JP2838415B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material having improved film properties without deteriorating photographic characteristics.

[Prior Art] In general, a hydrophilic colloid film used for producing a silver halide photographic light-sensitive material is required not only to have no adverse effect on photographic light-sensitive properties but also to have a predetermined strength with respect to film properties. Is done. Therefore, when a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer, and a protective layer is coated on a support, a water-soluble polymer or a polymer latex in which various monomers have been polymerized in the hydrophilic colloid layer is conventionally used. Various attempts have been made to improve the film material such as dimensional stability, scratching strength, flexibility, pressure resistance, and drying property of the formed hydrophilic colloid film by incorporating the compound.

From such a viewpoint, Japanese Patent Application Laid-Open Nos.
-151527 to use acrylamide derivatives, U.S. Pat.No. 2,376,005 to use polymer latex of vinyl acetate, and U.S. Pat.No. 3,325,286 to use polymer latex of alkyl acrylate, Tokiko Sho 45-53
No. 31, using a polymer latex such as n-butyl acrylate, ethyl acrylate, styrene, butadiene, vinyl acetate, acrylonitrile,
In Japanese Patent Publication No. 46-22506, a polymer latex of an alkyl acrylate, acrylic acid, or sulfoalkyl acrylate may be used.
In Japanese Patent Application Laid-Open Publication No. Hei 9 (1999) -176, it is proposed to use a polymer latex of 2-acrylamido-2-methylpropanesulfonic acid or the like.

JP-A-62-87952 discloses that a high molecular weight component
It has also been proposed to use gelatin containing more than 10% by weight. When this gelatin is used, not only the film strength but also the dimensional stability can be improved.

However, at the time of manufacture of gelatin will be picking up the just lot variation because there is extraction, it has been difficult to stably supply. Further, the low molecular weight component could not be completely cut, and the outflow into the developing solution could not be suppressed. The spilled gelatin causes contamination of the developing roller.

[Problems to be Solved by the Invention] Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having high-strength film physical properties which has eliminated such disadvantages.

[Means for Solving the Problems] In order to achieve the above object, the silver halide photographic light-sensitive material of the present invention has at least one layer of a hydrophilic colloid layer containing gelatin as a main component on a support. In a photographic light-sensitive material, at least one of the hydrophilic colloid layers contains chitosan and / or a chitosan derivative, and the hydrophilic colloid layer is hardened with a carboxyl group-activating hardener. .

 Hereinafter, the present invention will be described in detail.

The chitosan of the present invention is obtained by deacetylation of chitin. Chitin is mainly produced from crab shells.
In general, the crushed and washed crab shell is treated with dilute hydrochloric acid to remove inorganic substances, and treated with dilute caustic soda to remove organic substances, thereby obtaining chitin as an insoluble residue.
Deacetylation of chitin is performed by treating chitin with about 50% hot caustic soda solution. Usually, the degree of deacetylation is up to 80 to 90%, and those which are soluble in dilute acetic acid (1%) even if they are not 100% deacetylated are generally called chitosan and can be used in the present invention. .

In the present invention, film strength and solubility can be controlled by using chitosan as a chitosan derivative.

Examples of the derivative include acetylated, alkylated, carboxyalkylated, sulfonated, and alkylsulfonated derivatives.

Chitosan has a high affinity for gelatin and mixes very nicely.

In the present invention, the preferred molecular weight Mw of the chitosan or chitosan derivative is from 10,000 to 500,000.

The amount of chitosan or chitosan derivative to be added can be arbitrarily selected, but is preferably 5 to 50% by weight, more preferably 10 to 30% by weight of the total binder in the added layer.

The chitosan and chitosan derivative of the present invention can be used in any of the hydrophilic colloid layers of a silver halide photographic material, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, an antihalation layer,
Although it can be used for a back coat layer, an undercoat layer and the like, it is particularly preferable to use it for a silver halide emulsion layer, a protective layer, a back coat layer and the like.

In the present invention, it is advantageous to use gelatin as the hydrophilic colloid used together with the chitosan and chitosan derivative. Gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives A hydrophilic colloid such as a single or copolymerized hydrophilic polymer material such as a copolymer can also be used.

The hardener used in the present invention is a so-called carboxyl group-activated hardener that acts by activating the carboxyl group of a hydrophilic colloid such as gelatin.

Preferred examples of the carboxyl group-active hardener used in the present invention include the following general formulas (I) to (VI
The compounds represented by I) can be mentioned.

In the formula, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a 2-ethylhexyl group, etc.), an aryl group having 6 to 15 carbon atoms (eg, a phenyl group, a naphthyl group, etc.), Alternatively, it represents an aralkyl group having 7 to 15 carbon atoms (for example, a benzyl group or a phenethyl group), which may be the same or different. Here, the alkyl group, the aryl group and the aralkyl group include those substituted. R ¹ and R ² may combine with each other to form a heterocyclic ring together with the nitrogen atom. Examples of the ring formed include, for example, a pyrrolidine ring, a piperazine ring, a morpholine ring and the like.

 R^ThreeRepresents a hydrogen atom, a halogen atom, a carbamoyl group,
E group, ureido group, sulfooxy group, sulfoamino group,
C1-C10 alkoxy group, C1-C10 alkyl
Group, a substituent of a dialkyl-substituted amino group having 2 to 20 carbon atoms
It represents. R^ThreeIs an alkoxy group, an alkyl group, a dialkyl
When it is an amino group or an N-alkylcarbamoyl group,
These groups include those further substituted,
Examples of the group include, for example, a halogen atom, carbamoyl
Group, sulfo group, sulfooxy group, sulfoamino group, urea
Group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms.
Lucoxy group, dialkyl-substituted amino group having 2 to 20 carbon atoms, etc.
Is raised. X Represents an anion, and N-carba
It becomes a counter ion of moylpyridinium salt. R^ThreeTo the substituent of
When it contains a sulfo group, it forms an inner salt and forms X Is
You don't have to be. Preferred examples of anions include halo
Genide ion, sulfate ion, sulfonate ion, Cl
O_Four , BF_Four, PF₆And so on.

 R¹, R^Two, R^ThreeAnd X Are in the general formula (I)
R¹, R^Two, R^ThreeAnd X Is exactly the same as the definition.

R ¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group, a dodecyl group, etc.), an aralkyl group having 6 to 20 carbon atoms (For example, a benzyl group, a phenethyl group, a 3-pyridylmethyl group) or an aryl group having 5 to 20 carbon atoms (for example, a phenyl group, a naphthyl group, a pyridyl group, and the like), which may be the same or different. . Also R ¹ ,
R ² , R ³ and R ⁴ may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, N, And N-disubstituted carbamoyl groups.

Also, any two members out of R ¹ , R ² , R ³ and R ⁴ may combine to form a ring. For example, R ¹ and R ² or R ³
Examples of R ⁴ bonding to form a ring with a nitrogen atom include
Pyrrolidine ring, piperazine ring, perhydroazepine ring,
A morpholine ring may be formed. Also,
Examples of the case where R ¹ and R ³ or R ² and R ⁴ combine to form a ring together with two nitrogen atoms and a nitrogen atom sandwiched between them and a carbon atom sandwiched therebetween include an imidazoline ring, A case where a tetrahydropyrimidine ring, a tetrahydrodiazepine ring or the like is formed may be mentioned.

 X is a compound represented by the general formula (III):
Represents a group that can be eliminated when reacted with, preferred examples and
A halogen atom, a sulfonyloxy group, 1-pyridinyl
Umyl group and the like. Y Represents an anion
And halide ions, sulfonate ions, sulfate ions
ON, ClO_Four , BF_Four , PF₆ Are preferred. Y But
When expressing the rufonate ion, X, R¹, R^Two, R^ThreeMa
Or R^FourTo form an inner salt.

Formula (IV) R ¹ —N ＝ C—N—R ^{2 In the} formula, R ¹ is an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a 2-ethylhexyl group, etc.), and a carbon number of 5
A cycloalkyl group having 8 to 8 carbon atoms (eg, cyclohexyl group), an alkoxyalkyl group having 3 to 10 carbon atoms (eg, methoxyethyl group), or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenylyl group). .

Here, the alkyl group, cycloalkyl group, alkoxyalkyl group and aralkyl group include those substituted.

R ² is a group defined as R ¹ and Represents a group represented by

 Where R^ThreeIs an alkylene group having 2 to 4 carbon atoms (for example,
Styrene, propylene, trimethylene, etc.)
I forgot. R^FourAnd R^FiveMay be the same or different
Alkyl groups having 1 to 6 carbon atoms (eg, methyl group, ethyl
And the like, and includes those substituted. Ma
T, R^FourAnd R^FiveAre bonded together to form a heterocyclic ring with a nitrogen atom (eg,
For example, pyrrolidine ring, piperazine ring, morpholine ring, etc.)
May be formed. R⁶Is an alkyl group having 1 to 6 carbon atoms (eg,
For example, methyl, ethyl, butyl, etc.)
However, this alkyl group may be substituted with a substituent.
Examples of substituents include substituted or unsubstituted carbamoyl
And a sulfo group. X Represents an anion
And halide ions, sulfonate ions, sulfate ions
ON, ClO_Four , BF_Four , PF₆ Are preferred.

 Also, R⁶Is substituted with a sulfo group, the inner salt
To form X May not be present.

In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, or a butyl group), an aryl group having 6 to 15 carbon atoms (such as a phenyl group, a naphthyl group, or the like); 15 aralkyl groups (for example, benzyl group, phenethyl group, etc.). These groups may be substituted with a substituent, and examples of the substituent include a carbamoyl group, a sulfamoyl group, and a sulfo group. R ² and R ³ are a hydrogen atom, a halogen atom, an acylamide group, a nitro group,
It represents a substituent such as a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group and may be the same or different. It is also preferred that R ² and R ³ combine to form a condensed ring together with the pyridinium ring skeleton.

X represents a group that can be degreased when the compound represented by the general formula (V) reacts with a nucleophile, and preferred examples thereof include a halogen atom, a sulfonyloxy group and (R ⁴ represents an alkyl group or an aryl group) and the like. When X represents a sulfonyloxy group, it is also preferable that X and R ¹ are bonded.

 Y Represents an anion, a halide ion,
Rufonate ion, sulfate ion, ClO_Four , BF_Four , PF₆
Are preferred. Also R¹Is replaced by a sulfo group
Forms an inner salt and Y May not be present.

 Where R¹And R^TwoIs defined as R in the general formula (I)¹as well as
R^TwoIs exactly the same as the definition. R^ThreeIs alk having 1 to 10 carbon atoms
Groups (eg, methyl, ethyl, butyl, etc.), charcoal
Aryl groups having a prime number of 6 to 15 (for example, phenyl group, naphthyl
Group) or an aralkyl group having 7 to 15 carbon atoms (for example,
Benzyl group, phenethyl group, etc.). here,
Alkyl, aryl and aralkyl groups are substituted
Including those that are X Is an anion, such as halogen
Chloride ion, sulfonate ion, sulfate ion, ClO_Four
, BF_Four , PF₆ Are preferred.

Wherein R ¹ and R ² may be the same or different,
Represents an alkyl group, an aryl group or an aralkyl group,
These groups may be substituted and may be further bonded to each other to form a nitrogen-containing heterocyclic ring.

Z represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heteroaromatic ring.

 X Represents an anion, and R¹, R^Two, Z, etc.
An inner salt may be formed.

Y is an R ³ -group, an R ⁴ O- group, Or Represents

Here, R ³ represents an optionally substituted alkyl group or an aryl group, R ⁴ represents an optionally substituted alkyl group or an aralkyl group, and R ⁵ and R ⁶ represent R ¹ and R ² Represents the same group as defined above.

 A represents an alkylene group or an arylene group;
It may have a group. L₁And L_TwoIsOr a single bond, R⁷Is R¹, R^TwoSame group as defined in
Represents Where L₁And L_TwoBut at the same timeWhen it represents, it may form a ring together. Soshi
And n represents 0 or 1. In addition, two or more
R on¹, R^Two, X And when Z is present, the group is
Each may be the same or different.

Examples of the carboxyl group-active hardener used in the present invention include compounds represented by the above-mentioned general formulas (I) to (VII) and JP-A-50-38540 and JP-A-52-93470.
Nos. 56-43353 and 58-113929; U.S. Pat.
Compounds described in No. 1,313 are exemplified.

Hereinafter, specific examples of the carboxyl group-active hardener will be classified, but the present invention is not limited thereto.

a. Compound according to general formula (I) b. Compound according to general formula (II) c. Compound according to general formula (II) d. Compound according to general formula (IV) c. Compound according to general formula (V) f. Compound according to general formula (VI) g. Compound according to general formula (VII) Of the carboxyl group-active molecular hardeners, compounds represented by the general formula (I) are described in JP-A-49-51945 and JP-A-49-51945.
It can be synthesized by the method disclosed in 1-59625.
Similarly, the compound represented by the general formula (II) is a Belgian patent
No. 825726, the compound represented by the general formula (III) is described in JP-A-60-225148, and the compound represented by the general formula (IV) is disclosed in JP-A-51-126125 and JP-A-52-48311. Compounds represented by (V) are disclosed in JP-A-57-44140 and JP-A-57-44140.
-46538, JP-B-58-50669, and the compound represented by the general formula (VI) are described in JP-A-52-54427,
The compound represented by II) can be synthesized according to the synthesis methods disclosed in JP-A-61-9641.

Further, the following compounds can also be used as the carboxyl group-active hardener of the present invention.

h. Compound described in JP-A-50-38540 i. Compounds described in JP-A-52-93470 j. Compounds described in JP-A-56-43353 k. Compounds described in JP-A-58-113929 l. Compounds described in U.S. Patent No. 3,321,303 In the present invention, the amount of the carboxyl group-active hardener used varies depending on the type of the photosensitive material to be applied and the type of the hydrophilic binder, but is preferably 0.01 to 100% by weight, more preferably the dry weight of the binder. 0.1-10% by weight
Range.

Hydrophilicity such as silver halide, chemical sensitizer, silver halide solvent, spectral sensitizing dye, antifoggant, gelatin and the like used in the silver halide emulsion layer or other layers of the light-sensitive material in carrying out the present invention. The protective colloid, ultraviolet absorber, polymer latex, whitening agent, color coupler, anti-fading agent, dye, matting agent, surfactant and the like are not particularly limited. For example, Research Disclosure, Vol. December 1978), 22
To 31 can be used arbitrarily.

Further, the description in the above-mentioned Research Disclosure Magazine can be referred to for the support of the photosensitive material, the development processing method, the constituent layers of the photosensitive material, and the like.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to the following examples, but the present invention is not limited thereto.

Example 1 4-silver iodobromide gelatin emulsion containing 3 mol% of silver iodide
After addition of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,4-dichloro-6-hydroxy-s-triazine, the silver amount was 50 mg / dm on a subbed polyethylene terephthalate support. ² and then, as a protective layer, polymethyl methacrylate particles (particle size 0.5 μm).
m) 50 mg / m ² , C ₈ F ₁₇ SO ₃ Na ₅ mg / m ² , 1.0 g / m ² of gelatin was laminated and used as a reference sample EO (comparison).

Samples E1 to E4 and Comparative sample A were prepared in the same manner as the reference sample except that the chitosan and the hardener shown in Table 1 were added to the reference sample EO in an amount of 10 wt% based on the gelatin in the emulsion and the protective layer, respectively. Latex A) and a comparative sample B containing a repeating unit of And a comparative sample C (gelatin C having a high molecular weight component of 12% by weight).

Each of the samples was exposed to wedges and subjected to the following development processing, dried, and evaluated for the effects on the scratch strength, devitrification, photographic performance and roller contamination after the development processing. The results are shown in Table 1. Shown in

[Processing process] Process Temperature (° C) Time (second) Current image 30 45 Fixation 25 35 Rinse with water 15 35 Dry 60 20 [Developer composition] Phenidone 0.4 g Methol 5 g Hydroquinone 1 g Anhydrous sodium sulfite 60 g Carbonic acid Sodium H ₂ O 54 g 5-Nitroimidazole 100 mg Potassium bromide 2.5 g Water was added to 1 to adjust the pH to 10.20.

However, the evaluation methods of the scratching strength, devitrification, sensitivity and roller contamination shown in Table 1 are as follows.

[Scratch strength] The minimum weight at which the film surface is scratched with a metal needle (φ; 0.5 mil) that has been developed, fixed and washed in the above-mentioned processing steps, and then immersed in washing water, and then weighed (scratch strength) Was examined.

[Devitrification] A: No transparency reduction after development processing B: Very slightly milky white C: Slightly milky white A, B, C were visually judged. Incidentally, the devitrification indicates the gelatin compatibility of the polymer.

[Sensitivity] Measured using a Konica Corp. sensitometer KS-1. Cover +0.7
The sensitivity was defined as the reciprocal of the exposure amount given at the density of, and the specific sensitivity was set assuming that the sensitivity of the reference sample E0 was 100.

[Roller contamination degree] The sample was cut to 30.5 cm x 17.1 cm. After uniform exposure so that the optical density after the development processing becomes 1.0, an automatic development processing machine (having a silicone conveyance roller, a development bath,
(3 baths of a fixing bath and a washing bath). After the washing squeeze roller was sufficiently dried, the appearance of streaky density unevenness generated at the tip of the 51st sample was examined.

 The evaluation of the degree of roller contamination was based on the following four criteria.

A: No density unevenness is observed.

B: Density unevenness occurs slightly.

C: Density unevenness considerably occurs.

D: Density unevenness significantly occurs.

From the results shown in Table 1, it can be seen that the sample of the present invention exhibited better results in comparison with the comparative sample in all of the points of the scratch strength, the devitrification, the photographic characteristics, and the degree of roller contamination.

Example 2 In the following examples, the amounts of silver halide photographic materials are based on 1 m ² unless otherwise specified.
Further, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic light-sensitive material sample No. E0, E5, E6 and a comparative sample D in which each layer having the composition shown below was sequentially formed on a triacetyl cellulose film support from the support side
~ F was created.

First layer: Antihalation layer (HC) Gelatin layer containing black colloidal silver.

Gelatin 2.2 g / m ² Second layer; Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.2 g / m ² Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL) Average particle size () 0.30 μm, A containing 6 mol% of Ag I
Monodisperse emulsion composed of gBr I (emulsion I) Silver coating amount 1.8 g / m ² Sensitizing dye I 6 × 10 ^-5 mol per mol of silver Sensitizing dye II 1.0 × 10 ^-5 mol per mol of silver Molar cyan coupler (C-1) 0.06 mole per mole of silver Colored cyan coupler (CC-1) 0.003 mole per mole of silver DIR compound (D-1) 0.0015 mole per mole of silver DIR compound (D-1) D-2) 0.002 mol per mol of silver Gelatin 1.4 g / m ² Fourth layer; high-sensitivity red-sensitive silver halide emulsion layer (RH) Average particle size () 0.5 μm, containing Ag I 7.0 mol%
Monodisperse emulsion composed of AgBr I (emulsion II) Silver coating amount 1.3 g / m ² Sensitizing dye I 3 × 10 ^-5 mol per mol of silver Sensitizing dye II 1.0 × 10 ^-5 mol per mol of silver Molar cyan coupler (C-1) 0.02 mol per mol of silver Colored cyan coupler (CC-1) 0.0015 mol per mol of silver DIR compound (D-2) 0.001 mol per mol of silver Gelatin 1.0 g / m ² Fifth layer; Intermediate layer (IL) Same gelatin layer as the second layer.

Gelatin 1.0 g / m ² 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion I Silver coating weight 1.5 g / m ² Sensitizing dye III 2.5 × 10 ^-5 mol sensitization per mol of silver Dye IV 1.2 × 10 ^-5 mol per mol of silver Magenta coupler (M-1) 0.05 mol per mol of silver Colored magenta coupler (CM-1) 0.009 mol per mol of silver DIR compound (D- 1) 0.0010 mol per mol of silver DIR compound (D-3) 0.0030 mol per mol of silver Gelatin 2.0 g / m ² 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH) Emulsion I Silver Coating amount 1.4 g / m ² Sensitizing dye III 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV 1.0 × 10 ^-5 mol per mol of silver Magenta coupler (M-1) 1 mol of silver 0.020 mol to color magenta coupler (CM-1) 0.002 mol to 1 mol of silver DIR compound (D-3) 0.0010 mol to 1 mol of silver Gelatin 1.8 g / m ² Eighth layer: Yellow filter layer (YC) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.5 g / m ² 9th layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL) A containing 0.48 μm average particle size (A) and 6 mol% Ag I
Monodisperse emulsion composed of gBr I (Emulsion III) Silver coating amount 0.9 g / m ² Sensitizing dye V 1.3 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1) 0.29 mol per mol of silver Gelatin 1.9 g / m ² 10th layer; high-sensitivity blue-sensitive silver halide emulsion layer (BH) Average particle size () 0.8 μm, A containing 15 mol% of Ag I
Monodisperse emulsion composed of gBr I (Emulsion IV) Silver coating amount 0.5 g / m ² Sensitizing dye V 1.0 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1) 0.08 mol per mol of silver DIR compound (D-2) 0.0015 mol per mol of silver Gelatin 1.6 g / m ² 11th layer; 1st protective layer (Pro-1) Silver iodobromide [Ag I 1 mol%, average particle size () 0.07
μm] A gelatin layer containing a silver coating amount of 0.5 g / m ² UV absorbers (UV-1) and (UV-2).

Gelatin 1.2g / m ² In addition, in addition to the above, each layer contains 10 wt% of the chitosan P-1 of the present invention or a comparative binder with respect to the binder as shown in Table 2, and further contains a hardener and a surfactant (Table 2). 1), (2), (3) and (4) were added respectively.

The compounds contained in each layer of the sample are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; anhydro-9-ethyl-3,3 '-Di- (3
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide sensitizing dye III; anhydro-5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl Propyl) oxacarbocyanine hydroxide Sensitizing dye IV; anhydro-9-ethyl-3,3'-di- (3
-Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide sensitizing dye V; anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5' -Methoxythiocyanine hydroxide Surfactant After wedge exposure of these samples with white light, the following processing was performed, and the same evaluation as in Example 1 was performed.

 Table 2 also shows the results.

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

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

(Bleaching solution) Iron ammonium salt of ethylenediaminetetraacetate 100 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make 1 and adjust the pH to 6.0 using aqueous ammonia.
Adjust to

(Fixing solution) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 and adjust the pH to 6.0 using acetic acid.

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

From the results in Table 2, it is clear that the sample of the present invention shows excellent effects in all of the scratch strength, devitrification, photographic properties and roller contamination.

[Effects of the Invention] As described above in detail, according to the present invention, it is possible to provide a silver halide photographic material having improved film properties without deteriorating photographic characteristics.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/43 G03C 1/30

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer containing gelatin as a main component on a support, wherein at least one of the hydrophilic colloid layers contains chitosan and / or a chitosan derivative. A silver halide photographic light-sensitive material, wherein the hydrophilic colloid layer is hardened with a carboxyl group-active hardener.