JPH07301877A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce fog without lowering sensitivity and to enhance processing stability by chemically sensitizing a silver halide emulsion layer in the presence of a polysulfide compound and incorporating a specified aromatic polyhydroxy compound. CONSTITUTION:The photosensitive material having on a support at least one silver halide emulsion layer chemically sensitized in the presence of the polysulfide compound and containing the aromatic polyhydroxy compound represented by the formula in which R is alkyl, alkoxy, hydroxy, sulfo, carboxyl, nitro, or halogen: and Z is a hydrocarbon group necessary to form a condensed benzene ring or may be no existing. It is preferred that this photosensitive material is processed in a developing solution replenishing rate of <=250ml/m<2> and in a fixing solution replenishing rate of <=400ml/m<2> and dried in a relative humidity of >=60% and at a dry bulb temperature of >=20 deg.C at the time when a water to gelatin ratio is lowered to <=40% lowers in drying a coating material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for printing plate making, more specifically to provide a silver halide photographic light-sensitive material which has reduced fog and good processing stability without lowering sensitivity. .

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone image. As a method of reproducing this step, conventionally, a so-called lith photosensitive material, a method by a lith developing method has been used, but recently, due to its instability, a so-called contrast adjusting agent such as a hydrazine derivative or a tetrazolium compound is contained, The method of processing by stable PQ development has become popular.

However, there is a problem that fog is liable to occur when these hardening agents are contained, so that the sensitivity is lowered when a fog inhibitor is used or chemical aging is controlled. I have a problem. Further, there is also a problem that the sensitivity is likely to change due to the concentration or dilution of the processing solution due to the formulation of the developing solution or the running processing. Therefore, it is desired to develop a technique that reduces fog without lowering the sensitivity and has high processing stability.

[0004]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which has reduced fog and high processing stability without lowering sensitivity. Especially.

[0005]

The above object of the present invention can be achieved by the following silver halide photographic light-sensitive material.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer is chemically sensitized in the presence of a polysulfide compound and has the general formula A silver halide photographic light-sensitive material comprising an aromatic polyhydroxy compound represented by [P].

The photosensitive material has a developer replenishment amount of 250 m.
L / m ² or less, fixer replenisher replenishment rate 400ml / m ² or less low replenishment rate, relative humidity 60% or more, wet bulb temperature 20 ° C when water / gelatin ratio is 40% or less during coating and drying. It is a preferred embodiment that the drying is performed under the above conditions.

(2) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a tetrazolium compound in the silver halide emulsion layer, water / gelatin during coating and drying. A silver halide photographic light-sensitive material characterized by being dried at a relative humidity of 60% or more and a wet bulb temperature of 20 ° C. or more when the ratio is 40% or less.

(3) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer, water / gelatin during coating and drying. A silver halide photographic light-sensitive material characterized by being dried at a relative humidity of 60% or more and a wet bulb temperature of 20 ° C. or more when the ratio is 40% or less.

The present invention will be specifically described below.

First, the polysulfide compound according to the present invention will be described.

The polysulfide compound in the present invention is 3
Organic and inorganic compounds having one or more sites in which one or more sulfur atoms are linked. As the polysulfide compound, a linear, branched or cyclic compound may be used, but a compound having a cyclic polysulfide group is particularly preferable from the viewpoint of stability of the polysulfide compound. Specific examples of these compounds include the following compounds. Of course, the present invention is not limited to this.

[0013]

[Chemical 2]

Regarding the timing of adding the polysulfide compound, it can be added in any step as long as the silver halide grains are chemically sensitized in the presence of the polysulfide compound. Specifically, chemical sensitization is performed before the formation of silver halide grains, during the formation of silver halide grains, from the end of silver halide grain formation to the desalting step, and from the desalting step to the start of chemical sensitization. It may be at any time selected from the start of sensation and during chemical sensitization. Preferably, it is added at any time selected from the end of silver halide grain formation to before the desalting step, from after desalting to before the start of chemical sensitization, at the start of chemical sensitization and during chemical sensitization. . Of these, particularly good is at the start of chemical sensitization.

The addition amount of the polysulfide compound varies depending on the kind of silver halide emulsion to be applied and the magnitude of the expected effect, but is 1 × per mol of silver halide.
It is 10 ⁻⁵ mg to 100 mg. It is preferably 1 × 10 ^{−3 to} 10 mg.

Next, the aromatic polyhydroxy compound represented by the general formula [P] used in the present invention will be explained.

In the formula, R represents an alkyl group, an alkoxy group, a hydroxy group, a sulfonic acid group, a carboxyl group, a nitro group or a halogen atom, and Z represents a group of carbon atoms forming a condensed benzene nucleus. Z may or may not be present,
n is 0 to 4 when Z is absent, and 0 when Z is present.
It is 6.

The functions required of the chelating agent contained in the developer are, as described above, the function of preventing the precipitation of carbonates and sulfates due to the accumulation of calcium ions, magnesium ions, etc., and trace amounts of iron, copper ions, etc. It does not form a chelate with the heavy metal ions of the above to catalytically accelerate the air oxidation of the developing agent. The present inventor develops the performance satisfying the required functions when the developer contains the above-mentioned two kinds of compounds, that is, the aminopolycarboxylic acid type chelating agent and the compound represented by the general formula [P]. I found that. Examples of the aminopolycarboxylic acid type chelating agent of the present invention include diethylenetriaminetetraacetic acid (DTPA), glycol ether diaminetetraacetic acid (GEDTA), triethylenetetramine hexaacetic acid (TTHA), and 1,3-diamino.
It is preferable to use -2-propanoltetraacetic acid (DPTA-OH) and N-hydroxyethylenediaminetriacetic acid (HEDTA). The addition amount of the aminopolycarboxylic acid type chelating agent of the present invention is 1 × 10 ^{−3 to} 3 × 10 3 per 1 liter of the developing solution.
^-2 mol is convenient, and an appropriate amount depends on the composition of the developing solution, the quality of the diluting water, the characteristics of the photosensitive material to be processed, and the like.

The compound represented by the general formula [P] used in the present invention is characterized in that at least two hydroxy groups are adjacently substituted with a benzene ring, a naphthalene ring or the like. Further, in these benzene ring, naphthalene ring, etc., a C ₁ -C ₃ alkyl group is a C ₁ -C ₃ alkoxy group, a nitro group, a sulfonic acid group, a carboxylic acid group,
It may be substituted with a hydroxy group, a halogen atom, an aldehyde group or the like, and may be substituted with two or more kinds of substituents. The aromatic is preferably a benzene ring, and the substituent thereof is preferably a nitro group, a sulfonic acid group or a carboxylic acid group. Specific examples of the representative compounds are shown below, but the invention is not limited thereto.

[0020]

[Chemical 3]

[0021]

[Chemical 4]

Particularly preferred compounds are P-2, P-3 and P.
-5, P-11, P-15, and P-16. The amount of the aromatic polyhydroxy compound of the present invention added to the developer is 1/3 or less of the amount of the aminocarboxylic acid chelating agent added. Preferably 1 × 10 ⁻⁴ to 1 × per liter of developer.
It is used in an amount of 10 ^-2 mol, more preferably 1 x 10 ^{-4 to} 5 x 10 ^-3 mol.

Next, as the hydrazine derivative used in the present invention, a compound represented by the following general formula [H] is used.

[0024]

[Chemical 5]

The general formula [H] will be described in detail below.

In the formula, the aliphatic group represented by A is preferably one having 1 to 30 carbon atoms, particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group,
Examples thereof include a benzyl group and the like, and these are further suitable substituents (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group,
Sulfonamide group, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [H] is preferably a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, a pyrrolidine ring, Examples thereof include an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

Further, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group has 8 carbon atoms.
Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, an alkylphenoxy group and the like, which are relatively inactive to the above photographic properties.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), an aryloxycarbonyl Groups (eg phenoxycarbonyl etc.), sulfamoyl groups (eg dimethylsulfamoyl etc.), sulfinamoyl groups (eg methylsulfur) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group (the general formula [Ha] will be described later) or a heterocyclic group. (Eg, pyridine ring, pyridinium ring, etc.).

B in the general formula [H] represents A ₂ and the nitrogen atom to which they are attached.

[0035]

[Chemical 6]

May be formed.

R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

Among the hydrazine compounds used in the present invention, particularly preferred are the compounds represented by the following general formula [Ha].

[0041]

[Chemical 7]

In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ represents

[0043]

[Chemical 8]

Represents

R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Alternatively, it represents a heterocyclic oxy group, and R ₆ and R ₇ may form a ring together with an N atom. R ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ represent the same meanings groups as A ₁ and A ₂ in formula (H).

The general formula [Ha] will be described in more detail.

The aryl group represented by R ₄ is preferably a monocyclic ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₄ is preferably a 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, which is a monocyclic or condensed ring. Examples thereof include a ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₄ is a substituted or unsubstituted aryl group. Examples of the substituent include those having the same meaning as the substituent of A in the general formula [H].
When the contrast is increased with a developing solution of 1.2 or less, it is preferable to have at least one sulfamide group.

[0050] A ₁ and A _2, A ₁ and A ₂ of the formula H
And a hydrogen atom are the most preferable.

R ₅ is

[0052]

[Chemical 9]

Wherein R ₆ and R ₇ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.),
Alkenyl groups (allyl, butenyl, etc.), alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl) Nyl, quinolidinyl, N, N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy , Ethoxy, etc.), alkenyloxy group (allyloxy etc.), alkynyloxy group (propargyloxy etc.), aryloxy group (phenoxy etc.), or heterocyclic oxy group (pyridyloxy etc.), and R ₆ and R ₇ are nitrogen. A ring (piperidine, morpholine, etc.) may be formed together with the atom. R ₈ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocycle Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compounds represented by the general formulas [H] and [Ha] are shown below. However, the present invention is not limited to these.

[0055]

[Chemical 10]

[0056]

[Chemical 11]

[0057]

[Chemical 12]

[0058]

[Chemical 13]

[0059]

[Chemical 14]

[0060]

[Chemical 15]

[0061]

[Chemical 16]

[0062]

[Chemical 17]

The method of synthesizing the compound represented by the general formula [H] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European Patent 253.
The methods described in No. 665 and No. 333,435 can be referred to.

The amount of the compound represented by the general formula [H] used in the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, it is preferable to contain a nucleation accelerator in at least one hydrophilic colloid layer on the side containing the silver halide emulsion layer with respect to the support. Particularly preferably, it is contained in the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer. Further, in this case, the pH of the developer is preferably 9.5 to 11.5, and particularly preferably 9.7 to 11.0.

Next, as the nucleation accelerator, the following general formula [N
Examples thereof include those shown in a] or [Nb].

[0067]

[Chemical 18]

In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. A ring can be formed by R ₁ , R ₂ and R ₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is more preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific compounds include those shown below.

[0070]

[Chemical 19]

[0071]

[Chemical 20]

[0072]

[Chemical 21]

[0073]

[Chemical formula 22]

In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or heteroaromatic ring. R represents an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have a preferable diffusion resistant group, the molecular weight is preferably 120 or more, particularly preferably 300 or more.

Specific compounds include those shown below.

[0076]

[Chemical formula 23]

[0077]

[Chemical formula 24]

Among these nucleation accelerators, those having at least one-(CH ₂ CH ₂ O)-group in the molecule are particularly preferable.

The preferable tetrazolium compound used in the light-sensitive material used in the present invention is generally represented by the following general formula [T]. Those having an elution suppressing group are preferable, and the elution suppressing group is preferably a substituted or unsubstituted phenyl group.

[0080]

[Chemical 25]

In the present invention, the substituents R ₁ , R ₂ and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T] are hydrogen atoms or Hammett's sigma value (σP) showing electron withdrawing degree. Is preferably negative or positive. Particularly negative ones are preferable.

Hammett's sigma value for phenyl substitution is well documented, for example, Journal of Medical Chemistry, Vol. 20,
P. 304, 1977, C. It can be found in reports such as C. Hansch.

A particularly preferred group having a negative sigma value is, for example, a methyl group (σP = −0.17 or less, and σP
Value), ethyl group (-0.15), cyclopropyl group (-0.21),
n-propyl group (-0.13), iso-propyl group (-0.15), cyclobutyl group (-0.15), n-butyl group (-0.18), iso-butyl group (-0.20), n-pentyl group (-0.15 ), Cyclohexyl group
(-0.22), amino group (-0.66), acetylamino group (-0.1
5), hydroxyl group (-0.37), methoxy group (-0.27), ethoxy group (-0.24), propoxy group (-0.25), butoxy group
(-0.32), pentoxy group (-0.34) and the like are mentioned, and all of them are useful as a substituent of the compound of the general formula [T] of the present invention.

N represents 1 or 2.

Examples of the anion represented by X ⁻ include halogen ions such as chloride ions, bromide ions and iodide ions, acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid,
Acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion, lower alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate anion , Higher alkylbenzenesulfonate anions such as p-dodecylbenzenesulfonate anion, higher alkylsulfate anions such as laurylsulfate anion, borate anions such as tetraphenylpolone, dialkylsulfones such as di-2-ethylhexylsulfosuccinate anion. Polyether alcohol sulfate anion such as succinate anion and cetyl polyethenoxysulfate anion, higher aliphatic anion such as stearic acid anion, and acid radical of polymer such as polyacrylic acid anion. And the like can be mentioned those who were.

Specific examples of the compound represented by the formula [T] are shown below, but the tetrazolium compound is not limited to these.

[0087]

[Chemical formula 26]

The above tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, Volume 55, pp. 335 to 483.

The tetrazolium compound represented by the general formula [T] may be used alone or in combination of two or more kinds at an appropriate ratio.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as silver halide, ordinary silver halide such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide and the like. Any of those used in emulsions can be used, and silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer, and a latent image May be particles mainly formed on the surface or particles mainly formed inside the particles.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. or,
U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-26589
, Japanese Patent Publication No. 55-42737, J. Photgr. Sci. 2
By the method described in the literature such as 1.39 (1973), particles having a shape of octahedron, tetrahedron, dodecahedron, etc. can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape or a mixture of grains having various shapes.

Further, those having any grain size distribution may be used, and the polydisperse emulsion or monodisperse emulsion may be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the present invention, a monodisperse emulsion is preferred.
As a monodisperse silver halide emulsion in a monodisperse emulsion, when the weight of silver halide contained within a grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains, Some are preferable, particularly preferably 70% or more, further preferably 80% or more.

The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of a non-spherical grain when the projected image is converted into a circular image of the peripheral area. Is. The particle size is, for example, 10,000 times to 5 times with an electron microscope.
It can be obtained by enlarging the image by a factor of ten thousand, and measuring the particle diameter on the print or the area at the time of projection. (It is assumed that the number of measured grains is 1000 or more indiscriminately.) A particularly preferred highly monodisperse emulsion of the present invention has a monodispersity of 20 defined by grain size standard deviation / mean grain size × 100 = monodispersity It is as follows, more preferably 15 or less. Monodisperse emulsion is JP-A-54
-48521, 58-49938 and 60-122935 can be referred to.

The light-sensitive silver halide emulsion can be used as it is, without being chemically sensitized, as it is as a so-called unripened (Primitive) emulsion, but it is usually chemically sensitized. The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include Research Disclosure (RD) No. 1
Various compounds described in 7643, (RD) No. 18716 and (RD) No. 308119 (December 1989) can be used.

The types and locations of the compounds described in these three Research Disclosures (RD) are listed below.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 ~ 7 VI Hardener 26 X 651 Left 1004 ~ 5 X Surfactant 26 ~ 27 XI 650 Right 1005 ~ 6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 ~ 9 XVI Binder 26 XXII 1003 ~ 4 IX Support 28 XVII 1009 XVII Various kinds of photographic materials known in the photographic industry A treatment method can be applied.

[0100]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Preparation of silver halide emulsion A) A silver chlorobromide emulsion containing 77 mol% of silver chloride and 23 mol% of silver bromide was prepared by the simultaneous mixing method. During the mixing step, hexachloroiridate potassium salt was added at 6 × 10 ⁻⁷ mol per mol of silver. The emulsion thus obtained was desalted by a conventional flocculation method. The particles were cubic particles having an average particle size of 0.28 μm and were monodisperse particles having a coefficient of variation of 9%.

(Formulation of Emulsion Layer) This emulsion was adjusted to pH 5.8 and pAg 7.0 with citric acid and potassium bromide, and then chloroauric acid was added at 2 × 10 ^-5 mol per mol of silver and sulfur was added. Sensitizer (Table 1
2) per 1 mol of silver and 7 mg of sodium thiosulfate as a comparative compound were added, and the mixture was chemically ripened at 60 ° C. for 60 minutes to reach the maximum sensitivity. Next, sensitizing dye A was added in an amount of 250 mg per mol of silver halide, and then 4-hydroxy-6-
Aging was stopped by adding 60 mg of methyl-1,3,3a, 7-tetrazaindene.

Then, 200 mg of sensitizing dye B was added per mol of silver halide, and 700 mg of tetrazolium compound T-7 was added.
Was added. Further, sodium p-dodecylbenzenesulfonate 300 mg, styrene-maleic acid copolymer 2 g, compound of general formula [P] (shown in Table 1) 400 mg, and 1-phenyl-5-mercaptotetrazole as a comparative compound 400 mg, styrene- 1.5g of butyl acrylate-acrylic acid copolymer latex (average particle size 0.25μm) was added to give 4.1g / m of silver.
^{2. The} amount of gelatin was 1.7 g / m ² and coated on the polyethylene terephthalate film base having the undercoat described in Example 1 of JP-A-59-19941.

[0104]

[Chemical 27]

(Formulation of Emulsion Protective Layer) Gelatin 1.0 g / m ² Spreading agent Bis (2-ethylhexyl) sulfosuccinate 10 mg / m ² Hardener Formalin 25 mg / m ² (coating and drying conditions) Water / gelatin ratio is 40 %, The relative humidity was 60% or more, and the wet-bulb temperature was 20 ° C. or more.

(Development prescription) Composition A Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-phenyl -5-Mercaptotetrazole 30mg Potassium hydroxide Amount to adjust the pH of the used solution to 10.5 Potassium bromide 4.5g Composition B Pure water (ion exchanged water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in this order to make 1 liter (Developer 1) and 0.8 liter (Developer) 2), using 3 kinds of developing solution, which is finished to 1.2 liters (Developing solution 3) Processed.

(Fixer formulation) (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% w / w aqueous solution) 8.1 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% w / w aqueous solution) 5.8 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) 26.5 g When the fixer was used, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 liter. Of this fixer
The pH was about 4.3.

(Development processing conditions) (Process) (Temperature) (Time) Image 28 ° C 30 sec Settling 28 ° C 20 sec Water washing 20 ° C normal temperature 20 sec Dry 40 ° C 20 sec Including time.

Developer Replenishment Amount 250 ml / m ² or Less Fixer Replenisher Amount 400 ml / m ² or Less (Evaluation of Sample) The film thus obtained was exposed through a wedge by a tungsten light source. Table 1 shows the photographic characteristics of the sample obtained by the processing. The processing stability was evaluated based on the rate of change in relative sensitivity due to the difference between the processing solutions when the developing solution 1 was used as a reference. For evaluation of fog, the density of the film when unexposed was measured.

[0110]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention has a low rate of change in sensitivity and little fog.

Example 2 (Preparation of silver halide emulsion B) A silver chlorobromide emulsion containing 98 mol% of silver chloride and 2 mol% of silver bromide was prepared by the simultaneous mixing method. During the mixing step, hexachloroiridate potassium salt was added at 6 × 10 ⁻⁷ mol per mol of silver. The emulsion thus obtained was desalted by a conventional flocculation method. The particles were cubic particles having an average particle size of 0.28 μm and were monodisperse particles having a coefficient of variation of 9%.

(Formulation of Emulsion Layer) This emulsion was adjusted to pH 5.8 and pH 7.0 with citric acid and potassium bromide, and then chloroauric acid was added in an amount of 2 × 10 ^-5 mol per mol of silver and S- 2 was added per 1 mol of silver, and 7 mg of sodium thiosulfate was added as a comparative compound, and the mixture was chemically ripened at 60 ° C. for 60 minutes to reach the maximum sensitivity. Next, the sensitizing dye A was added to 25 mol per mol of silver halide.
After adding 0 mg, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (60 mg) was added to stop the ripening.

Then, 200 mg of sensitizing dye B was added per mol of silver halide, and 700 mg of tetrazolium compound T-7 was added.
Was added. Further, sodium p-dodecylbenzenesulfonate 300 mg, styrene-maleic acid copolymer 2 g, compound (P-20) 400 mg of general formula [P], and 1-phenyl-5-mercaptotetrazole 400 mg and styrene-butyl as comparative compounds Add 1.5g of acrylate-acrylic acid copolymer latex (average particle size 0.25μm), silver amount 4.1g / m
^{2. The} amount of gelatin was 1.7 g / m ² and coated on the polyethylene terephthalate film base having the undercoat described in Example 1 of JP-A-59-19941.

(Formulation of Emulsion Protective Layer) Gelatin 1.0 g / m ² Spreading agent Bis (2-ethylhexyl) sulfosuccinate 10 mg / m ² Hardener Formalin 25 mg / m ² (coating drying conditions) Coating drying conditions are water / 40% gelatin ratio
In the following, coating was performed under various conditions as shown in Table 2.

[0116]

[Table 2]

From the results of Table 2, in the case of the drying conditions of the present invention,
It can be seen that the fog density is low.

Example 3 (Preparation of Silver Halide Emulsion C) A silver chlorobromide emulsion consisting of 70 mol% of silver chloride and the rest of silver bromide was prepared by the simultaneous mixing method. K ₃ RhBr ₆ at the time of simultaneous mixing 8.1 × 10 ^-8 per mol of silver
Mol added. The obtained emulsion was a cubic emulsion having an average grain size of 0.20 μm and monodisperse grains (variation coefficient: 9%). Then, the emulsion was desalted with a modified gelatin described in JP-A-2-280139 (one in which the amino group in gelatin was substituted with henylcarbamyl, for example, G-8 in JP-A-2-280139). The EAg after desalting was 190 mv at 50 ° C.

The emulsion thus obtained was adjusted to pH 5.58 and EAg123mv, and then the temperature was adjusted to 60 ° C., and chloroauric acid was added to 2.2 mol per mol of silver.
After adding ^{x10 -5} mol and stirring for 2 minutes, S-7 was added in an amount of 2.9 x 10 ^-6 mol per mol of silver, and chemical ripening was further performed for 78 minutes.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175, the following formulation The silver halide emulsion of No. 1 was coated such that the silver amount was 3.3 g / m ² and the gelatin amount was 1.7 g / m ² .

Furthermore, the following formulation 2 was used as a protective layer on the upper layer.
Was coated so that the amount of gelatin would be 1 g / m ² .
On the undercoat layer on the opposite side, a backing layer of the following formulation 3 is coated so that the amount of gelatin is 1.5 g / m ^2, and a protective layer of the following formulation 4 is 1 g / m ^{2 of} gelatin on the upper layer. Thus, 9 kinds of samples shown in Table 1 were prepared.

[0123] Formulation 1 (silver halide emulsion layer composition) Sensitizing dye A 6.0 mg / m ² Sensitizing dye B 2.5 mg / ^{m 2}

[0124]

[Chemical 28]

S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.64 mg / m ² 2-mercapto-6-hydroxypurine 1.7 g / m ² EDTA 50 mg / m ² hydroquinone 50 mg / m ² formulation 2 (Emulsion protective layer composition) S-1 12 mg / m ² Matting agent: Monodisperse silica 22 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ^{2 with an} average particle size of 3.5 μm

[0126]

[Chemical 29]

4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone (dimezone S) 1.5 mg / m ² Each coating solution on the emulsion side was adjusted with sodium acetate to the film surface pH as shown in Table 1. .

[0128] Formulation 3 (backing layer composition) saponin ^{133mg / m 2 S-1 6mg} / m 2 Colloidal silica 100 mg / ^{m 2}

[0129]

[Chemical 30]

Formulation 4 (Backing protective layer composition) Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5.0 μm 50 mg / m
² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10mg / m ² (coating drying conditions) Coating drying conditions: water / gelatin ratio 40%
In the following, coating was performed under various conditions as shown in Table 3. The obtained sample was brought into close contact with a step wedge and exposed at a wavelength of 488 nm as a substitute characteristic of Ar laser light, and then an automatic developing machine for rapid processing (GR-26SR Konica Corporation ]) Under the following conditions.

(Developer Formulation) Sodium sulfite 40 g Potassium carbonate 50 g Hydroquinone 15 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (Dimeson S) 1.5 g Potassium bromide 5 g 5-Methyl-benzotriazole 0.5 g Boric acid 5 g Diethylene glycol 50 g 2-Mercapto-hypoxanthine 80 mg Water and potassium hydroxide are added to make 1 liter / pH 10.4.

(Fixing solution formulation) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate / trihydrate 6.5 g Boric acid 6.0 g Boric acid 10 g Tartaric acid 1 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W Aqueous solution of / V) 26.5 g It was used after finishing to 1 liter. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Step) (Temperature) (Time) Development 35 ° C. 14 seconds Fixing 34 ° C. 10 seconds Water washing 10 minutes normal temperature 10 seconds Drying 40 ° C. 11 seconds Each step time includes the time for feeding to the next step. Replenisher of developer: 250 ml / m ² or less Fixer: Replenisher of 400 ml / m ² or less (Sample evaluation)
Shown in. The sensitivities in the table are relative sensitivities when the sensitivity of Sample No. 1 at a concentration of 3.0 is 100. For evaluation of fog, the density of the film when unexposed was measured.

[0134]

[Table 3]

The results in Table 3 also show that the sample of the present invention has a low fog density.

[0136]

According to the present invention, without lowering the sensitivity,
It was possible to provide a silver halide photographic light-sensitive material with reduced fog and good processing stability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area G03C 5/395

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that the silver halide emulsion layer is chemically sensitized in the presence of a polysulfide compound and contains an aromatic polyhydroxy compound represented by the general formula [P]. [Chemical 1] [In the formula, R represents an alkyl group, an alkoxy group, a hydroxy group, a sulfonic acid group, a carboxyl group, a nitro group or a halogen atom, and Z represents a group of carbon atoms forming a condensed benzene nucleus. Z may or may not be present, and n is 0 to 4 when Z is absent, and 0 to 6 when Z is present. ] 2. A silver halide photographic light-sensitive material according to claim 1, wherein the processing is carried out at a low replenishing rate of a developing solution replenishing amount of 250 ml / m ² or less and a fixing solution replenishing amount of 400 ml / m ² or less. . 3. The silver halide according to claim 1, wherein at the time of coating / drying, when the water / gelatin ratio is 40% or less, the relative humidity is 60% or more and the wet bulb temperature is 20 ° C. or more. Photographic material. 4. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a tetrazolium compound in the silver halide emulsion layer, wherein a water / gelatin ratio is obtained during coating and drying. A silver halide photographic light-sensitive material characterized by being dried at a relative humidity of 60% or more and a wet-bulb temperature of 20 ° C or more at a temperature of 40% or less. 5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer.
A silver halide photographic light-sensitive material characterized by being dried at a relative humidity of 60% or more and a wet-bulb temperature of 20 ° C. or more when the water / gelatin ratio is 40% or less during coating and drying.