JPH04157453A - 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 formula III. In the formulas II-III, 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, aryl group, etc., and Z is an atomic group which is necessary for forming a penta or hexa heterocyclic ring, and each of R3-R7 is a hydrogen atom or a substituted group. Accordingly, the silver halide photosensitive material for photograph which does not deteriorate the photograph performance and efficiently performs film hardening action with a little quantity of the film hardening agent 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] 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, an undercoat layer, and an anti-nolation layer. ,
It consists of various photographic constituent layers, such as an ultraviolet absorbing layer, an antistatic layer, and a backing layer, placed on a support such as glass, paper, or synthetic resin film.

Since these photographic constituent layers are coated with an aqueous coating solution composed of 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. 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 curcuraldehyde, US Pat. No. 2,732.303,
No. 3,288,775, British Patent No. 974.723,
1,187,207, 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. 3,63
No. 5,718, compounds having reactive olefins as described in British Patent No. 994.809, etc., U.S. Patent No. 3,539,
No. 644, No. 3,642,486, Special Publication No. 1973-13
No. 563, No. 53-47271, No. 56-48860
No., JP-A-53-57257, JP-A No. 61-128240
No. 82-4275, No. 63-53541, No. 6
Vinylsulfonyl compounds described in No. 3-264572 etc., N-hydroxymethylphthalimide, U.S. Patent No. 2,7
N described in No. 32,316, No. 2.588.188, etc.
- Methylol compounds, U.S. Pat. No. 3. Isocyanates described in LO3,437 etc., U.S. Patent No. 2,983.61
No. 1, aziridine compounds described in U.S. Pat. No. 3,107.280, etc., U.S. Pat.
, No. 295, etc., U.S. Patent No. 3,100
, 704, etc., epoxy compounds described in U.S. Patent No. 3,091,537, etc.
US patent a,! 321.313, 3,543,29
Organic hardeners such as isoxazole compounds described in No. 2, 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 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, or 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 have a small amount of posterior hardening, there are compounds having a dihydro-pre-noline skeleton described in JP-A-50-38540, and JP-A-51-5.
No. 9625, No. 62-282854, No. 62-264
No. 044, N-carbamoylpyridinium salts described in Japanese Patent Publication No. 63-184741, acylimidazoles described in Japanese Patent Publication No. 55-38855, Japanese Patent Publication No. 53-22089
Compounds containing two or more N-acyloxyimino groups in the molecule as described in JP-A No. 52-93470, compounds having an N-sulfonyloxyimide group as described in JP-A No. 58-113929, Compound having linno\logen bond, JP-A No. 60-225148, 461-
Chloroformamidinium compounds described in No. 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. 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.

[Purpose of the Invention] Accordingly, 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.

[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 general formula [
This was achieved by hardening with at least one compound represented by I.

General formula [I] (A)e P-(B)= [wherein A represents a group selected from the groups represented by the following general formula [■].

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

General formula [ml (In the above general formula [n], X is -CO- or -5
Represents O2-, and Y is 10-1-S-1R,R.

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 [III], R1 to R7 each represent a hydrogen atom or a substituent. ) 2 and m represent 1 or 2, and are l+m-3. ] The present invention will be further explained in detail.

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

In the margin below, write 1-Total--N-N-N- to 1-N-Isake-N-N- RLI R12RLO R1bi1 Here, R1 is a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. represent.

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

Also, R6, R9, RIOSRsrs R12 and RI
3 is a substituted or unsubstituted alkyl group, aralkyl group, alkylaryl group, aryl group or hydrogen atom,
Or -CO, -1-CONH-1-OCO-1-NH
CO-1-SO, -1-502NH-1-NHSO2-
At least 1 selected from 1-SO, -1-〇502-
A straight-chain, branched, or cyclic hydrocarbon group containing two linking groups.

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 the formula [II[], the substituent represented by %R, ~R7 includes a halogen atom, an alkyl group, an aryl group,
Examples include an alkoxy group, an aryloxy group, a -Co, M group, and a -So, M 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 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, chloroethyl 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, and p-sulfoxyphenyl group. be able to.

M represents a hydrogen atom, an ammonium group, an alkaline earth 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 formula [I] are listed below, but the present invention is not limited thereto.

Below are blank examples of exemplified compounds Hi CH3 CIbCH2SOJ! CH2CH25O3N1 GHzCH*SOJ! CH2CToSOJx CH2CH2SOIN1 The compound of the present invention can be easily synthesized by a known method. For example, a phenol represented by the following general formula [IV] and a phosphorus oxyhalide represented by the general formula [V] are reacted at a molar ratio of 1:1 or 2:1 in the presence of a base, and Easily synthesized by preparing a phosphoric acid phenol ester dihalide or a phosphoric acid diphenol ester halide represented by the formula [V[], and then reacting it with a compound represented by the general formula [■] in the presence of a base. can do.

General formula [IV] -B General formula [V] -p-x Art-Math formula [VI] (B) -P-(X) t General formula [■] -A [Above-Math formula [■], -Math formula [ ■] , - Formula [VI]
And in the general formula [■ko], A and B are the general formula [■ko]
I] and X represents /XX rosin child.

S and t represent 1 or 2, and are 5+t-3.

] Next, the synthesis method will be specifically explained using the above Exemplified Compound 2 as an example.

Synthesis of Exemplary Compound 2 (Synthesis of bis-4-methoxyphenyl chlorophosphate) A solution of 12.4 g (0.10 mol) of 4-methoxyphenol in 250 ml of methylene chloride was vigorously stirred, and under water cooling, oxychloride phosphoric acid, 87 g (0.05 mol)
After adding 10.1 g of triethylamine (0,
A solution of 10 mol) of methylene chloride in 50 ml 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 2> 9.9 g of bis-4-methoxyphenyl chlorophosphate (
0,030 mol) acetonitrile 20ml solution number;
Under ice cooling, 3,5-dioxo-4-methyl-1,2゜4-
3.6 g (0,031 mol) of oxadiazolidine was added, and then a solution of 3.3 g (0,033 mol) of triethylamine 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. The residue was recrystallized from ethyl acetate to obtain 8.5 tr (yield: 70%) of colorless crystals of Exemplary Compound 2.

Each of the above compounds was confirmed to be the target compound 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., but is preferably 0.01 to 10% of the dry weight of the binder.
0% by weight, more preferably 0.1-30% by weight.

In addition, the hydrophilic binder used when carrying out the present invention is
Any commonly used gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, etc. 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, ultraviolet 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
8, pp. 22-31 (December 1978) can be used. -- Also, 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 below with reference to Examples, but the present invention is not limited thereto.

Example 1 In the following examples, the amount added in a silver halide photographic light-sensitive material is expressed in grams per 1 ri'' unless otherwise specified. In addition, silver halide and colloidal silver are expressed in terms of silver. The sensitizing dye is 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 (OiR-1) 0.20 High Boiling point solvent (OiN-2) 0.20 gelatin
L, S second layer; intermediate layer (IL-1
) Gelatin 1.3 Third layer; Low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (E m -
1) 0.4 silver iodobromide emulsion (E m -2)
0.3 sensitizing dye (S-1)
3.2x 10-' sensitizing dye (S-2)
3.2xlO-' sensitizing dye (S-3)
0.2x 10-' cyan coupler (C-1)
0.50 cyan coupler (C-2)
O,1,3 colored cyan coupler (CC-1) 0.07Di
R compound (D-1) 0.006DIR
Compound (D-2) 0.01 high boiling point solvent (
OiΩ-1) 0.55 Additive (S C-1
) 0.003 gelatin
1.0 4th layer High sensitivity red sensitive emulsion layer (R
-H) Silver iodobromide emulsion (E m -3) 0.
9 Sensitizing dye (S-1) L, 7X 10
-'Sensitizing dye (S-2) 1.6x 1
0-' Sensitizing dye (S-3) O, 1xL
O'Cyan Cub Imaichi (C-2) 0.23 Colored Cyan Coupler (CC-1) 0.03DI
R compound (D-2) 0.02 High boiling point solvent (Oil-1) 0.25 Additive (S
C, 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 (E m -
1) 0.6 silver iodobromide emulsion (E m -2)
0.2 sensitizing dye (S-4)
6.7X 1 (1-'sensitizing dye (S-5)
0.8X 10-' Magenta Coupler (M-1)
0.17 magenta coupler = (M-2)
0.43 Colored Magenta Coupler (CM-1) 0.10DI
R compound (D-3) 0.02 High boiling point solvent (Oil-2) 0.70 Additive (SC,
-1) 0.0OS gelatin
1.0 7th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (E m -3)
0.9 Sensitizing dye (S-6) 1.1Xlo
-' Sensitizing dye (S-7) 2. Ox t
o-' Sensitizing dye (S-8) 0.3x
10-' Magenta coupler (M-1) 0.0
3 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. (1 (13 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 (S C-2) 0.12 High boiling point solvent (Oif-2) 0.15 Gelatin
1.0 9th layer - low sensitivity 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-' Yellow coupler (Y-1) 0.
60 yellow coupler (Y-2) 0.32
DIR compound (D-1) 0.003
DIR compound (D-2) 0.006 High boiling point solvent (OiN-2) O, LIll additive (SC-1) 0.004 Gelatin 1.3 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)
i, 2xlo-' yellow coupler (Y-1)
0.18 yellow coupler (Y-2)
0. LO high boiling point solvent (Ofit-2)
0.05 Additive (, SC-1) 0
．． 002 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 (MS-2)
0.1 high boiling point solvent (Oil-1)
0.07 High boiling point solvent (Oin) -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 magnets I to B were prepared by adding the hardener of the present invention or a comparative hardener 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), 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 or less margin-I CI I C-I M-1 I I V-1 I V-2 2H5 S-1 S-2 ■ 5U-1 NaOtS-CH-COOCH2 (CFzCF2) JC
H2-C00CH2(CFzCF2)JU-2 U-3 U-4 N10tS-CH-COOCa[(r7CHz-COO
CH27-I C2H5CvH9 C2H.

C.J.

C-1 H OUCtJ2s(fi) 5C-2 Oi party-1 Js Lfl-2 I-1 I-2 T-1 (')I( Decrease A) (Component B) (Component C) (Component molar ratio Component A: Component B Two-component C-50
+46:4) AX-1 F-1 F-2 Each of the samples with the following margins prepared was taken as a fresh sample, and this sample was left at room temperature for 7 days, and the sample left at 50°C and 50% RH for 2 days. Samples with forced deterioration 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, where the sensitivity of sample NG, 1, which was left under the chamber for 7 days after coating, is 100.

In addition, the sample that had been left at the above room temperature for 7 days was immersed in 30°C water for 5 minutes, and a sapphire needle with a radius of 0.31 was pressed against the sample surface, moving parallel to the membrane surface at a speed of 2 times per second. The pressure load of the sapphire needle was continuously changed in the range of 0 to 200 g without moving the sample, 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 processing solution used in each treatment step (as shown in the figure below).

(Color developer) 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline/i M&Salt 4,75, anhydrous sodium sulfite 4.25g Hydroxylamine/L/2 sulfate 2. 0g anhydrous potassium carbonate 37.5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to make 1fI.

(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 g, and adjust the pH to -6.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 g, 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 1 g.

The following margins Comparative compound (1) (Compound described in JP-A No. 51-59625) Comparative compound (II) I (Compound described in JP-A-58-113929) Comparative compound (m) CH2<tlso□ C1 (zCONHCH2CH2
OCH25O2CH=CH2 (JP-A-53-41221
As is clear from the results in Table 1 above, samples N11.1 to 5 using the hardening agent according to the present invention were all compared to comparative samples NQ and 8 to 8. In comparison, there is only a slight decrease in relative sensitivity and no deterioration in fogging is observed.

Furthermore, even when forced deterioration is performed, comparative sample N[L6
Compared to samples Nos. 1 to 8, samples Nos. 1 to 5 of the present invention show a slight decrease in sensitivity and only a slight increase in fog.

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

Furthermore, from the results of scratch resistance, which indicates film strength, samples 1 to 5 of the present invention all showed higher film strength compared to comparative samples N11L6 to 7. It can be seen that the film hardens more efficiently than the compound.

Example 2 Layers having the compositions shown below were sequentially formed on both sides of an undercoated polyethylene terephthalate support from the support side to obtain X-ray photosensitive material samples Na 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 (1) 3mg/Bo mordant (I
[) O, 1,2g/rrf gelatin
02g/2nd layer: emulsion layer average grain size 0.57 μm, AgBr containing 2 mol% AgI
Emulsion coating amount consisting of 1: 4.5 g/sensitizing dye (A) 450 mg sensitizing dye (B) 20 mg 4-hydroxy-6
-Methyl- 1,3,3a,7-chitrazaindene 3. Ogt-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10.000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g p-nitrophenyl-triphenylphosphonium chloride 50 w + g 1.3-dihydroxybenzene- Ammonium 4-sulfonate 4g Sodium 2-mercaptobenzimidazole-5-sulfonate 15mgH 1,1-dimethylol-1-promo-1-nitromethane 101g gelatin
2g/3rd resistance layer 3 protective layer polymethyl methacrylate (average particle size 5μm) 7mg/Icoloidal silicone force (average particle size 0.013μm) 70+I1g/rrf
CH2COO(CH2)9CH1 C)IcOO(CH2)2cH(CH3)z
7mg/rrr0Ja (mixture of n-2 to 5) Gelatin Ig/rrf hardener (
(described in Table 2) Dye (1) Mordant (n) 1 (SC2CJs 1/25 (L = x: y -25: 75) Preservative DI-1 was appropriately added to each sample.

l-1 (Component molar ratio Component A: Component B: Component C-50:41
1i:4) After a 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 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 No. 9, 7 days after application, as 100.

The results are shown in Table-2.

(Processing process) Insert 1.2 seconds development + transition
35℃ 146 seconds fixing + transition 33℃
8.2 seconds water wash + crossing 25℃ 7.2
Second squeeze 40℃ 57 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
113.0g potassium bromide
4.0g triethylenetetraminehexaacetic acid 2.
Add 5g of water to make 1g.

(Fixer) Ammonium thiosulfate 130.9g Anhydrous sodium sulfite 7.3g Boric acid
7.0g acetic acid (90νt%) 55g Sodium acetate (trihydrate) 25.8g aluminum sulfate (18hydrate) L4.8g sulfuric acid (50
wt%) 6.7” Add 1g water to make 1g.

In addition, the samples were kept at 25°C and 50% RH, and 2 hours, 1 day, and 7 days after application, a portion of each sample was taken out and allowed to swell in water at 30°C for 5 minutes. The film thickness was measured, the swelling degree V expressed by the following formula was calculated, and the change over time in the curing effect (post-hardening property) 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, sensitivity decreased in X-ray photosensitive material samples Nos. 9 to 11 in which the hardener of the present invention was added to the protective layer. There is almost no change in photographic properties such as an increase in fog or increase in fog, and changes in the degree of swelling are small and stable after one day or more after coating and drying. sex has significantly improved. Also, if you compare it with sample 12, you can see that the dura mater was made more 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 hardening agent without impairing photographic performance and has no post-hardening effect. A photographic material can be provided.

Applicant Co., Ltd. Agent Iwa, Yoshio Hama

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]. General formula [III] ▲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], R_3 to R_7 each represent a hydrogen atom or a substituent. ) l and m represent 1 or 2, and l+m=3. ]