agent that achieves sufficient hardness without any adverse effect on the photographic properties. It is about providing.

Secondly, it has a rapid curing action and is hardened with a hardening agent without a post-hardening film, t': 4I, which provides a photographic light-sensitive material.

The third object is to provide a photographic light-sensitive material that is hardened with a hardening agent that reacts with reactive residues in gelatin with a high diffraction property of 1-2 and hardens gelatin efficiently.

[Structure of the Invention] The object of the present invention is to provide 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 has the following general formula [
This was achieved by hardening with at least one compound represented by 'l].

General formula [I] -P-A 3 [wherein A is selected from the group represented by F general formula [■], general formula [1,], general formula 'IN/] and general formula [V] Indicates cotton group.

General formula [n] - Format [11T] General formula [IV] 7 8 General formula [V] R13R12 In the above general formula [■] 5 General formula I format, General formula [IV] and General formula V], R3- R and 13 each represent a hydrogen atom or a substituent. ] The present invention will be further explained in detail.

The substituents represented by -R613 to R and l and j- include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a -CO2M group, and a -SodaM group.

The alkyl group, aryl group, alkoxy group, and aryloxy group may be unsubstituted or 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, sulfamino groups, and sulfoxy groups.

Examples of the alkyl group include methyl group, ethyl group,
Examples include propyl group, methoxyethyl group, chloromethyl group, taloloethyl group, sulfomethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, carboxymethyl group, 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. be able to.

M represents a hydrogen atom, an ammonium group, an alkali metal atom or an alkaline earth metal atom.

Examples of the ammonium group include ammonium group, trimethylammonium group, tetramethylammonium group,
Examples include a tetraethylammonium group and a butyltrimethylammonium group.

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

Stone compound O2K H9OJa CH20SOJa 5O3HNH3 The following system 0 The compound of the present invention can be easily synthesized by a known method. For example, a compound represented by the following general formula [VI] and a phosphorus oxyhalide represented by the general formula [■],
In the presence of a base, anti-J15 was reacted at a molar ratio of 2:1 to form the general formula [
[2] After the phosphoric acid diamide halide Lj- is reacted with an azide compound represented by the general formula [IX], or a phenol represented by the general formula [X] is reacted with the phosphoric acid diamide halide Lj- represented by the general formula [IX]. ■ Phosphorus oxyhalide represented by the formula [X
It can be easily synthesized by preparing a phosphoric acid diphenol ester halide represented by ll and then reacting it with an azide compound represented by the general formula [■].

General formula [VI] -A -Math [■ko0 -p-x General formula [■Ko-PA+ General formula [■KoM'N3] General formula [X] A2 General formula [XI] A2 P A2 [Above - formula [■], -Formula [vffl, -Formula [■]
In the - formula [■ Co, - formula [X] and - formula [XI], A+ is a group selected from the groups represented by general formula [■], - formula [11 [] and general formula IV]. represents A
2 represents a group selected from the groups represented by the general formula [V], X represents a halogen atom, and M' represents an alkali metal atom or an alkaline earth metal atom.] Next, the above exemplary compounds 1 and The synthesis method will be specifically explained using No. 16 as an example.

Synthesis of Exemplary Compound 1 <Synthesis of chlorophosphate N,N-bis[2-oxo-3-oxazolidinyl coamide>] A solution of 8.7 g (0.10 mol) of oxazolidone in 250 ml of methylene chloride was vigorously stirred, and the mixture was cooled with water. After adding oxychloride phosphorus, 67, (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 removed, and the liquid was concentrated to dryness. The residue was recrystallized with acetonitrile to obtain colorless granular chlorurin 1112N,N-bis[2-oxo-3-oxazolidinyl coamide 8.9
．． (yield 70%).

Synthesis of Exemplified Compound 1> Suspension of 7-6 g (0,030 mol) of chlorophosphate N,N-bis[2-oxo-3oxazolidinyl]amide and 29 g (0,045 mol) of sodium azide in 50 ml of acetonitrile Heat to reflux for 3 hours. After cooling, insoluble matter was removed, and the r liquid was concentrated to dryness. When recrystallized from alcohol, colorless crystals of Exemplified Compound 1 are obtained as 6.3.
(yield: 80%).

Synthesis of Exemplary Compound 16 (Synthesis of bis-4-methoxyphenyl chlorophosphate) A solution of 4-methoxyphenol 12.4 (0.10 mol) in 250 ml of methylene chloride was vigorously stirred, and under water cooling, 67 g of oxychloride phosphorus was added. After adding (0,05 mol), 10.1 t (0,10 mol) of triethylamine 50 methylene chloride! The solution was added dropwise.

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

<Synthesis of Exemplary Compound 16> Bis-4-methoxyphenyl chlorophosphate 9.9. (
0,030 mol) and sodium azide 2,9, (0
,045 mol) of acetonitrile 50 ml! I! The suspension is heated to reflux for 3 hours. After cooling with water, insoluble matter was removed, and the r solution was concentrated to dryness. Recrystallization from alcohol gave colorless crystals of Exemplified Compound 16 (yield: 80%).

Each of the above compounds was confirmed to be the target compound by NMR and IR.

The compound of the present invention can also be synthesized at a high rate by the same method.

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., but is preferably 0.01 to 10% of the dry weight of the binder.
0% by weight, more preferably 0.1-30% by weight? The aqueous binder used in carrying out the present invention may be any of the commonly used gelatin, gelatin derivatives, gelatin and other polymers, and graft polymers. ′
be.

1. 1. Contained in the photographic constituent layer. Examples of water-dispersible polymers include hydrophobic polymers obtained from vinyl compounds,
1. Aqueous Dispersion of Copolymer 1 Of course, it is too difficult to use an aqueous dispersion of a polycondensation polymer such as polyester.

Silver halide, chemical sensitizer I, silver halide ax 1, spectral sensitizing dye used in the silver halide emulsion layer or other layers of the light-sensitive material in the solid line of the present invention , antifoggant, hydrophilic protective colloid such as gelatin, Shiyu F
Line absorbent, polymer latex, brightener, color coupler, anti-fade agent, dye, pine? = There are no particular restrictions on FJ, surface active agents, etc.
sure) Volume 176, pp. 22-31 (1978 1)
February> C=Items marked with R can be used.

Further, regarding the support of the photosensitive material, the development method, the structure M of the photosensitive material, etc., the description in the above-mentioned Research Disclosure magazine can be referred to.

[Example 1] The present invention will be further explained below with reference to Examples, 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 does not indicate the number of grams per ffllf unless otherwise specified. Also, silver halide and colloidal silver are converted to silverj7
It was shown. The sensitizing dye is expressed in moles per mo/i- of silver.

A multilayer color photographic material was prepared by sequentially forming each layer having the composition shown below on a 1-lyacetyl heptalulose film support from the support side.

1st layer: Antihalation layer (HC) Black colloidal silver 0.15 Ultraviolet absorber (tJV-i) 0.20 Colored cyan coupler (CC-1) High boiling point solvent (OI view-1) High boiling point solvent (Ol, Tomoe-2) Gelatin 2nd layer; Intermediate layer (IL-1 gelatin 3N; Low sensitivity red-sensitive emulsion layer (R).

Silver iodobromide emulsion (Ern-t) Silver iodobromide emulsion (Em-2) Sensitizing dye (S 1) Sensitizing dye (S-2) Sensitizing color $ (S-3) Cyan coupler (C-1 ) b Uncoupler ((>2) Colored cyan coupler (C(, -1) DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oij-1) 0.02 0.20 0.20 1.6 1.3 L) 0.4 0.3 3.2X 10-' 3.2X 10-' 0.2X 10-' 0.50 0.13 0.07 0.006 0.01 0.55 Additive (SCI) Gelatin 4th layer; high sensitivity red-sensitive emulsion layer (R Silver iodobromide emulsion (Em-3) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S- 3) Cyan coupler (C-2) Colored cyan coupler (CC-1) DIR compound (D-2) High boiling point solvent (Oij-1) Additive (SC-1) Gelatin 5th layer; Intermediate layer (IL-2 > Gelatin 6th layer; low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Bm-2) Sensitized color! (F, -4) (GL) 0.003 1.0 ■) 0.9 1.7x 10-'1.6X10-' 0.1 x 10-' 0.23 0.03 0.02 0.25 0.003 1, C 0,8 0,6 0,2 6,7x 10-' Sensitizing dye (S-5) 0.8X10-' Magenta coupler (M-1> 0.17 Magenta coupler <M-2) 0.43 colored magenta coupler (CM-1) 0.10DIR
Compound (D-3) 0.02 high boiling point solvent (
Oij-2>0.70 additive (SC-1)
0.003 gelatin
1.0 7th layer; high-sensitivity green-sensitive emulsion layer (G-
H) Silver iodobromide emulsion (Em-3) 0.9 sensitizing dye (S-6) 1.1xlO-' sensitizing dye (S-7) 2.0x10-' sensitizing dye (S-8) 0 .3x10-' 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 (SC
-1) 0.003 gelatin
1.0 8th layer; yellow filter layer (yc) yellow colloidal silver 0.1
Additive (MS-1) 0.07 additive (MS-2) 0.07 additive (SC
-2) 0.12 high boiling point solution 11X (
Oij-2) 0.15 gelatin
1.0 9th layer; low-speed blue-sensitive emulsion layer (
BL) Silver iodobromide emulsion (Em-1) 0.2
5 silver iodobromide emulsion (Em-2) 0.25 sensitizing dye (S-9) 5.8X10-' yellow coupler (Y-1) 0.60 yellow coupler (Y-2) 0.32 DIR compound (D
-1) 0.003DIR compound (D-2
) 0.006 high boiling point molten g (Oij-2)
0.18 additive (SC-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) 3.0X10-' sensitizing dye (S-
11) 1.2X10-' Yellow coupler (Y-1) 0.18 Yellow coupler (Y-
2) 0.10 high boiling point molten g (Oij-2)
0.05 additive (SC-1)
0.002 gelatin 1.
0 11th layer; 1st protective layer (PRO-1) Silver iodobromide emulsion (Em-5) 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (
UV-2) 0.1 additive (MS-1)
0.2 additive (MS-2)
0.1 High boiling point solvent (Oij-1) 0
．． 07 High boiling point melt! (Oij-3) 0.07
Gelatin 0.8 12th layer;
Second 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% e-electromodulator (S
U-2) 0.02 gelatin
In addition to the above, a hardening agent of the present invention or a comparative hardening agent as shown in Table 1 was added to each of the O and S layers to prepare sample vessels 1 to 8.

In addition, each layer contains a coating aid (SU-4) and a dispersion aid (s).
tr-3>, stable jFIl<s'r-1, vBg agent (
DI-1), antifoggant (AP-1), (AP-
2), 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 63 Average grain size 0.84JJrtx Grain shape Octahedral Eyn-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
,08μm Below margin j -1 I -2 j -1 C~2 -1 C-3 M-1 2 -3 H U-1 NaOJ-CH-COOCH2 (CF2CF213HC
H2-COOCH2 (CF2CF2) JU-2 U-3 U-4 NaOzS-CH-COOCJ 17 CL-COOCH+7 V-1 H V-2 eHs S-1 S-2 -1 aHs QHs 2H6 -4 2Hs 5 2Hs 2H5 - 6 C.J.

−7 C,l(5 −8 Ca)! s ((:H214st)3 d5 S(>2 mixture (2:3) LL-1 2k 2H5 0i?2 1-3 -10 (C1(2) 3S03 (CH2) 3SO3HN (C2[(513-11 C -1 I COOC+2H2s [Ill I-1 I-2 03K O3K T-1 I I-1 WAX-1 AP-1 AP-2 Each sample prepared below is a fresh sample, and this sample is stored at room temperature for 7 days. A sample that was left to stand and a sample that was forced to deteriorate by being left at 50° C. and 50% RH for 2 days were prepared.

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

Sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog + 0.5.
The relative sensitivity is expressed as 00.

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 m was pressed against the sample surface and moved parallel to the membrane surface at a speed of 2 am per second. While moving, the pressure load of the sapphire needle was continuously changed in the range of 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 Cloth-1 below.

Processing process Color development 38℃ 3 minutes 15 seconds Bleaching
Wash with water at 38℃ for 6 minutes and 30 seconds 38
℃ 3 minutes 15 seconds Fixation 38℃
Washing with water for 6 minutes and 30 seconds 38°C Stabilization for 3 minutes and 15 seconds 25°C for 1 minute and 30 seconds Drying 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 4.75° anhydrous sodium sulfite 4.25° hydroxylamine, 1/2 sulfate 260 g anhydrous Potassium carbonate 37.5g Sodium bromide
1.3f Nitrilotri# acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1. Add water to make 1j.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10.Of ammonium bromide 150.0g Glacial acetic acid
Add 10.0ml water to 11
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 11, and adjust to pH=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 11.

The following margins Comparison compound <I) 0 (Compound described in JP-A-51-59625) Comparison compound (II) j (Compound described in JP-A-58-113929) Comparison specialty (group) CH2 < I(S02CkCONHCH2(JJI(CO
CToSOaC! (=Ck (compound described in Japanese Unexamined Patent Publication No. 53-41221)) Below the margin As is clear from the results in Table 1 above, samples NG1 to NG using the hardening agent according to the present invention were .

Compared with comparative samples Nos. 6 to 8, there was only a slight decrease in relative sensitivity (1), and no deterioration of capri was observed.

In addition, even if forced deterioration is performed, comparison sample shame6-8
Compared to Jt and Jt, the present invention sample NQ 1''-s showed a decrease in sensitivity, and no increase in fog was observed.

Therefore, the hardening agent according to the present invention is suitable for use as a hardener according to the present invention. It can be seen that the properties are hardly affected.

Also, from the results of the flange resistance strength, which showed no film strength, 1, the present invention sample No. 1''-5, and the comparative sample N11.
6=Exhibits higher film strength compared to 7.1. Because of this,
The hardener of the present invention hardens more efficiently than comparative compounds! ! i~
I can see that it is.

Example 2 Undercoated poly, 7:,
- Form each layer of the composition shown below on both sides of the support sequentially from the support side.
I got 4.

Additives other than silver halide are used (,,': Unless otherwise specified, amounts are shown per mole of silver halide. 6 1st layer: Crossover layer 1-layer dye (■) 3 ■/rr? Mordant (I
I) 0.12. /rrr gelatin
0°2. /rd second secondary milk = emulsion average grain size 0.57μrn, AgB containing 2 mol% of AgI
Emulsion-coated silver 11 consisting of rI 4.5+r/ is sensitizing dye (A) 450■ Sensitizing dye (
B) 20rw: 4-hydroxy-
6-methyl 1,. 3.3a,7-chitrazaindene 3. Ogt-butyrocatechol 400■ Polyvinylpyrrolidone (molecule i10,000) 1. Oi Styrene-anhydride mal/inic acid copolymer 2.5g Trimethylolpropane diethylene glycol p-nitrophenyl-triphenylphosphonium chloride 1.3-dihydrooxybenzene-4-ammonium sulfonate 2-mercaptobenzimidazole-5 - Sodium sulfonate 10゜g 50■ g 15■ Colloidal silica (average particle size 0.013 μm) CH2COO (CHal 5cH3 70■/- 03Na H 1,1-dimethylol-1 Mo 1-nitromethane gelatin 3rd layer: eA protective layer polymethyl methacrylate (average particle size 5 μm) 1Pro 10■ 2, /rrf 7mt/rrf Gelatin hardener (listed in Table-2) 1.7d 1j!c fee (I) Mordant (n) [CH21zsOJ H5C2C2h 1/2 SO2" x : y = 25 : 75 (CH213SOz (CeHg12N) After a storage test for each sample in the same manner as in Example 1, exposure was applied and the following processing was performed, and photographic properties were measured in the same manner as in Example 1. did.

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

The results are shown in Table-2.

(Processing process) Insert 1-2 second development
35℃ 14.6 seconds fixation 33℃
8. 2 seconds water wash + crossing 25℃ 7.
Squeeze for 2 seconds, dry at 40℃ for 5.7 seconds
45°C 8.1 seconds (Developer) Hydroquinone 25.0 g Phenidone Potassium sulfite Boric acid I Lithium 1-Liethyl 1/N glycol 5-nitroimitazole 5-21 Robenz imidazole Glutaraldehyde Heavy Add sulfite, glacial acetic acid, potassium bromide, triethylene, tetramine, hexaacetic acid water and 1! Finish to J.

(Fixer) ammonium thiosulfate I-lium sulfite anhydride Boric acid #Acid (90wt%) #Sodium acid (trihydrate) Aluminum sulfate (18 hydrate) Sulfuric acid (50wt%) 1.2t 55.0g 10゜0g 21.0g 17.5° 0, IQ.

o, iog 15.OfE '+e, o,.

4.Og 2.5g 130.9° 7.3g 7.Og 5.5fr 25.8ir 14.6° 6.77.

Add water to bring the temperature to 1.9.6 Also, heat the sample at 25'C, 50% R,! A portion of each sample was taken out 2 hours, 1B, and 7 days after application while maintaining the humidity at Calculate the swelling degree V L, and observe the change over time in curing action (post-hardening property).The results are shown in Table 2 below. Comparative Compound (IV) HCHO (V) CHO CHO Below System O As is clear from the results in Table 2, X-ray photosensitive material samples NQ9 to -11 in which the hardening agent of the present invention was added to the protective layer showed changes in photographic properties such as a decrease in sensitivity and an increase in fog. It was hardly observed, and the change in the degree of swelling became stable after one day or more after coating and drying, and the post-hardening properties were significantly improved compared to comparative samples 8013 and 14. Also, sample 12 If you compare it with the image below, you can see that the dura mater is efficiently formed.

[Effects of the Invention] According to the present invention, there are 5, 4, and 2 things that impair photographic performance.
It is possible to provide a silver halide photographic X-sensitive material containing a novel hardening agent that exhibits efficient hardening action even with a small amount of hardening agent and is also free from post-hardening action.

Kushiganjin Konica 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] ▲ Numerical formulas, chemical formulas, tables, etc. Indicates a group selected from General formula [II] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above general formula [II], general formula [III], general formula [IV] and general formula [V], R_1 to R_1_3 each represent a hydrogen atom or a substituent. ]