JPH06175264A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material hardened to a sufficient hardness without adversely affecting photographic characteristics and freed of any post-hardening by rapid hardening and efficiently hardened with high selectivity to reactive residues in a gelatin by selecting a specified compound to harden a hydrophilic colloidal layer. CONSTITUTION:The silver halide photographic sensitive material has at least one hydrophilic colloidal layer on a support and at least one of the hydrophilic colloidal layers is hardened by using at least one of the compounds represented by formula in which L1 is a releasable group, such as halogen, sulfonyloxy, ammonium on an N-containing 5- or 6-membered aromatic hetero ring, or a residue obtained by removing H from a compound having a releasable H atom on an 0, S, or N atom: and R1 is alkyl or the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having a photographic constituent layer hardened with a specific compound.

[0002]

BACKGROUND OF THE INVENTION Generally, a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) includes, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, an undercoat layer, an antihalation layer and an ultraviolet ray. Various photographic constituent layers such as an absorption layer, an antistatic layer and a backing layer are provided on a support such as glass, paper and synthetic resin film.

Since these photographic constituent layers are formed by coating an aqueous coating solution composed of a hydrophilic polymer and / or a water-dispersible polymer, the mechanical strength is weak as it is. For example, gelatin films have low melting points and are overly water-swellable.
Further, the latex film has a drawback that the adhesion to the support is extremely poor and the latex film is easily peeled off.

Therefore, it is known that a compound called "hardener" is added to a photographic constituent layer to improve its mechanical strength. Aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732,30
3, 3,288,775, British Patent 974,723, 1,167,207
Compounds having a reactive halogen as described in No.
Ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3,5-triazine, divinyl sulfone, 5-acetyl-1,3-diacryloylhexa Hydro-1,3,5-triazine, U.S. Patents 3,232,763, 3,635,718, British Patent 99
Compounds having a reactive olefin as described in 4,809,
U.S. Pat.Nos. 3,539,644, 3,642,486, Japanese Patent Publication No. 49-13563
No. 53-47271, 56-48860, JP-A-53-57257,
61-128240, 62-4275, 63-53541, 63-26457
No. 2, etc., vinylsulfonyl compounds, N-hydroxymethylphthalimide, U.S. Patents 2,732,316, 2,586,1
N-methylol compounds described in No. 68, U.S. Patent 3,103,43
Isocyanates described in U.S. Pat. No. 7,983,611
No. 3,107,280, etc., aziridine compounds, U.S. Pat.Nos. 2,725,294, 2,725,295, etc. acid derivatives, U.S. Pat.No. 3,100,704, etc., carbodiimide compounds, U.S. Pat. Compounds, U.S. Pat.Nos. 3,321,313, isoxazole compounds described in 3,543,292 and the like, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane, organic hardeners such as dioxane derivatives such as dichlorodioxane, and chromium alum, It is an inorganic hardener such as zirconium sulfate and chromium trichloride.

However, these known hardeners, when used in a light-sensitive material, have insufficient curing action,
There is a long-term change in the hardening action called "post-hardening" that occurs because the hardening reaction to gelatin is slow, and it adversely affects the performance of the light-sensitive material (especially increased fog, decreased sensitivity or maximum density, soft gradation). Etc.), loss of curing effect due to coexisting other photographic additives, reduction of the efficacy of other photographic additives (eg couplers in internal color emulsions), or contamination. , And each had some drawbacks.

The hardening action on gelatin is relatively fast,
As a hardener with less post-hardening, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-5
9625, 62-262854, 62-264044, 63-184741
N-carbamoylpyridinium salts described in No. 55
-38655, acyl imidazoles, JP-B-53-220
Compounds containing two or more N-acyloxyimino groups in the molecule described in JP-A No. 89, compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113929
Compounds having a phosphorus-halogen bond described in JP-A-60-
The chloroformamidinium compounds described in 225148, 61-240236, and 63-41580 are known.

These hardeners are characterized in that they have a fast hardening action and therefore little post-hardening. However, many of these hardeners affect the photographic properties, and the curing reaction of gelatin is fast and the side reaction that is decomposed by water is also rapid, so that in a general method for producing a photographic light-sensitive material using an aqueous gelatin solution. The effective use efficiency of the hardener is extremely low, and it has a drawback that a large amount of hardener must be used in order to obtain a gelatin film having a sufficient hardness.

[0008]

SUMMARY OF THE INVENTION Therefore, firstly, the object of the present invention is to provide a photographic light-sensitive material hardened by a novel hardener which achieves sufficient hardness without adversely affecting photographic characteristics. Especially.

Secondly, it is to provide a photographic light-sensitive material which is hardened by a hardening agent having a quick hardening action and without post-hardening.

A third object is to provide a photographic light-sensitive material which is hardened by a hardener which reacts with high reactivity to reactive residues in gelatin and hardens gelatin efficiently.

[0011]

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, wherein at least one of the hydrophilic colloid layers is represented by the following general formula [I]. At least one of the compounds represented by
Achieved by hardening with seeds.

[0012]

[Chemical 8]

In the formula, L ₁ represents a releasable group, and R ₁ represents a substituent. m represents 0 or 1. Hereinafter, the present invention will be described in more detail.

In the above general formula [I], the substituent represented by R ₁ is an alkyl group (methyl, ethyl, etc.), an aryl group (phenyl, naphthyl, etc.), an alkoxy group (methoxy, ethoxy, etc.), aryl. Oxy group (phenoxy, naphthoxy, etc.), acyl group (acetyl, propionyl, etc.), carbamoyl group, sulfamoyl group, N, N-disubstituted amino group, sulfo group, sulfoamino group (including salt),
Examples thereof include a sulfooxy group. Of these, an alkoxy group and a sulfo group are preferable.

Examples of the releasable group represented by L ₁ include a halogen atom, a sulfonyloxy group, an ammonio group of a 5- or 6-membered nitrogen-containing aromatic heterocycle and an oxygen atom,
A group formed by removing the hydrogen atom from a compound (hereinafter, referred to as an acidic compound) having a removable hydrogen atom (hereinafter, referred to as active hydrogen) on a sulfur atom or a nitrogen atom is included.

In order to prevent the pH of the photographic light-sensitive material from being lowered by the product formed by the hardening reaction, a group formed by removing active hydrogen from an acidic compound having a pKa of 1 or more or a nitrogen-containing aroma having a pKa of a conjugate acid of 1 or more. Ammonio groups of group heterocycles are preferred.

As the nitrogen-containing aromatic heterocycle, pyridine,
Heterocycles such as pyridazine, pyrazine, quinoline, N-substituted imidazole, N-substituted benzimidazole, oxazole, benzoxazole, thiazole, and benzothiazole can be mentioned. Among these, a pyridine ring, an N-substituted imidazole ring, and an N-substituted benzimidazole ring are preferable.

Examples of the acidic compound having active hydrogen on the oxygen atom include phenol, hydroxypyridine, N-substituted hydroxypyridinium, hydroxyquinoline, N-substituted hydroxyquinolinium, N-hydroxyimide (eg N-hydroxysuccinimide, N -Hydroxyphthalimide, etc.), N-hydroxybenzotriazole, 2-hydroxybenzoxazole, 2-hydroxybenzothiazole,
3-hydroxybenzoxazole and the like can be mentioned.

As the acidic compound having active hydrogen on the sulfur atom, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 5-mercapto-1,3,4-oxadiazole, 5-mercapto-1,3, 4-thiadiazole, 5-mercapto-1,2,4-oxadiazole, 5-mercapto-1,2,4-
Examples thereof include thiadiazole.

The acidic compound having active hydrogen on the nitrogen atom is preferably a compound represented by the following general formula [VIII].

[0021]

[Chemical 9]

In the formula, X ₁ , Y ₁ and Z ₁ are the same as those in formula [II].

Typical examples of the heterocyclic compound represented by the general formula [VIII] are shown below, but the invention is not limited thereto.

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

In the above structure, R ₂ represents the same as in formula [II], and R ₇ and R ₈ each represent an alkyl group or an aryl group.

Each of the nitrogen-containing aromatic heterocycle and the acidic compound mentioned here may be further substituted. Substituents include alkyl groups (methyl, ethyl, propyl, butyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (pyridyl, N-substituted pyridinium-yl, piperidyl, etc.), alkoxy groups (methoxy, ethoxy, etc.). , Propoxy, etc.), aryloxy groups (phenoxy, naphthoxy, etc.), alkylthio groups (methylthio, ethylthio, propylthio, etc.), arylthio groups (phenylthio, naphthylthio, etc.), sulfonio groups (dimethylsulfonio, methylethylsulfonio, diethylsulfonio). Etc.), sulfonyl groups (methylsulfonyl, ethylsulfonyl, phenylsulfonyl, etc.), acyl groups (acetyl, propionyl, benzoyl, etc.), sulfo groups, sulfooxy groups, sulfoamino groups and the like.

These substituents may further have a substituent, and the substituent is preferably an alkoxy group, a sulfo group and an alkyl group or an aryl group having an alkoxy group or a sulfo group as a substituent. Pyridyl group and N-substituted pyridinium-yl group are also preferable as the substituent.

Among the compounds represented by the general formula [I], the following three compound groups are preferred.

One is a group of compounds represented by the following general formula [II].

[0038]

[Chemical 19]

In the formula, R ₁ represents a substituent, and m is 0 or 1.
Represents X ₁ represents -CO-, -CS- or -SO _2- , and Y ₁
Single bond, -O is -, - S -, - N (R 2) -, - CO -, - C (R 3)
= N- or -N = C (R ₄₎ - represents a. R ₂ represents an alkyl group or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. These alkyl group, aryl group and heterocyclic group may be further substituted.

Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. Examples of preferred heterocyclic groups include those mentioned above as examples of the heterocyclic compound of the general formula [VIII] from which active hydrogen has been removed.

Another is a group of compounds represented by the following general formula [III]

[0042]

[Chemical 20]

In the formula, R ₁ represents a substituent, and m is 0 or 1.
Represents Z ₂ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle. Examples of the 5- or 6-membered nitrogen-containing aromatic heterocycle include pyridine, quinoline, N-substituted imidazole, N-substituted benzimidazole, oxazole, benzoxazole, thiazole, benzothiazole, and the like. Among these, a pyridine ring, an N-substituted imidazole ring, and an N-substituted benzimidazole ring are preferable. R ₅ represents a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, etc.), an alkyl group (methyl, ethyl,
Propyl, etc.), aryl groups (phenyl, naphthyl, etc.),
Heterocyclic groups (pyridyl, piperidyl, etc.), alkoxy groups (methoxy, ethoxy, etc.), aryloxy groups (phenoxy, naphthoxy, etc.), hydroxyalkyl groups (hydroxymethyl, hydroxyethyl, etc.), acyl groups (acetyl, propionyl, benzoyl, etc.) ), N, N-disubstituted amino groups (including dimethylamino, diethylamino, and other cyclic amino groups such as pyrrolidino, piperidino, and morpholino), carbamoyl groups, sulfamoyl groups, sulfo groups,
Examples thereof include a sulfonamide group and a sulfooxy group.
_{Also, R 9 -CO 2 -R 10 -} , R 9 -OCO-R 10 -, R 9 -CON (R 11) -
_{R 10 -, R 9 -N (} R 11) CO-R 10 -, R 9 -SO 2 -R 10 -, R 9 -SO
_The groups represented by ₂ N (R ₁₁ ) —R ₁₀ — and R ₉ —N (R ₁₁ ) SO ₂ —R ₁₀ — are also examples of the substituent. Here, R ₉ represents an alkyl group or an aryl group, and R ₁₀ represents a single bond, an alkylene group or an aralkylene group. R ₁₁ represents a hydrogen atom, an alkyl group or an aralkyl group.

These substituents may be further substituted. Examples of the substituent include an alkyl group, an alkoxy group,
Examples thereof include an aryloxy group, an acyl group, an N, N-disubstituted amino group, a carbamoyl group, a sulfamoyl group, a sulfo group, a sulfoamino group (including a salt), and a sulfooxy group.
_{Also, R 12 -CO 2 -, R} 12 -OCO-, R 12 -CON (R 13) -, R 12 -
N (R ₁₃ ) CO-, R-SO _2- , R ₁₂ -SO ₂ N (R ₁₃ )-, R ₁₂ -N
The group represented by (R ₁₃ ) SO ₂ — is also exemplified as the substituent. Here, R ₁₂ represents an alkyl group, and R ₁₃ represents a hydrogen atom or an alkyl group. This alkyl group may be substituted.

The substituent is preferably an alkoxy group,
N, N-disubstituted amino group, sulfo group, sulfoamino group (including salt), sulfooxy group and R ₁₂ —CO ₂ —, R ₁₂ —OCO—,
_{R 12 -CON (R 13) -} , R 12 -N (R 13) CO-, R-SO 2 -, R 12 -S
It is a group represented by O ₂ N (R ₁₃ ) − and R ₁₂ —N (R ₁₃ ) SO ₂ —.

An alkyl group having as a substituent a group selected from an alkoxy group, an N, N-disubstituted amino group, a sulfooxy group, a sulfoamino group (including a salt) and a sulfooxy group,
Alkoxy group and _{R 12 -CO 2 -, R 12} -OCO-, R 12 -CON
_{-, R 12 -N (R 13} ) CO-, R-SO 2 -, R 12 -SO 2 N (R 13) -, R
_{12 -N (R 13) SO 2} - group represented by is preferable as the substituent. Here, R ₁₂ represents an alkyl group, and R ₁₃ represents a hydrogen atom or an alkyl group. The substitution position of the substituent is preferably a position other than the α-position of the quaternary nitrogen.

N represents 0, 1 or 2, and 1 is preferable.
X ⁻ represents an anion portion in the molecule or a free anion. As the anion portion in the molecule, a sulfo group, a sulfoamino group or a sulfooxy group is preferable. Examples of the free anion include halide ion (Cl ⁻ , Br ^−, etc.), sulfonate ion, sulfate ion, ClO ₄ , BF ₄ ⁻ , PF ₆ ^{− and the} like. Preferred are Cl ⁻ , BF ₄ ⁻ , PF ₆ ⁻ and sulfonate ions.

The other one is a group of compounds represented by the following general formula [IV].

[0049]

[Chemical 21]

In the formula, R ₁ represents a substituent, and m is 0 or 1.
Represents L ₂ represents a group selected from the groups represented by the following general formula [V], general formula [VI] or general formula [VII].

[0051]

[Chemical formula 22]

In the formula, Z ₃ represents an atomic group necessary for forming a nitrogen-containing heterocycle. An example of such a heterocycle is N-
Hydroxyimide (N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyphthalimide, etc.),
Examples thereof include N-hydroxybenzotriazole.

[0053]

[Chemical formula 23]

In the formula, Y ₂ represents an oxygen atom or a sulfur atom, and Z ₄ represents an atomic group necessary for forming a nitrogen-containing heterocycle.

Examples of such a heterocycle include 2-hydroxybenzoxazole, 2-hydroxybenzothiazole, 5-hydroxy-1,3,4-oxadiazole and 5-hydroxy-1,3,4-thiadiazole. , 3-hydroxybenzisoxazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 5-mercapto-1,3,4-oxadiazole, 5-mercapto-1,3,4-thiadiazole, 5
-Mercapto-1,2,4-oxadiazole, 5-mercapto-
1,2,4-thiadiazole and the like can be mentioned.

[0056]

[Chemical formula 24]

In the formula, R ₆ represents an alkyl group or an aralkyl group, and Z ₅ represents an atomic group necessary for forming a nitrogen-containing heterocycle.

Examples of such a heterocycle include 2-hydroxy-N-substituted-pyridinium, 2-hydroxy-N-substituted quinolinium and the like. Preferred is 2-hydroxy-N-substituted pyridinium.

R ₆ is preferably a lower alkyl group such as methyl and ethyl, and a lower alkyl group substituted with a sulfo group such as sulfopropyl and sulfobutyl.

Y ⁻ is an anion necessary for canceling the charges in the molecule, and is, for example, a halogen ion (Cl ⁻ , I
^- etc.), sulfonate _{^{ion, BF 4 -, PF 6 -}} , ClO 4 - , and the like. When R ₆ is substituted with a sulfo group Y ^- it is not necessary.

The groups represented by the general formula [V], the general formula [VI] and the general formula [VII] may be further substituted.

As the substituent, an alkyl group (methyl,
Ethyl, propyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (pyridyl, piperidyl, N-substituted pyridinium-yl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, etc.), aryloxy groups (phenoxy,
Naphthoxy etc.), acyl groups (acetyl, propionyl,
Benzoyl, etc.), sulfo group, sulfoamino group (including salt), sulfooxy group and the like.

These substituents may further have a substituent. Preferred are an alkoxy group, a pyridyl group, an N-substituted pyridinium-yl group and a sulfo group.

Typical examples of the compounds represented by the general formulas [I] to [IV] are shown below, but the invention is not limited thereto.

[0065]

[Chemical 25]

[0066]

[Chemical formula 26]

[0067]

[Chemical 27]

[0068]

[Chemical 28]

[0069]

[Chemical 29]

[0070]

[Chemical 30]

[0071]

[Chemical 31]

[0072]

[Chemical 32]

[0073]

[Chemical 33]

The compound of the present invention can be easily synthesized by a known method. For example, it can be easily synthesized by reacting 3-chloro-1,2-benzisothiazole-1,1-dioxide with an acidic compound and a deoxidizing agent, or with a nitrogen-containing aromatic heterocyclic compound.

3-chloro-1,2-benzisothiazole-1,1-
Dioxide is saccharin (1,2-benzisothiazole
-3 [2H] -one-1,1-dioxide) can be easily obtained by chlorination with a chlorinating agent such as thionyl chloride.

As a method for synthesizing the compound of the present invention, the methods described in the following documents can be referred to (Synthesis 1981 edition, page 993, Chemistry Letters, 1979 edition, page 1265, Chemistry Letters, 1980 edition, page 1161). .

Next, the synthesis method will be specifically described by taking Exemplified Compound 20 as an example.

<Synthesis of Exemplified Compound 20> Nicotinamide 1
2.2 g (0.10 mol) of acetonitrile in 30 cc under ice-cooling 3-
Chloro-1,2-benzisothiazole-1,1-dioxide 20.2
A 30 cc solution of g (0.10 mol) in acetonitrile was added dropwise and mixed. The reaction mixture was stirred at room temperature for 5 hours, and the precipitated crystals were filtered, washed with ether and dried to give 31.1 g (yield 96%) of white crystals of Exemplified Compound 20. This is NM
The structure was confirmed by R and IR.

Other compounds of the present invention can also be synthesized in good yield by the same method.

The amount of the hardener used in carrying out the present invention is
It depends on the type of the light-sensitive material applied and the type of hydrophilic binder, but is preferably 0.
It is in the range of 01 to 100% by weight, more preferably 0.1 to 30% by weight.

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

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, or an aqueous dispersion of a polycondensation polymer such as polyester can be used. .

Silver halides, chemical sensitizers, silver halide solvents, spectral sensitizing dyes used in the silver halide emulsion layer or other layers of the light-sensitive material in carrying out the present invention,
Antifoggants, hydrophilic protective colloids such as gelatin, ultraviolet absorbers, polymer latexes, brighteners, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc. are not particularly limited, for example, Research Disclosure. (Research Disclosure) Volume 176, 22-31 (1978 12
Monthly) can be used.

Regarding the support of the light-sensitive material, the developing method, the constituent layers of the light-sensitive material, etc., the description in the above-mentioned Research Disclosure can be referred to.

[0085]

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Example 1 In the following examples, the addition amount in the light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is silver 1
It is shown by the number of moles per mole.

On the triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color light-sensitive material sample.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (O-1) 0.20 High boiling point solvent (O-) 2) 0.20 Gelatin 1.6 Second layer: Intermediate layer (IL-1) Gelatin 1.3 Third layer: Low sensitivity red sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em- 2) 0.3 sensitizing dye (S-1) 3.2 × 10 ^-4 sensitizing dye (S-2) 3.2 × 10 ^-4 sensitizing dye (S-3) 0.2 × 10 ^-4 cyan coupler (C-1) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 High boiling point solvent (O-1) 0.55 Additive (SC-1) 0.003 Gelatin 1.0 Fourth layer: High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 0.9 Sensitized color (S-1) 1.7 × 10 -4 Sensitizing dye (S-2) 1.6 × 10 -4 Sensitizing dye (S-3) 0.1 × 10 -4 Cyan coupler (C-2) 0.23 Colored cyan coupler (CC- 1) 0.03 DIR compound (D-2) 0.02 High boiling point solvent (O-1) 0.25 Additive (SC-1) 0.003 Gelatin 1.0 Fifth layer: Intermediate layer (IL-2) Gelatin 0.8 Sixth layer: Low sensitivity green Sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion (Em-2) 0.2 Sensitizing dye (S-4) 6.7 × 10 ^-4 Sensitizing dye (S-5) 0.8 × 10 ^-4 Magenta coupler (M-1) 0.17 Magenta coupler (M-2) 0.43 Colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 High boiling point solvent (O-2) 0.70 Additive (SC -1) 0.003 gelatin 1.0 Seventh layer: high-sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-6) 1.1 × 10 ^-4 Sensitizing dye (S-7) 2.0 × 10 ^-4 Sensitizing dye (S-8) 0.3 × 10 ^-4 Magenta coupler (M-1) 0.03 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.004 High boiling point solvent (O-2) 0.35 Additive (SC-1) 0.003 Gelatin 1.0 Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Agent (HS-2) 0.07 Additive (SC-2) 0.12 High boiling point solvent (O-2) 0.15 Gelatin 1.0 9th layer: Low sensitivity blue sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-9) 5.8 × 10 ^-4 Yellow coupler (Y-1) 0.60 Yellow coupler (Y-2) 0.32 DIR compound (D-1) 0.003 DIR compound (D-2) 0.006 High boiling point solvent (O-2) 0.18 Additive (SC-1) 0.004 Gelatin 1.3 Layer 10: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.5 Sensitizing dye (S-10) 3.0 × 10 ^-4 Sensitizing dye (S-11) 1.2 × 10 ^-4 Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) 0.10 High boiling point solvent (O-2) 0.05 Additive (SC-1) 0.002 Gelatin 1.0 11th layer: 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 (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (O -1) 0.07 High boiling point solvent (O-3) 0.07 Gelatin 0.8 12th layer: 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate (average particle size 3 μm) 0.02 Lubricant (WAX-1) 0.04 Charge control agent (SU-1) 0.004 Charge control agent (SU-2) 0.02 Gelatin 0.5 In each layer, Other serial as shown in Table 1 by adding a hardener or a comparison of the hardening agent of the present invention to produce a sample 50.

In each layer, a coating aid (SU-4), a dispersion aid (SU-3), a stabilizer (ST-1), an antiseptic (D).
I-1), antifoggants (AF-1), (AF-2),
Dyes (AI-1) and (AI-2) were added appropriately.

The emulsions used in the above samples are as follows. Both are high internal iodine type monodisperse emulsions.

Em-1: average silver iodide content 7.5 mol%
Average grain size 0.55 μm Grain shape Octahedron Em-2: Average silver iodide content 2.5 mol% Average grain size 0.36
μm Grain shape Octahedron Em-3: Average silver iodide content 8.0 mol% Average grain size 0.84
μm Grain shape Octahedron Em-4: Average silver iodide content 8.5 mol% Average grain size 1.02
μm Grain shape Octahedron Em-5: Average silver iodide content 2.0 mol% Average grain size 0.08
The additives used to make the μm photosensitive material are shown below.

SU-1: sulfosuccinate di (2,2,3,3,4,4,
5,5,6,6,7,7-Dodecylfluoropeptyl) -sodium salt SU-2: 2,4-di-t-nonylphenol-ethylene oxide 12 mol Sulfate ester-sodium salt of adduct SU-3: tri- Sodium i-propylnaphthalene sulfonate SU-4: Dioctyl sulfosuccinate sodium salt SC-1: Dodecyl gallate SC-2: 2-Methyl-5-sec-octadecylhydroquinone and 2-sec-hexadecylhydroquinone 2 : 3 mixture O-1: di (2-ethylhexyl) phthalate O-2: tricresyl phosphate O-3: dibutyl phthalate ST-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetra Zaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: Polyvinylpyrrolidone (average molecular weight = 9000)

[0093]

[Chemical 34]

[0094]

[Chemical 35]

[0095]

[Chemical 36]

[0096]

[Chemical 37]

[0097]

[Chemical 38]

[0098]

[Chemical Formula 39]

[0099]

[Chemical 40]

[0100]

[Chemical 41]

Each of the prepared samples was used as a fresh sample,
This sample was left at 25 ° C and 50% RH for 7 days, and 50
Samples that were forcibly deteriorated by leaving them for 2 days at 50 ° C / 50% RH or 50 ° C / 80% RH were prepared.

After subjecting these samples to wedge exposure with white light, the following processing was carried out to measure sensitivity and fog.

The sensitivity was expressed by the reciprocal of the exposure amount that gives a density of fog +0.5, and was shown as a relative sensitivity with 100 being the sensitivity of Sample 1 which was left at 25 ° C. and 50% RH for 7 days after coating.

Also, at 25 ° C. and 50% RH for 2 hours, 8 hours, 1
The sample that was left for 7 days was immersed in water at 30 ° C for 5 minutes, a sapphire needle with a radius of 0.3 mm was pressed against the surface of the sample, and the sample surface was moved in parallel at a speed of 2 mm at a rate of 0 to 200 g. The pressure contact load of the sapphire needle was continuously changed within the range of, and the load when the film surface of the sample was damaged was determined as the scratch resistance.

The results are also shown in Table 1, Table 2 and Table 3.

(Processing step) Color development 38 ° C. 3 minutes 15 seconds Bleach 38 ° C. 6 minutes 30 seconds Washing 38 ° C. 3 minutes 15 seconds Fixing 38 ° C. 6 minutes 30 seconds Water washing 38 ° C. 3 minutes 15 seconds Stabilization 25 ° C 1 minute 30 seconds Dry 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 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 Water is added to make 1 liter.

Bleaching solution Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 cc Add water to make 1 liter, and use ammonia water to adjust pH =
Adjust to 6.0.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

Stabilizer Formalin (37% aqueous solution) 1.5 cc Conidax (Konica Corporation) 7.5 cc Add water to make 1 liter.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

As is clear from the results of Tables 1 to 3 above, Samples 1 to 45 using the hardener according to the present invention all show a slight decrease in relative sensitivity as compared with Comparative Samples 46 to 50. There is no fog deterioration.

In addition, when the sample was forcibly deteriorated, the comparative sample 46
Samples 1 to 45 of the present invention showed a slight decrease in sensitivity and a slight increase in fog as compared with -50. Therefore, it is understood that the hardener according to the present invention hardly impairs photographic characteristics.

Further, from the results of the scratch resistance indicating the film strength, all of Samples 1 to 45 of the present invention showed higher film strength as compared with Comparative Samples 46 to 50. It can be seen that is hardened more efficiently than the comparative compound.

Further, looking at the change in the scratch resistance, it can be seen that the samples 1 to 45 of the present invention have almost no post-hardening property since the change disappears after one day or more.

Example 2 X-ray photosensitive materials 51 to 100 were obtained by sequentially forming layers having the compositions shown below on both sides of a subbed polyethylene terephthalate support from the side of the support.

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

First layer: crossover cut layer Dye (I) 3 mg / m ² mordant (II) 0.12 g / m ² gelatin 0.2 g / m ² Second layer: emulsion layer Average grain size 0.57 μm, silver iodide 2 Emulsion consisting of silver iodobromide containing mol% Coating amount of silver 4.5 g / m ² Sensitizing dye (A) 450 mg Sensitizing dye (B) 20 mg ST-1 3.0 g t-Butylcatechol 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 mg Resorcin-4-ammonium sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg Additive A 70mg additive B 1 g 1,1-dimethylol-1-bromo-1-nitromethane 10mg gelatin 2 g / m ² layer 3: protective layer of polymethyl methacrylate (average particle size 5μm) 7mg / m ² colloidal silica The average particle diameter 0.013μm) 70mg / m ² Additives C 10 mg / m ² Additives D 2 mg / m ² Additives E 7 mg / m ² Additives F 15 mg / m ² of gelatin 1 g / m ² hardener (Table 4 In addition, preservative DI-1 was added to each sample.

Additive C: ethylene oxide 12 mol of dinonylphenol Sulfate / sodium salt of adduct Additive D: ethylene oxide 12 mo of dinonylphenol
Adduct additive E: sulfosuccinic acid-i-amyl decyl sodium salt

[0122]

[Chemical 42]

[0123]

[Chemical 43]

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

The sensitivity was shown as a relative sensitivity with the sensitivity of Sample 51 7 days after application as 100.

The results are shown in Tables 4, 5 and 6.

(Processing step) Insertion 1.2 seconds Development + Crossover 35 ° C 14.6 seconds Fixing + Crossover 33 ° C 8.2 seconds Washing + Crossover 25 ° C 7.2 seconds Squeeze 40 ° C 5.7 seconds Dry 45 ° C 8.1 seconds Developer Hydroquinone 25.0g 1-phenyl- 3-pyrazolidone 1.2g potassium sulfite 55.0g boric acid 10.0g sodium hydroxide 21.0g triethylene glycol 17.5g 5-nitroimidazole 0.10g 5-nitrobenzimidazole 0.10g glutaraldehyde bisulfite adduct 15.0g glacial acetic acid 16.0g bromide Potassium 4.0g Triethylenetetramine hexaacetic acid 2.5g Add water to make 1 liter. Fixer Ammonium thiosulfate 130.9g Anhydrous sodium sulfite 7.3g Boric acid 7.0g Acetic acid (90wt%) 5.5g Sodium acetate (trihydrate) 25.8g Aluminum sulfate (18hydrate) 14.6g Sulfuric acid (50wt%) 6.77g Add water Finish to 1 liter.

While the samples were kept at a humidity of 25 ° C. and 50% RH, 2 hours, 8 hours, 1 day, and 7 days after application, a part of each sample was taken out and swollen in water at 30 ° C. for 5 minutes. The film thickness of each sample was measured, the swelling degree V represented by the following formula was calculated, and the change over time of the curing action (post-hardening property) was observed. This result is also in Table 4
~ 6.

V = film thickness increased by swelling / film thickness when dried

[0130]

[Table 4]

[0131]

[Table 5]

[0132]

[Table 6]

As is clear from the results of Tables 4 to 6, X-ray light-sensitive material samples 51 to 51 in which the hardener of the present invention was added to the protective layer.
In 95, variations in photographic characteristics such as a decrease in sensitivity and an increase in fog are hardly seen as compared with Comparative Samples 96 to 100. Moreover, after one day or more after coating and drying, the change in the degree of swelling is small and stable, and the post-hardening property is remarkably improved. Comparing the final degree of swelling with the comparative samples 96 to 100, it can be seen that the dura mater is effectively made.

[0134]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide photograph containing a novel hardener which can effectively perform a hardener even with a small amount of hardener without impairing photographic performance and has no post-hardener effect. A photosensitive material can be provided.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers comprises a compound represented by the following general formula [I]: A silver halide photographic light-sensitive material characterized by being hardened with at least one kind. [Chemical 1] [In the formula, L ₁ represents a releasable group, and R ₁ represents a substituent. m represents 0 or 1. ] 2. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula [I
A silver halide photographic light-sensitive material characterized by being hardened with at least one compound represented by the formula [I]. [Chemical 2] [In the formula, R ₁ represents a substituent, and m represents 0 or 1. X ₁
Represents —CO—, —CS— or —SO ₂ —, Y ₁ represents a single bond,
O -, - S -, - N (R 2) -, - CO -, - C (R 3) = N- or -
Represents N = C (R ₄ ) −. R ₂ represents an alkyl group or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. ] 3. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula [II
A silver halide photographic light-sensitive material characterized by being hardened with at least one compound represented by the formula [I]. [Chemical 3] [In the formula, R ₁ represents a substituent, and m represents 0 or 1. Z ₂
Represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle. R ₅ represents a substituent, and n represents 0, 1 or 2. X ⁻ represents an anion portion in the molecule or a free anion. ] 4. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula [I
V] A silver halide photographic light-sensitive material characterized by being hardened with at least one compound represented by the formula [V]. [Chemical 4] [In the formula, R ₁ represents a substituent, and m represents 0 or 1. L ₂
Represents a group selected from the groups represented by the following general formula [V], general formula [VI] or general formula [VII]. ] [Chemical 5] [In the formula, Z ₃ represents an atomic group necessary for forming a nitrogen-containing heterocycle. ] [Chemical 6] [In the formula, Y ₂ represents an oxygen atom or a sulfur atom, and Z ₄ represents an atomic group necessary for forming a nitrogen-containing heterocycle. ] [Chemical 7] [In the formula, R ₆ represents an alkyl group or an aralkyl group, and Z ₅
Represents an atomic group necessary for forming a nitrogen-containing heterocycle. Y
^- represents an anion required to offset the charge in the molecule. ]