JPH06308656A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material high in sensitivity and low in fog and improved in pressure characteristics in a dry state. CONSTITUTION:The silver halide photographic sensitive material is formed by adding an antifoggant as a solution containing it with its dissociation degree of >=0.99 from the end of a nucleus-forming process to the end of a coating fluid-preparing process. The contained silver halide grains have high silver chloride content and each grain has a localized part different in silver bromide content and contains a gold compound in the inside of each grain.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a high sensitivity, a low fog, a high gradation, a high quality image, and a small amount of an organic solvent used in the production, and therefore an organic solvent. A silver halide photographic light-sensitive material having improved pressure characteristics when dried in the case of an emulsion using a high silver chloride grain having a small amount of silver and a part of the grain having a different localized portion of silver bromide It is a thing.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials, are widely used today because of their high sensitivity, excellent gradation and sharpness.

In these silver halide photographic light-sensitive materials, a plurality of photosensitive layers and non-light-sensitive layers containing photosensitive silver halide grains are generally coated on a support.
Even if the silver halide photographic light-sensitive material is unexposed, minute photographic density and fog are generated by development. Fog has a great influence on the expressiveness of the depiction of the highlight portion, especially in print materials, so techniques for preventing the fog have been studied. There are various methods to prevent fog, but it is usually done by adding an antifoggant. Regarding these antifoggants, for example, Stabilizatio by EJBirr
n of Photogaphic Silver Halide Emulsions 1st edition (1974 published by Focal) and
The James of The Theory of Photographic Process
(The Theory of Photographic Process)
The fourth edition (1977, published by Macmillan) is described.
However, while the antifoggant can prevent fog, it has drawbacks such as lowering sensitivity, softening gradation, and deactivating development processing. Therefore, an antifoggant that does not have these drawbacks has been desired. Efforts have been made to improve this problem with various compounds. For example, JP-A-62-177539 and JP-A-62-25
0436, JP 62-253142, JP 62-253165, JP 63-44650, JP 63-46440, JP 63-46442,
JP-A-63-46445 and JP-A-63-311245 disclose antifoggants that do not inactivate the development process. Further, in JP-A-51-36130, a heterocyclic compound having a mercapto group and having at least two aza nitrogen atoms in the molecule and having a pKa of not more than 7.6 is added. A technique for suppressing fog and realizing sensitization during sulfur sensitization is disclosed. JP-A-62-177539 describes an antifoggant such as a nitrogen-containing heterocyclic compound having a mercapto group contained in a silver halide emulsion layer consisting essentially of silver chloride. JP-A-62-253142, JP-A-62-25
No. 3165 discloses a technique using a heterocyclic compound having a mercapto group and containing nitrogen as an antifoggant. Japanese Patent Laid-Open No. 63-46445 discloses a technique of using either a compound containing a heterocyclic residue having a mercapto group or a nitrogen-containing heterocyclic compound having no mercapto group as an antifoggant. However, in recent years, there has been a demand for speeding up development processing and further higher sensitivity.
The antifoggant ability of these antifoggants has become insufficient. Up to now, there has been no mention of improving the antifoggant ability by the method of adding the antifoggant. For example, the above-mentioned JP-A-51-36130 and JP-A-62-177539.
JP-A-62-253142 and JP-A-62-253165 do not describe any addition method. In Japanese Patent Laid-Open No. 63-46445, there is some mention of the addition method, water,
Alternatively, an acid or alkaline aqueous solution having an appropriate pH value,
Alternatively, it is described as being dissolved in an organic solvent such as methanol or ethanol and added. However, there is no description about which method is preferable, and no description about the dissociation degree of the fog inhibitor. In Japanese Patent Laid-Open No. 61-290441,
A technique for adding a sensitizing dye in a solution containing water and having a pH value adjusted to 7.6 to 10.0 is disclosed, and it is stated that the stability of the sensitizing dye is enhanced. However, this technique is based on a sensitizing dye, and its compound skeleton is basically different from that of an antifoggant, and no mention is made about how its action changes depending on the degree of dissociation of the compound. No, no suggestion.

On the other hand, in recent years, in the production of silver halide photographic light-sensitive materials, from the standpoint of the working environment in use, there has been a movement to reduce the amount of organic solvent used in the preparation of silver halide photographic light-sensitive materials. Since the antifoggant is required to be adsorbed on the surface of silver halide grains having a hydrophobic surface due to its function, most of them are insoluble in water and have low solubility. Therefore, in the art, the antifoggant is usually dissolved in a low boiling point organic solvent such as alcohol and added. In order to reduce the amount of organic solvent used, techniques such as reducing the amount of various additives added, increasing the concentration of the additive liquid, and using the additive liquid as an aqueous solution can be considered. However, it is difficult to complete these techniques due to the low solubility of antifoggants in water, and so far there has been no mention of a technique for solving these problems.

Techniques for achieving high sensitivity in silver chloride emulsions include a technique of using a high silver chloride emulsion which imparts localized portions having different silver bromide contents, and a technique of incorporating a gold compound into grains. Has been done. For example, in the technique of using a high silver chloride emulsion which imparts localized portions having different silver bromide contents, JP-A-58-95736, JP-A-58-108533, and JP-A-60-222844 are known.
No. 60-222845, and Japanese Patent Laid-Open No. 62-7042. However, this technique is inferior in the pressure characteristics during drying, and various techniques have been applied to improve these.

For example, JP-A-62-253145 and JP-A-3-132
No. 647, Japanese Patent Application Laid-Open No. 3-180836, and Japanese Patent Application Laid-Open No. 4-9035 disclose a technique of incorporating a metal in particles.
Japanese Patent No. 54139 discloses a technique in which a sensitizing dye is present inside a silver bromide-rich region of a grain. JP-A-63-46440 discloses that a compound having a solubility product with silver ion of 1 × 10 ^-10 or less, specifically a nitrogen-containing heterocyclic compound, is contained inside the high silver bromide phase of the outermost shell of the grain. Techniques are disclosed that improve pressure resistance in the dry state. In this technique, a nitrogen-containing heterocyclic compound is used to improve pressure resistance, but on the other hand, sensitivity is lowered. In this technique, the method for adding the nitrogen-containing heterocyclic compound is water or an appropriate pH.
It is described that the compound is added by being dissolved in an acid or alkaline aqueous solution having a value or an organic solvent such as methanol and ethanol, and there is no description of which method is preferable, and the dissociation degree of the added solution is not mentioned. Absent. On the other hand, the technique of containing a gold compound inside the particles is described in International Patent WO
/ 93-2390. Among them, an antifoggant was used when chemically ripening an emulsion containing a gold compound inside the grains, but the addition method of the antifoggant was not mentioned, and the dissociation degree was not described. Absent.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide high sensitivity, low fog, high gradation, high quality image, and small amount of organic solvent used during production. Therefore, in the case of an emulsion using a high silver chloride grain having a small content of organic solvent and a localized portion having a different silver bromide content in a part of the grain, a silver halide having improved pressure characteristics during drying. To provide a photographic light-sensitive material.

[0008]

The above object of the present invention can be achieved by the following constitutions.

1. A silver halide photographic light-sensitive material, which is formed by adding an antifoggant as a solution having a dissociation degree of 0.99 or more.

2. 2. The silver halide photographic light-sensitive material as described in 1 above, which contains a high silver chloride emulsion.

3. The antifoggant described in 1 above has a dissociation degree of 0.
1 or 2 above, which is formed by adding 99 or more solutions during the period from the end of the nucleation step of the silver halide grains contained in the silver halide emulsion layer to the end of the coating solution adjusting step. The described silver halide photographic light-sensitive material.

4. The silver halide grains contained are high silver chloride grains having localized portions having different silver bromide contents in a part of the grains, and the antifoggant has a dissociation degree of 0.99 or more. The silver halide photographic light-sensitive material, which is added and formed between the end of the nucleation step and the end of the coating solution adjusting step.

5. The silver halide grains contained are high silver chloride grains containing a gold compound inside the grains, and the antifoggant agent is applied from the end of the nucleation step of the silver halide grains by a solution having a dissociation degree of 0.99 or more. A silver halide photographic light-sensitive material, characterized by being formed by addition until the end of the liquid adjusting step.

The silver halide photographic emulsion according to the present invention may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable.

The content of silver chloride is preferably 97 mol% or more, more preferably 98 to 99.9 mol%. The high silver chloride emulsion referred to in the specification of the present application is a silver chlorobromide emulsion containing 95 mol% or more of silver chloride and substantially containing no silver iodide.

The composition of the silver halide emulsion may be uniform or may have a portion containing a high concentration of silver bromide. In this case, the portion containing silver bromide in a high concentration may be either epitaxy bonded to the silver halide emulsion grains or a so-called core-shell emulsion, or may not form a complete layer and may be partially formed. There may be only regions having different compositions. The composition may change continuously or discontinuously. The portion having a high concentration of silver bromide may be on the surface of the silver halide grain or on the inside thereof, but is preferably on the surface of the silver halide grain. The silver bromide content of the portion containing silver bromide in a high concentration is 10 mol% or more, preferably
20 to 50 mol%.

The present invention is described in detail below. The antifoggant according to the present invention is a known antifoggant for the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing the rise of fog during storage, and preventing fog that occurs during development. Although agents can be used, compounds represented by the following general formula (I), general formula (II) and general formula (III) are preferable as the antifoggant according to the present invention.

[0018]

[Chemical 1]

In the above general formula (I), Q is 5 condensed with a 5-membered heterocyclic ring which may have a substituent or a benzene ring.
Represents a group of atoms required to form a member heterocycle.

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

The 5-membered heterocyclic ring formed by Q in the general formula (I) is, for example, an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring,
Examples thereof include a benzimidazole ring, a naphthimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, and a benzoxazole ring.

In the general formula (II), X represents the general formula (IIa) or the general formula (IIb).

[0023]

[Chemical 2]

R ₂₁ , R ₂₂ and R ₂₃ may be the same or different and each is a hydrogen atom, a halogen atom, an amino group, an amino group derivative, an alkyl group, an alkyl group derivative, an aryl group or an aryl group derivative. , A cycloalkyl group, a cycloalkyl group derivative, a mercapto group, a mercapto group derivative or -CONH-R ₂₄ (R ₂₄ is a hydrogen atom, a halogen atom,
Amino group, amino group derivative, alkyl group, alkyl group derivative, aryl group, aryl group derivative, cycloalkyl group, and cycloalkyl group derivative. ), And R ₂₁ and R ₂₂ are condensed to form a ring (for example, a 5- to 7-membered carbocycle,
A heterocycle) may be formed.

In the general formula (III), Y is a hydrogen atom, amino group, alkyl group, alkenyl group, cycloalkyl group, aryl group, -CONHR ₃₂ group, -COR ₃₃ group, -NHCOR.
Represents a ₃₄ group or a -HNSO ₂ R ₃₄ group. Z represents a nitrogen atom, a sulfur atom or an oxygen atom. n represents 1 when Z is a nitrogen atom, and 0 when Z is an oxygen atom or a sulfur atom.

R ₃₁ is a hydrogen atom, amino group, hydroxyl group, hydrazino group, alkyl group, alkenyl group, aryl group, cycloalkyl group, mercapto group, —NHCOR ₃₅ group,
It represents a -NHSO ₂ R ₃₅ group or a -SR ₃₆ group. R ₃₂ , R ₃₃ , R ₃₄ ,
R ₃₅ and R ₃₆ each represent an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.

Specific examples of the compounds represented by formulas (I) to (III) are shown below. However, it is not limited to the following exemplified compounds.

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

Of these compounds, the exemplified compound (I-9)
Particularly preferred are mercaptotetrazole compounds represented by the compounds (1-19) to (I-19).

The silver halide emulsion is prepared by a nucleation step for producing nuclei of silver halide microcrystals, a subsequent crystal growth step, a physical ripening step, a desalting step for removing excess salts, and a photosensitive nucleus. The chemical / color sensitization step of forming and color sensitizing, and the chemical / color sensitization stopping step of stopping the formation of the photosensitive nucleus and the color sensitization. The silver halide emulsion is completed as a silver halide photographic light-sensitive material through a coating solution preparation step of preparing a coating solution suitable for coating, a coating step, and a subsequent drying step. The antifoggant according to the present invention can be added in any step from the nucleation step to the coating solution preparation step, but it is preferably added after the completion of the nucleation step.

The antifoggant according to the present invention is used between the end of the nucleation step and the end of the desalting step for the purpose of improving the performance change of the silver halide emulsion during long-term storage and improving the pressure characteristics. It is preferable to add. In this case, the antifoggant is 1 × 10 ^-6 mol to 1 × 10 ⁶ mol per mol of silver halide.
It is preferably used in an amount of about ^-2 mol. When it is added in the chemical / color sensitization step, it can be used for the purpose of preventing fogging occurring during this step and controlling the formation of photosensitive nuclei. In this case, per mol of silver halide
It is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol. When it is added in the chemical / color sensitization stopping step, it can be used for the purpose of preventing fog occurring between the present step and the coating step and stopping the formation of photosensitive nuclei. In this case, 1 × 10 ⁻⁶ mol to 1 mol per mol of silver halide
It is preferably an amount of about × 10 ^-2 mol, 1 × 10 ^-5 mol to 5 × 10 ^-3.
Molar is more preferred. For the purpose of preventing fog during storage of the silver halide light-sensitive material, it can be added in the coating solution preparation step. In this case, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide.
More preferably, it is from x10 ^-5 mol to 1 x 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol / m ² to 1 × 10 ⁻³ mol / m ² . Among these steps, addition from the end of the nucleation step to the end of the desalting step is preferable in the chemical / color sensitization step and the chemical / color sensitization stop step, because the effect of the present invention is remarkably obtained.

The dissociation degree of the antifoggant according to the present invention is 0.
A solution of 99 or more can be prepared by selecting a solvent and other additives so that the antifoggant dissociation degree is 0.99 or more, or by leaving the dissolved solution for a certain period of time, but the dissociation degree is 0.999 or more. It is more preferable to use a solution prepared so that The dissociation degree of the antifoggant is defined as the concentration of the dissociated antifoggant in the solution divided by the concentration of all antifoggants. To determine the dissociation degree, for example, the spectral absorption of the antifoggant can be measured to obtain the concentration of the dissociated antifoggant, and then the concentration can be determined. For these methods, see "Experimental Chemistry Course, Cont.
Volume pp. 524 to 552 (Maruzen, 1965), etc. can be referred to. Various inorganic compounds and organic compounds can be used for the purpose of adjusting the dissociation degree. , A compound which is added to the silver halide photographic light-sensitive material and does not substantially affect the silver halide photographic light-sensitive material, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate. , Potassium carbonate, sodium acetate, triethylamine, triethanolamine and the like,
Particularly, those having a buffer effect in the solution are preferably used. As the solvent, water, a low boiling point alcohol, or a mixture thereof can be used, but it is preferable to use water because the degree of dissociation of the solution with time and the change in pH are small.

The gold compound contained in the silver halide grains contained in the silver halide emulsion layer according to the present invention will be described. As the gold compound used in the present invention, those used as general gold sensitizers in the art can be used, and the following general formulas (IV) and (VI) can be used.
It is preferable to use the compounds represented by formula (I) and general formula (VIII).

Formula (IV) [QmAun (L) p (M) q] r [In the formula, L represents a 5- or 6-membered heterocyclic ligand, and
Represents an anion group. m represents an integer of 0 to 2, n represents an integer of 1 or 2, p represents an integer of 0 to 3, q represents an integer of 1 to 3, and r represents an integer of 1 to 4. ] General formula (VII)

[0053]

[Chemical formula 22]

General formula (VIII)

[0055]

[Chemical formula 23]

In the above general formula (IV), Q represents a hydrogen atom or a cation group. Examples of the cation group include ammonium ion and alkaline metal ion. The anion group represented by Q includes a halide ion (eg, fluoride, chloride, bromide, iodide ion), perchlorate ion, borofluoride ion, sulfate ion, nitrate ion, cyanide ion, Examples thereof include groups such as thiocyanate ion and thiosulfate ion.

The 5- or 6-membered heterocyclic ligand represented by L is an anionic, cationic or neutral monocyclic group and is represented by the following general formula (V) or (VI). Selected from those shown.

General formula (V)

[0059]

[Chemical formula 24]

General formula (VI)

[0061]

[Chemical 25]

In the general formula (V), Y ₁ represents an oxygen atom, a sulfur atom, a selenium atom or a ═NR ₁ group, and Z ₁ , Z ₂ , Z ₃ and Z ₄ are each ═C (R ₂ ) R ₃ , = C
_{(R 3) -, = C} = W, = NR 1, -N = group, an oxygen atom,
Represents a sulfur atom or a selenium atom, and at least one of Z ₁ to Z ₄ represents a ═C═W group or a ═CHSH group,
And at least one is = NR ₁ , -N = group, oxygen atom,
Represents a sulfur atom or a selenium atom.

In the general formula (VI), Y ₂ each represents an oxygen atom, a sulfur atom, a selenium atom or a ═NR ₁ group, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are each = C
(R ₂ ) R ₃ , = C (R ₃ )-, = C = W, = NR ₁ , -N
= Group, oxygen atom, sulfur atom or selenium atom, and at least one of Z ₁ to Z ₄ = C = W group or =
Represents a CHSH group.

W represents an oxygen atom, a sulfur atom, a selenium atom or a = NR1 group. R1 is a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group, R ₂ and R ₃ are each an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, Heterocyclic oxy group, heterocyclic thio group, amino group, phosphonyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, imide group, carbamoyl group, sulfamoyl group, acyl group, cyano group, acyloxy group, carbamoyl Oxy group, silyloxy group,
It represents each group such as ureido group, sulfamoylamino group, nitro group, sulfonyl group, sulfinyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group and sulfonamide group.

In the general formula (V), Y ₁ , Z ₁ , Z ₂ ,
Specific examples of the 5-membered heterocyclic group formed by Z ₃ and Z ₄ include imidazole compounds (for example, 2 (3H) -imidazoline, 2-imidazolinium, 2 (3H) -imidazoline,
Groups such as imidazolium), oxazoles (eg 2
(3H) -oxazolidine, 2-oxazolinium, 2
(3H) -Oxazoline, oxazolium, etc. groups, isoxazole-based (eg, 3 (2H) -isoxazoline, 3-isoxazolium, etc.), thiazole-based (eg, 2 (3H) -thiazolidine, 2-thiazolium ,
Groups such as 2 (3H) -thiazoline, thiazolium), isothiazoles (eg, 3 (2H) -isothiazoline,
Groups such as 3-isothiazolium), selenazoles (eg, groups such as 2 (3H) -selenazolidine, selenazolium), oxazolidines (eg, 2-thio-oxazolidine-2,4dione, 2,4-oxazolidinedione, oxazolidine) -4-one, groups such as 2-oxazolidin-4-one), thiazolidine-based compounds (eg, 2-thio-thiazoline)
Groups such as -2,4-dione, 2,4-thiazolidinedione, thiazolidin-4-one and 2-thiazolin-4-one), imidazolidine series (eg 2-thioimidazolidine-2,4)
Groups such as dione, 2,4 imidazolidinedione, isothiazolidin-4-one, 2-imidazolidin-4-one), selenazolidine system (eg 2-thioselenazolidine-2,4)
-Dione, 2,4-selenazolidinedione, selenazolidin-4-one, 2-selenazolidin-4-one and the like), triazole, tetrazole and the like.

In the general formula (VI), Y ₂ ,
Specific examples of the 6-membered heterocyclic group formed by Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ include pyridine-based compounds (eg, 1,2-dihydro-2-pyridylidene, 2-pyridinium, tetrahydropyridine). -2,4-dione, tetrahydropyridine-
Groups such as 2,6-dione), pyrimidines (eg, tetrahydropyrimidine-2,4-dione, tetrahydropyrimidine-2,6-dione, hexahydropyridine-2,4,4)
6-trione, 2-thio-hexahydropyridine-2,4
6-trione, etc.), pyrazoline type (pyrazolin-5
Groups such as -one, pyrazolidine-3,5-dione) and triazine.

In the groups substituting on these rings,
The alkyl group represented by R ₁ , R ₂ and R ₃ includes, for example, methyl, ethyl, propyl, amyl, 2-ethylhexyl, dodecyl, 2-hexyldecyl, octadecyl and other straight chain / branched unsubstituted groups. A cyclic group such as cyclopentyl, cyclohexyl, or 2-carboxyethyl, 2-hydroxylethyl, 2-methanesulfonylaminoethyl, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, 2-methanesulfonylethyl, Examples thereof include substituted groups such as 3-sulfopropyl and trifluoromethyl.

In the groups substituting on these rings,
Examples of the aryl group represented by R ₁ , R ₂ and R ₃ include phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-nitrophenyl, 3-nitrophenyl and 4 -Methanesulfonylphenyl, 3-methanesulfonylaminophenyl, 2,4,6, -trichlorophenyl, 4-fluorophenyl 2-methoxyphenyl, 2-acetylaminophenyl, 2- (2-ethylureido) phenyl substitution, etc., Each unsubstituted group is mentioned.

In the groups substituting on these rings,
Examples of the heterocyclic group represented by R ₁ , R ₂ and R ₃ include 2-pyridyl, 2-furyl, 2-pyrimidyl, 2-thienyl, 5-nitro-2-thienyl, 4-methyl-2- Examples thereof include substituted and unsubstituted groups such as thiazolyl and 1-pyridinyl.

The halogen atom represented by R ₂ and R ₃ is
Examples thereof include fluorine, chlorine, bromine and iodine atoms, and examples of the alkoxy group include methoxy, ethoxy, propoxy, 2-methoxyethoxy, 2-methylthioethoxy, 2
-Methanesulfonylethoxy, 2-dodecyloxy, and other substituted and unsubstituted groups.

The aryloxy group represented by R ₂ and R ₃ is, for example, substituted or unsubstituted group such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, etc., and the heterocyclic oxy group is, for example, 1 Each group such as -phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy and the like can be mentioned.

Examples of the acyloxy group represented by R ₂ and R ₃ include acetoxy and butanoyloxy groups.
Examples of the carbamoyloxy group include groups such as methylcarbamoyloxy and phenylcarbamoyloxy, and examples of the silyloxy group include groups such as trimethylsilyloxy and dibutylmethylsilyloxy.

The alkylthio group represented by R ₂ and R ₃ includes, for example, methylthio, octylthio, tetradecylthio, octadecylthio, 3-phenoxypropylthio,
Substitution such as 3- (4-t-butylphenoxy) propylthio,
There are each unsubstituted group, and examples of the arylthio group include phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio and the like. Examples of the heterocyclic thio group include 2-benzothiazolylthio and 2,4-diphenoxy-1,3,5.
Each group such as -triazole-6-thio, 2-pyridylthio and the like can be mentioned.

Examples of the acylamino group represented by R ₂ and R ₃ include acetamide, butanamide and benzamide groups.

Examples of the amino group represented by R ₂ and R ₃ include amino, anilino, 2-hydroxyanilino, 2-mercaptoanilino, N-acetylanilino, methylamino and N, N-diethylamino. There is a basis.

Examples of the ureido group represented by R ₂ and R ₃ include 2-phenylureido, 2-methylureido, and 2,2.
Examples of the sulfamoylamino group as each group such as -dibutylureido and the like include each group such as N, N-dipropylsulfamoylamino and N-methyl-N-decylsulfamoylamino.

Examples of the sulfonamide group represented by R ₂ and R ₃ include methanesulfonamide, butanesulfonamide, hexanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, 2-methylthio-5-hydroxybenzenesulfonamide and the like. Each group of
Examples of the alkoxycarbonylamino group include groups such as methoxycarbonylamino and butoxycarbonylamino.

Examples of the carbamoyl group represented by R ₂ and R ₃ include N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-methoxyethyl) carbamoyl,
Each group such as N, N-dimethylcarbamoyl can be mentioned.

The sulfonyl group represented by R ₂ and R ₃ is
Examples include groups such as methanesulfonyl, butanesulfonyl, benzenesulfonyl, and p-toluenesulfonyl. Examples of the sulfinyl group include groups such as ethanesulfinyl and 3-phenoxypropylsulfinyl, and examples of the phosphonyl group include phenoxy group. Each group such as phosphonyl, ethoxyphosphonyl, phenylphosphonyl and the like can be mentioned.

Examples of the alkoxycarbonyl group represented by R ₂ and R ₃ include groups such as methoxycarbonyl and butoxycarbonyl, and examples of the aryloxycarbonyl group include groups such as phenoxycarbonyl and p-anisidyl. Examples of the acyl group include acetyl groups, 3-carboxypropanoyl, benzoyl, p-mercaptobenzoyl and the like.

Examples of the imide group represented by R ₂ and R ₃ include groups such as N-succinimide, N-phthalic acid imide and 3-allyl succinimide.

The general formula (VII) and the general formula (VI)
In II), R, V, W, and Y represent a hydrogen atom or a substitutable group, and X ⁻ represents an ion that cancels the intramolecular charge. l represents an integer of 1 to 3 and m represents 2 or 3. However, m-1 represents an integer of 0 to 2, and n represents the number of ions necessary to cancel the intramolecular charge.

General formula (VII) and general formula (VII
Examples of the substitutable group represented by R, V, W, and Y in I) include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylamino group, a ureido group, an amino group, an acyl group, and Represents a carboxyl group.

The alkyl group may be a linear, branched or cyclic alkyl group, and is preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl and isopropyl. , Butyl, t-butyl, i-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl group, sulfopropyl group and the like.

The aralkyl group includes, for example, a benzyl group, a phenethyl group and the like, the alkenyl group includes, for example, an allyl group and a 2-butenyl group, and the aryl group includes a phenyl group and a naphthyl group. It may be substituted with a substitutable group.

Examples of the heterocyclic group include nitrogen atom, oxygen atom,
Represents a 5 to 6 membered optionally fused heterocycle containing at least one heteroatom of a sulfur atom. The heterocycle may have a substituent such as an alkyl group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, a halogen atom (eg, fluorine, chlorine, bromine atom).

Examples of the acyl group include acetyl group and benzoyl group, examples of the acylamino group include acetylamino group and benzoylamino group, and examples of the ureido group include ureido group, methylureido group and phenylureido group. .

[0088] by X ^- as the ions to offset intramolecular charge, represented, halide ions (chloride, bromide etc.), perchloric acid ion, a hydroxide ion, p-
Toluene sulfonate ion etc. are mentioned.

Specific examples of the gold compounds represented by the general formula (IV), the general formula (VII) and the general formula (VIII) are shown below, but the present invention is not limited thereto.

[0090]

[Chemical formula 26]

[0091]

[Chemical 27]

[0092]

[Chemical 28]

[0093]

[Chemical 29]

The compound of the present invention can be synthesized by a known method, for example, Bull. Chem. Soc. Japan, 48 (3), 102.
4-9 (1975), J. Inorg. Nucl. Chem., 38 (1), 1-11 (1
076), Transition Met. Chem., 2 (6), 224-227 (197
7), JP-A 1-147537, U.S. Pat.
It can be synthesized according to the method described in No. 85.

The gold compound of the present invention is preferably added to the silver halide emulsion after being dissolved in water or a water-miscible solvent such as methanol, ethanol or fluorinated alcohol, alone or in a mixed solvent. Further, in the case of a compound which is hardly soluble in a suitable solvent, it may be added in the form of a dispersion.

Regarding the timing of adding the gold compound according to the present invention, nucleation may be carried out by mixing a silver salt and a halide salt in the place where the gold compound is present in advance, or the gold compound may be added after completion of the nucleation. You may add. The gold compound may be added so as to have a uniform concentration inside the silver halide grain,
You may control the addition amount so that it may become different concentration.

Above all, the effect of the present invention is remarkably exhibited and advantageous when a region 2 to 50 nm inside from the surface of the grain at the end of growth is added during the formation of silver halide grains. More preferably 2.5 to 20 nm from the surface of the grain after growth
It is preferable to add it in the region.

The method of adding the gold compound according to the present invention includes a method of dissolving the gold compound together with a halide salt and continuously adding it over a part or the whole of the grain forming step, or a method of mixing with a silver salt solution. It is possible to use a method of continuously adding a part or all of the grain forming step, or a method of adding the silver salt and the halide salt by an independent route.

It is advantageous that the silver halide emulsion according to the present invention contains heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt, and Group 12 metals such as cadmium, zinc, and mercury. Examples include group transition metals, and ions of lead, rhenium, molybdenum, tungsten, and chromium. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt. Above all, it is preferable to add it in the form of a complex salt to the emulsion because it is easily incorporated into the silver halide emulsion and the effect of the present invention becomes large.

When the heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

The heavy metal compounds which can be preferably used in the silver halide emulsion according to the present invention are shown below, but the present invention is not limited thereto.

(1) FeCl ₂ (2) FeCl ₃ (3) (NH ₄ ) Fe (SO ₄ ) ₂ (4) K ₃ [Fe (CN) ₆ ] (5) K ₄ [Fe (CN) ₆ ] (6) K ₂ [IrCl ₆ ] (7) K ₃ [IrCl ₆ ] (8) K ₂ [PtCl ₆ ] (9) K ₂ [Pt (SCN) ₄ (10) K ₂ [NiCl ₄ ] (11) K ₂ [PdCl ₆ ] (12) K ₃ [RdCl ₆ ] (13) CdCl ₂ (14) ZnCl ₂ (15) K ₂ [Mo (CO) ₄ (CNO) ₂ ] (16) K ₃ [Re (CNO ) ₆ ] (17) K ₃ [Mo (OCN) ₆ ] (18) K ₄ [Fe (CNO) ₆ ] (19) K ₂ [W (CO) ₄ (CNO) ₂ ] (20) K ₂ [Cr (CO) ₄ (CNO) ₂ ] (21) K ₄ [Ru (CNO) ₆ ] (22) K ₂ [Ni (CN) ₄ ] (23) PbCl ₂ (24) K ₃ [Co (NH ₃ ) ₆ ] (25) K ₅ [Co (CNO) ₁₁ ] (26) K ₃ [Re (CNO) ₆ ] (27) K ₄ [Os (CNO) ₆ ] (28) K ₂ [Cd (CNO) ₄ ] ( 29) K ₂ [Pt (CNO) ₄ ] (30) K ₃ [IrBr ₆ ] (31) K ₂ [IrBr ₆ ] (32) Ga (NO ₃ ) ₃ Heavy metal ions are added to the silver halide emulsion according to the present invention. In order to contain the heavy metal compound, the heavy metal compound may be added at any place in each step before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. The heavy metal compound may be dissolved together with the halide salt and continuously added over the whole or a part of the grain forming step, or silver bromide may be localized at a high concentration in a localized portion.

The amount of the above-mentioned heavy metal ions added to the silver halide emulsion is more preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and particularly preferably 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably not less than 5 mol and not more than 5 × 10 ⁻⁵ mol.

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. Also,
U.S. Pat.Nos. 4,183,756, 4,225,666, JP-A-55-26589,
Japanese Examined Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39 (19
It is also possible to prepare particles having a shape such as an octahedron, a dodecahedron, and a dodecahedron by the method described in the literature such as 73) and use them. 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 may be a mixture of grains having various shapes.

The grain size of the silver halide grain according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2. The range is to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on Light Microscopy, 94-122).
Page, 1955) or "Theory of Photographic Processes, 3rd Edition"
(Mies and James, co-authored, Chapter 2, Macmillan, 1966).

This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The coefficient of variation is preferably 0.22 or less, more preferably 0.12.
It is a monodisperse silver halide grain of 5 or less. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution, and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area. As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor as described in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a sulfur sensitizer.

As the sulfur sensitizer applied to the silver halide emulsion according to the present invention, thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p
-Toluene thiosulfonate, rhodanine, inorganic sulfur and the like.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of silver halide emulsion to be applied and the magnitude of expected effect, but it is 5 × 10 5 per mol of silver halide. A range of ^{−10 to} 5 × 10 ⁻⁵ mol, preferably a range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. Among these compounds, those having a fog-preventing ability that are released after the ligand is added are substantially Not included. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably 1 × 10 ^-5
The molar amount is 1 × 10 ⁻⁸ mol.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
JP-A-3-251840, AI-1 to 1 described on page 308
The dye of No. 1 is preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left column are preferable. It is preferable because it has characteristics, does not affect the photographic characteristics of the silver halide photographic emulsion, and does not cause contamination due to residual color. As specific examples of preferable compounds, the exemplified compounds (1) listed in page 3, lower left column to page 5, lower left column of the same publication
(45) can be mentioned.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it was spectrally sensitized to a specific region in the wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention.
BS-1 to BS-8 described on page 28 of JP 1840 can be preferably used alone or in combination. Examples of the green-sensitizing sensitizing dye include GS-1 to GS-1 described on page 28 of the same publication.
5 is preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When image exposure is performed by infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye needs to be used.
The dyes of IRS-1 to 11 described in 4-285950, pages 6 to 8 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the publication in combination with these dyes.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and adding it as a solution, or as a solid dispersion. Although it may be added, it is preferable to add it as a solid dispersion because the effect of the present invention is enhanced.

As a method for obtaining a solid dispersion of a sensitizing dye, other than a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system using a high speed stirring type disperser, JP-A-58-105
As described in No. 141, a method of mechanically pulverizing and dispersing into 1 μm or less fine particles in a water system under the conditions of pH 6 to 8 and 60 to 80 ° C., the surface tension described in Japanese Patent Publication No. 60-6496 is 38 dyne / It is possible to use a method of dispersing in the presence of a surfactant whose size is kept below cm.

As a dispersion device that can be used for preparing a dispersion liquid, for example, Japanese Patent Laid-Open No. 4-125631 can be used.
In addition to the high-speed stirring type disperser shown in the figure, a ball mill, a sand mill, an ultrasonic disperser, etc. may be mentioned.

Further, in using these dispersing devices, as described in JP-A-4-125632, a method such as performing a pretreatment such as dry pulverization in advance and then performing a wet dispersion may be adopted.

As the coupler used in the silver halide photographic light-sensitive material of the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm is formed by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
The general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC-1 on pages 18 to 21 of the publication.
To those described as CC-9 can be mentioned.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a general formula (M-
Examples thereof include couplers represented by I) and (M-II). Specific compounds are described in MC-1 on pages 13 to 16 of the publication.
To those described as MC-11 can be mentioned. Among them, MC- described in pages 15 to 16 of the same publication
8 to MC-11 are preferable because they are excellent in reproducing colors from blue to purple and red, and are also excellent in detail descriptive power.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (Y-
The couplers represented by I) can be mentioned. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the publication. Above all, the publication 11
YC-8 and YC-9 described on the page are preferable because they can reproduce yellow of a preferable color tone.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic-solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. The water-insoluble organic solvent-soluble polymer used at this time is poly (Nt-
Butyl acrylamide) and the like.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-1 described in JP-A-4-114152, page 33)
1), compounds such as the compound (A'-1) described on page 35 of the same publication can be used. Other than this, US patents
The fluorescent dye-releasing compounds described in 4774187 can also be used.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin, etc. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

Any material may be used as the support for the silver halide photographic light-sensitive material of the present invention. White pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, polypropylene containing white pigment. ,
A polyethylene terephthalate support or the like can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina,
Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support is preferably 10% by weight or more, more preferably 13% by weight or more as the content in the water-resistant resin layer. Is preferred, and more preferably 15% by weight or more. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be determined according to
It can be measured by the method described in Japanese Patent No. 28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

The silver halide photographic light-sensitive material according to the present invention may be directly or undercoated (adhesiveness of the surface of the support) after corona discharge, ultraviolet irradiation, flame treatment or the like on the surface of the support, if necessary. Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

In the silver halide photographic light-sensitive material of the present invention, various hardeners are used for the purpose of preventing damage or dissolution of the film during processing. As these hardeners, many compounds such as epoxy compounds, aziridine compounds, acryloyl compounds, vinylsulfonyl compounds, chlorotriazine compounds are known, and the silver halide photographic light-sensitive material according to the present invention. Any known hardener can be preferably used for the above. Among these hardeners,
Carboxyl group-activating low-molecular hardeners are preferred because they have a fast-acting effect and the resulting coating strength is high.

Examples of the carboxyl group-activating hardener include compounds of the general formulas (HI) to (H-VIII) described on pages 10 to 17 of Japanese Patent Application No. 4-4946. . Furthermore, in addition to the compounds represented by these general formulas, JP-A-50-38540, 52-93470, 56-43353,
The compounds described in JP-A-58-113929 and US Pat. No. 3,321,313 can also be mentioned. Specific compounds of the carboxyl group-activating low-molecular hardener are disclosed in JP-A-62-286034.
(H-1) to (H-6) described on pages 13 to 16 of the issue
0) can be mentioned.

Among the carboxyl group-activating low molecular hardeners, the compounds represented by the general formula (HI) are disclosed in JP-A-49-519.
No. 45, No. 51-59625, No. 61-9641, No. 62-262854, No.
It can be synthesized by the method disclosed in, for example, 62-264044. Similarly, the compound represented by the general formula (H-II) is disclosed in JP-A-51-126125 and JP-A-52-48311, and the compound represented by the general formula (H-III) is disclosed in JP-A-57-44140. ,
Japanese Patent Publications No. 57-46538 and No. 58-50669 have the general formula (HI
The compound represented by V) is described in JP-A-52-54427, and the compound represented by the general formula (HV) is disclosed in JP-A-60-225148 and JP-A-6-225148.
The compounds represented by the general formula (H-VI) in 1-240236 are described in JP-A Nos. 62-68866 and 62-68867, and are described in the general formula (H-VI).
The compounds represented by I) are described in JP-A-61-128241, and
The compound represented by formula (H-VIII) is described in JP-A-62-2.
No. 34152, the respective synthetic methods are disclosed.

The amount of the carboxyl group-activating type hardener used is
It can be arbitrarily selected according to the purpose. Usually, it can be used in a proportion of 0.01 to 10% by weight based on dry gelatin. It is particularly preferably used in a proportion of 0.05 to 5% by weight.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed by changing the intensity of the laser light based on digital information and scanning.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4-Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) Aniline CD-6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfone Amido CD-8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl-N- Ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the color developing solution, in addition to the above color developing agent, , Known developer component Compounds can be added. Usually pH
A buffering alkali agent, a chloride ion, a development inhibitor such as benzotriazole, a preservative, and a chelating agent are used. The color development temperature of the silver halide photographic light-sensitive material of the present invention is usually 15 ° C. or higher, and generally 20
The range is up to 50 ° C. In addition, it is preferable that the temperature is 30 ° C. or higher for rapid treatment.

The color development time of the silver halide photographic light-sensitive material according to the present invention is generally 10 seconds to 4 minutes, but in the case of rapid processing, it is less than 30 seconds, in the range of 10 to 30 seconds. Is preferably carried out.

When the silver halide photographic light-sensitive material according to the present invention is subjected to a running process while continuously replenishing the color developing solution, in order to reduce the overflow solution of the color developing solution and to reduce the environmental damage due to the waste solution. In particular, the replenishing amount of the color developing solution is preferably 20 to 150 ml / m ² of the light-sensitive material. Further, it is more preferable to set the replenishment amount so that waste liquid due to overflow is not substantially generated, and the concrete replenishment amount is 20 per 1 m ² of the light-sensitive material.
More preferably, it is -60 ml.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. The development processing device used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is sandwiched between rollers arranged in a processing tank, and a photosensitive material may be used for the belt. It may be an endless belt method of fixing and transporting, but a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and the photosensitive material is transported, and the processing solution is atomized. Spray method,
A web method by contact with a carrier impregnated with a treatment liquid,
A method using a viscous treatment liquid can also be used.

[0149]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 500 mg of the exemplified compound (I-15) was added to 100 ml of ethanol and stirred to prepare a completely dissolved solution to obtain an addition solution F-1.

Similarly, an additive solution was prepared as follows.

(Preparation of Additive Solution F-2) The exemplified compound (I-1
5) 500 mg and 400 mg of sodium carbonate were added to 100 ml of pure water and stirred to completely dissolve it.

(Preparation of Additive Solution F-3) The exemplified compound (I-1
5) 500 mg and 150 mg of sodium carbonate were added to 100 ml of pure water and stirred to completely dissolve it.

(Preparation of Additive Solution F-4) The exemplified compound (I-1
5) 500 mg and 50 mg of sodium carbonate were added to 100 ml of pure water and stirred to completely dissolve it.

An additive solution was prepared for the exemplified compound (I-10) as follows.

(Preparation of Additive Solution F-5) The exemplified compound (I-1
0) 500 mg was added to 100 ml of ethanol and stirred to completely dissolve it.

(Preparation of Additive Solution F-6) The above exemplified compound (I-1
O) 500 mg and sodium carbonate 350 mg were added to 100 ml of pure water and stirred to completely dissolve.

(Preparation of Additive Solution F-7) The exemplified compound (I-1
0) 500 mg and 120 mg of sodium carbonate were added to 100 ml of pure water and stirred to completely dissolve it.

(Preparation of Additive Solution F-8) The above exemplified compound (I-1
0) 500 mg and 20 mg of sodium carbonate were added to 100 ml of pure water and stirred to completely dissolve it.

The pH and dissociation degree of each of these additive liquids (F-1) to (F-8) were measured immediately after dissolution, 2 hours later, and 4 hours later. The results are shown below.

[0161]

[Table 1]

As can be seen from Table 1, a solution having a low dissociation degree of the antifoggant and a water solvent is not stable in pH and dissociation degree. It can be seen that the pH and dissociation degree of the solution are stable in the aqueous solution prepared so that the dissociation degree is 0.99 or more. In the conventional method of dissolving with ethanol, the pH was stable, but the dissociation degree was 0.99 or less.

Example 2 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

Magenta coupler (M-1) 17.5 g, additive (ST-1) 7.5 g, (ST-2) 7.5 g, (ST-3)
To 7.5 g and 10.0 g of high boiling organic solvent DNP (dinonyl phthalate), 60 ml of ethyl acetate was added and dissolved.
A magenta coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 15.0 ml of 5% surfactant (SU-1) using an ultrasonic homogenizer.

This dispersion was mixed with a silver halide emulsion (Em-G1) (containing 8.50 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second layer coating liquid was also prepared in the same manner as the first layer coating liquid. In addition, the second layer (H
-1) was added. As a coating aid, a surfactant (S
U-2) and (SU-3) were added to adjust the surface tension.

Sample 201 was prepared as described above. The layer structure is shown in Table 2 below.

[0167]

[Table 2]

[0168]

[Chemical 30]

(Preparation of silver halide emulsion) In 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were simultaneously added over 30 minutes while controlling pAg = 6.5 and pH = 3.0. Add (C solution) and (D solution) below to pAg
= 7.3 and pH = 5.5 were added simultaneously over 120 minutes. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water is added to make up to 200 ml. (Solution B) Silver nitrate 10g Add water to make 200ml. (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water is added to make 600 ml. (Solution D) Silver nitrate 300g Add water to make 600ml. After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N and a 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.43 μm and a coefficient of variation (S / R). ) = 0.07 and a silver chloride content of 99.0 mol%, to obtain a monodisperse cubic emulsion (EMP-201).

The above emulsion (EMP-201) was chemically ripened at 55 ° C. for 90 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-G201). The antifoggant was added by the additive solution (F-1) of Example 1 when the chemical ripening was stopped. Sensitizing dye GS-
1 was added as a methanol solution.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Addition of antifoggant in preparation of green-sensitive emulsion (Em-G201) Green-sensitive emulsions (Em-G202) to (Em-G210) were prepared in the same manner except that the amount and the addition liquid were changed as shown below.

In preparing Sample 201, a green-sensitive emulsion (Em-G20
Samples 202 to 210 were prepared in the same manner except that green-sensitive emulsions (Em-G202) to (Em-G210) were used instead of 1).

These samples were subjected to optical wedge exposure by an ordinary method with an exposure time of 1 second, and then developed by the following developing process. In addition, a product which was subjected to development processing in the following development processing step without being exposed was also prepared.

The processing steps are shown below.

Treatment process Treatment temperature Time Replenishment amount Color development 35.0 ± 0.3 ℃ 45 seconds 162ml / m ² Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds 216ml / m ² Water wash 30-34 ° C 90 seconds 248ml / m ² Dry 60-80 ° C The composition of the developing solution for 60 seconds is shown below.

Color developer tank solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine tetra Acetic acid 1.0g Catechol-3,5-diphosphonate disodium 1.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4 ' -Diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to bring the total volume to 1 liter, and adjust the pH to 10.60 with potassium hydroxide or sulfuric acid.

Color developer replenishing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5 -Disodium diphosphonate 1.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.3 g Potassium carbonate 30 g Add water to bring the total volume to 1 liter, and adjust to pH = 10.60 with potassium hydroxide or sulfuric acid.

Bleach-fixing solution Tank solution and replenishing solution Ethylenediaminetetraacetic acid Ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to bring the total volume to 1 Adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

Washing liquid tank liquid and replenishing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Water Ammonium oxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

The green density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation). The sensitivity and gradation of the sample subjected to optical wedge exposure were determined. Sensitivity is density
It was defined based on the reciprocal of the exposure amount that gives 0.75 and expressed as a relative value with the sensitivity of Sample 201 as 100. The gradation is represented by the slope of density 2.0 and density 1.0 of the characteristic curve. The fog value was obtained from the unexposed sample. The fog value was the density value of the unexposed sample.

[0182]

[Table 3]

In the sample to which the antifoggant was added by the ethanol solution without adjusting the dissociation degree to 0.99 or more, the gradation was hard, but the fog was slightly high. If the addition amount is increased so that the fog is reduced, the sensitivity is remarkably lowered. On the other hand, the dissociation degree is 0.
The sample added with an aqueous solution of 99 or less has high fog and soft gradation. On the other hand, in the sample in which the antifoggant of the present invention is added in the form of an aqueous solution having a dissociation degree of 0.99 or more, the fog is low, the gradation is hard, and the sensitivity is high.

As described above, according to the present invention, the necessary antifoggant ability can be imparted to the silver halide light-sensitive material with a small amount of antifoggant, and further, high sensitivity and high gradation are provided, resulting in high image quality. It can be seen that it is possible to give an image.

Example 3 In the preparation of (EMP-201) of Example 2, addition of Example 1 after addition of (Solution A) and (Solution B) and before addition of (Solution C) and (Solution D) A monodispersed cubic emulsion (EMP-301) having an average particle size of 0.43 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained in the same manner except that the liquid (F-5) was added. It was The addition amount of the antifoggant was 1 × 10 ⁻⁴ (mol / mol AgX).

Immediately after emulsion preparation, the above emulsion (EMP-301) was chemically ripened at 55 ° C. for 90 minutes to give a green-sensitive silver halide emulsion (Em-G301). Sensitizing dye GS-1
Was added as a methanol solution.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX In the preparation of Sample 201 of Example 2, a green light sensitive emulsion (Em -G
201) was changed to a green photosensitive emulsion (Em-G301), and sample 3 was similarly used.
01 created. Further, in the preparation of Sample 301, after preparing the silver halide emulsion (EMP-301) and leaving it at 60 ° C. for 2 hours, chemical sensitization was carried out in the same manner as the green photosensitive emulsion (Em-G301).
A sample 302 was prepared by applying in the same manner as the sample 301. (EMP-301)
(EMP-302) to (EM) in the same manner except that the additive solution (F-5) added in the preparation of Example 1 was changed to the additive solutions (F-6) to (F-8) of Example 1.
P-304) was prepared.

In the preparation of the green photosensitive emulsion (Em-G301) (EM
Green photosensitive emulsions (Em-G302) to (Em-G304) were prepared in the same manner except that (P-301) was changed to (EMP-302) to (EMP-304).

Samples 303 and 304 were prepared in the same manner as in Samples 301 and 302, except that the green photosensitive emulsion (Em-G301) was changed to the green photosensitive emulsion (Em-G302). Green sensitive emulsion as well
(Em-G303), green photosensitive emulsion (Em-G304)
5, 306 and samples 307, 308 were prepared.

The sensitivity, gradation and fog of these samples 301 to 308 were evaluated in the same manner as in Example 2, and the emulsion was allowed to stand at 60 ° C. for 2 hours from the change in these values between sample 302 and sample 301. The resulting changes were evaluated. The change after standing was evaluated as follows. Sensitivity was expressed as a change rate with respect to that which was exposed and developed immediately after preparation of the sample, and gradation and fog were expressed as a difference with respect to what was exposed and developed immediately after preparation of the sample. The results are shown below.

[0191]

[Table 4]

In the sample added with the additive solution in which the dissociation degree of the antifoggant is 0.99 or more, the increase of the fog by leaving the emulsion at 60 ° C. for 2 hours is small, and is smaller than the sample added in the ethanol solution. I understand. Furthermore, it can be seen that the increase in sensitivity and the softening of gradation seen in the sample added with the ethanol solution are not seen in the sample added with the additive solution having a dissociation degree of the antifoggant of 0.99 or more. On the other hand, it can be seen that not only the fog is increased but also the gradation and sensitivity are greatly changed in the sample added with the additive solution in which the dissociation degree of the antifoggant is 0.99 or less.

Example 4 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Sample 401 was prepared by coating each layer having the following constitution on the reflective support to prepare a multilayer silver halide photographic light-sensitive material. As the green light-sensitive silver chlorobromide emulsion added to the third layer, the green light-sensitive silver halide emulsion of Example 2 (Em-G201) was used.

As a hardening agent, (H-2) was added to the second and fourth layers, and (H-1) was added to the seventh layer. Surfactants (SU-1) and (SU-3) were added as coating aids to adjust the surface tension.

The layer structure is as shown in the table below.

[0196]

[Table 5]

[0197]

[Table 6]

[0198]

[Chemical 31]

[0199]

[Chemical 32]

PVP Polyvinylpyrrolidone DIDP Di (iso-decyl) phthalate HBS-11-dodecyl-4- (p-toluenesulfonamide) benzene DOP Dioctylphthalate (Preparation of blue-sensitive silver halide emulsion) Emulsion of Example 2 ( EMP
-201) was prepared in the same manner except that the addition times of (Solution A) and (Solution B) and the addition times of (Solution C) and (Solution D) were changed. As a result, average particle size 0.85μm, coefficient of variation (S / R) = 0.07, silver chloride content
A 99.0 mol% monodisperse cubic emulsion (EMP-401) was obtained.

Next, the above emulsion (EMP-401) was chemically sensitized with the following compound at 55 ° C. for 130 minutes to obtain a blue-sensitive silver halide emulsion (Em-B401). The sensitizing dye was added in an ethanol solution.

Sodium thiosulfate 0.15 mg / mol AgX chloroauric acid 0.5 mg / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX ( Method for preparing red-sensitive silver halide emulsion) Emulsion of Example 2
In the preparation of (EMP-201), the average particle size was 0.50 μm and the coefficient of variation was the same except that the addition time of (A solution) and (B solution) and the addition time of (C solution) and (D solution) were changed. (S / R) = 0.0
8. Monodisperse cubic emulsion with silver chloride content of 99.0 mol% (EMP-40
2) got.

Further, a silver halide emulsion (EMP-402) was chemically sensitized with the following compounds at 60 ° C. for 120 minutes,
A red-sensitive silver halide emulsion (Em-R401) was obtained. The sensitizing dye was added in an ethanol solution.

Sodium thiosulfate 0.2 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Sensitizing dye RS-1 2 × 10 ⁻⁴ mol / mol AgX

[0205]

[Chemical 33]

In the same manner as in the preparation of Sample 401, the green-sensitive silver halide emulsions (Em-G202) to (Em-G210) of Example 2 were used instead of the green-sensitive silver halide emulsion (Em-G201). Samples 402-410 were made. The obtained sample was exposed and developed in the same manner as in Example 2, the green density was measured, and the sensitivity, gradation and fog were evaluated. The sensitivity was expressed as a relative sensitivity with the sensitivity of Sample 401 being 100. The results are shown below.

[0207]

[Table 7]

It can be seen that the sample added with the additive solution of the present invention having a dissociation degree of 0.99 or more has high sensitivity, high gradation, and low fog even in the multi-layer.

Example 5 A sample was prepared in the same manner as in Example 4, except that the following green-sensitive silver halide emulsion (Em-G501) was used in place of the green-sensitive silver halide emulsion (Em-G201). Created 501.

(Preparation of Green-Sensitive Silver Halide Emulsion (Em-G501)) The emulsion (EMP-201) of Example 2 was chemically sensitized with the following compound at 55 ° C. for 130 minutes to give a green-sensitive halogen. A silver halide emulsion (Em-G501) was obtained. The sensitizing dye GS-1 was added as a methanol solution.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Sample 501 was prepared in the third layer to prepare an exemplary compound (I-10 ) Was added in the same manner as in Example 1 except that the addition solution (F-5) of Example 1 was added to 0.1 (g / m ² ). Similarly sample 5
In the preparation of 02, instead of the additive solution (F-5), the additive solutions (F-6) to (F-8) of Example 1 and the following additive solutions (F-9) to (F-18) were used. Samples 503-515 were prepared in the same manner except for. Additive solution (F
-9) to (F-18) were prepared in the same manner as the additive solution (F-2) of Example 1 using the types and amounts of the additives shown in the table below.
Table 8 below shows the types of additives used, the amount added, and the degree of dissociation.

[0212]

[Table 8]

Samples 501 to 515 were exposed and developed in the same manner as in Example 4, and the sensitivity and fog were evaluated. The sensitivity was expressed as a relative value with the sensitivity of each photosensitive layer of Sample 502 being 100. Further, the obtained sample was temporarily stored at 60 ° C. under the condition of 40% relative humidity for 1 week, and then exposed and developed in the same manner as in Example 4 to obtain the sensitivity of green density, gradation and fog, and Changes in the green density sensitivity, gradation, and fog during storage of the exposed and developed samples were determined. Sensitivity is expressed as a relative value, with exposure and development processed immediately after sample preparation as 100, and gradation is a decrease from that exposed and developed immediately after sample preparation, and fog is expressed as an increase. . The results are shown below.

[0214]

[Table 9]

In the comparative sample in which the antifoggant was added to the third layer in the ethanol solution without adjusting the dissociation degree to 0.99 or more, the sensitivity of the green photosensitive layer was low, and the sensitivity of the red photosensitive layer and the blue photosensitive layer was further improved. You can see that it will lower it. Dissociation degree is 0.
It can be seen that in the comparative sample added with the additive liquid of 99 or less, the sensitivity of the green photosensitive layer is slightly low and the fog is slightly high. However, the sample added by the additive solution having the dissociation degree of 0.99 or more according to the present invention has high sensitivity of the green photosensitive layer and low fog, and the sensitivity of the red photosensitive layer and the blue photosensitive layer is different from that of the antifoggant. It is similar to the sample without addition, and it can be seen that there is little adverse effect on other emulsion layers.

Regarding the change in performance during storage, in the case where the antifoggant was not added to the third layer, an extreme increase in fog, softening of gradation and increase in sensitivity were observed during storage. In the sample added as an ethanol solution, the increase in fog can be suppressed to some extent, but it is insufficient, and the gradation becomes softer. When the dissociation degree is 0.99 or less, the fog increases,
The softening of the gradation is largely seen. The dissociation degree of the present invention is 0.99
It can be seen that the sample added with the above-described additive solution has sufficiently suppressed fog and small changes in sensitivity and gradation.

Example 6 The following (E) was added to 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C.
Solution) and (F solution) are simultaneously added over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and further (G solution) and (H solution) below.
Was simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide. Then, (solution I) and (solution J) were simultaneously added over 2 minutes. Thus, the average particle size is 0.43μ
m, coefficient of variation (S / R) = 0.08, silver chloride content 99.0 mol%
A monodisperse cubic emulsion EMP-601 was obtained. Analysis using X-ray revealed that the maximum value of the silver bromide content in the portion containing a high concentration of silver bromide was 31 mol%.

(Solution E) 3.44 g of sodium chloride Water is added to make up to 200 ml.

(Solution F) Silver nitrate 9.9 g Add water to make up to 200 ml. (Solution G) Sodium chloride 103.2g (Solution K) 50ml Add water to make 600ml. (Solution H) Silver nitrate 297g Add water to make 600ml. (Solution I) 2.17 g potassium bromide Add water to make 15 ml. (Solution J) 3.1g silver nitrate Add water to make 15ml. (I solution) and (J solution) in the preparation of the above emulsion (EMP-601)
(EMP-602) to (EMP-603) were prepared in the same manner except that the antifoggant was added in the amount shown in the table below with the addition liquid (F-15), and the addition liquid (F-16 (EMP-604) to (EMP-605) were prepared in the same manner except that the addition amount shown in Table 10 below was added. The dissociation degree is shown in Table 10.

[0220]

[Table 10]

Next, the above emulsions (EMP-601) to (EMP-605) were chemically sensitized with the following compounds at 55 ° C. for 130 minutes to produce green-sensitive silver halide emulsions (Em-G601) to ( Em-G605) was obtained. The sensitizing dye GS-1 was added as a methanol solution.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX In the preparation of Sample 401 of Example 4, a green-sensitive silver halide emulsion ( Instead of (Em-G201), a green-sensitive silver halide emulsion (Em-G201)
601) to (Em-G605) in the same manner as in Samples 601 to 605.
It was created.

The samples 601 to 612 were exposed and developed in the same manner as in Example 4 to evaluate the sensitivity and fog of the green-sensitive layer. The sensitivity of the green-sensitive layer was expressed as a relative value with the sensitivity of Sample 401 being 100. Further, the pressure characteristic during drying was evaluated by the following method.

(Evaluation of pressure characteristics during drying) Sphere diameter 0.1 mm
Stand the ball point needle on the sample surface vertically
The ball point needle was simultaneously loaded while moving in parallel at a speed of 1 cm / sec.

Thereafter, each sample was subjected to optical wedge exposure in the same manner as in Example 3 and then subjected to development processing to determine the color density of the pressure-applied portion and the non-pressure-applied portion at a color development density of about 0.3 in Konica stock. The following evaluation was performed by measuring with a company-made microdensitometer (PDM-5). In this case, the smaller the dD value, the better the pressure resistance.

DD = (concentration of pressured portion)-
(Concentration of the part where pressure was not applied) The results are shown below.

[0227]

[Table 11]

In the case of an emulsion in which silver bromide was localized, the sensitivity was high, but there was a defect in the pressure characteristic during drying. Exemplified compound (I
Although the pressure characteristics are improved by adding I-2) to the localized portion, it is slightly desensitized. When the additive of the present invention is used, there is little desensitization when improving the pressure characteristics. Further, it can be seen that the pressure characteristics are further improved by increasing the addition amount.

Example 7 In the preparation of the silver halide emulsion (EMP-301) of Example 3, the exemplified compound (IV-23) was added to the (D liquid) (EMP-701).
To prepare a green-sensitive silver halide emulsion (Em-G301) to (Em-G30
Chemical sensitization was performed in the same manner as 4) to obtain (Em-G701) to (Em-G704). (EMP-701) average particle size, the coefficient of variation is the same as (EMP-201), exemplary compound added during the formation of silver halide grains
The amount of (IV-23) was 5 × 10 ^-7 mol per mol of silver halide. In the preparation of Samples 301 to 308 of Example 3, Samples 701 to 708 were prepared in the same manner by using the above-mentioned green-sensitive silver halide emulsions (Em-G301) to (Em-G304). These samples were tested for sensitivity, gradation, fog and emulsion at 60 ° C as in Example 3.
The performance change due to leaving for 2 hours was evaluated. The results are shown below.

[0230]

[Table 12]

The samples using the emulsion in which the gold compound was present in the grains were high in sensitivity, but the fog generated when the emulsion was stored at high temperature was larger than that in the case where the emulsion did not contain gold. When the antifoggant is added to the solution in which the dissociation degree is not adjusted, the fog is still increased and the sensitivity is largely changed. In the sample to which the antifoggant was added by the additive solution in which the dissociation degree according to the present invention was adjusted to 0.99 or more, the fog that occurs during storage of the emulsion at high temperature can be suppressed without changing the characteristics of the high sensitivity, and the high sensitivity can be obtained. It can be seen that a high-quality silver halide photographic light-sensitive material can be produced.

Example 8 In the preparation of the sample 501 of Example 5, the addition solution of the sensitizing dye used in the preparation of the green-sensitive silver halide emulsion was added with the following sensitizing dye in the form of solid fine particles. Sample 801 was prepared in the same manner except that the liquid was replaced with a liquid. For Samples 502 to 505, samples 802 to 805 were prepared in the same manner by changing the sensitizing dye addition liquid to the addition liquid in which the following sensitizing dye was present as solid fine particles. The blue-sensitive silver halide emulsion of Example 4 (Em-B40
In the preparation of 1), the addition liquid of the sensitizing dye is changed to the addition liquid in which the sensitizing dye is present as solid fine particles, and the antifoggant is added with the addition liquid of the following table to 6 × 10 ⁻⁴ mol / mol AgX. A blue-sensitive silver halide emulsion was prepared in the same manner except that it was added as described above and coexisted during chemical ripening, and was used instead of the blue-sensitive silver halide emulsion (Em-B401) of Sample 502 of Example 5. Samples 806 to 809 were prepared in the same manner. Similarly, Example 4
For the red-sensitive silver halide emulsion (Em-R401) of Sample No. 810 to 8
Created 13.

(Preparation of Additive Solution of Green Sensitizing Dye) Sensitizing Dye GS-1 1.5 g Water 100 ml The above mixture was thermostated at 40 ° C. and the high speed shown in FIG. 1 of JP-A-4-125631. The mixture was dispersed with a stirring type disperser at 5000 rpm for 120 minutes to obtain a dispersion liquid.

(Preparation of Additive Solution of Blue Sensitizing Dye) Sensitizing Dye BS-1 1.5 g Sensitizing Dye BS-2 0.4 g Water 100 ml The above mixture was adjusted to 40 ° C. A high-speed stirring type disperser shown in FIG. 1 was used to disperse the dispersion liquid at 5,500 rpm for 100 minutes to obtain a dispersion liquid.

(Preparation of Additive Solution of Red Sensitizing Dye) Sensitizing Dye RS-1 0.8 g Water 100 ml The above mixture was adjusted to 40 ° C., and the high speed shown in FIG. 1 was used. A stirring type disperser was used to disperse the mixture at 5000 rpm for 150 minutes to obtain a dispersion.

[0236]

[Table 13]

The sensitivity, gradation and fog of Samples 801 to 813 were evaluated in the same manner as in Example 4. The sensitivity was expressed as a relative value with the sensitivity of each photosensitive layer of Sample 802 being 100. In addition, prepare a sample that was applied after being stored in the state of the coating solution at 40 ° C for 2 hours, and then prepare the coating solution immediately after the preparation.
The evaluation of the change in fog was performed as follows. Sensitivity was expressed as a relative value by setting the value of 100 which was exposed and developed immediately after preparation of the sample as 100, and the fog was expressed as an increase from that which was exposed and developed immediately after preparation of the sample. The results are shown below.

[0238]

[Table 14]

The sensitizing dye using the additive liquid present in the form of solid fine particles has a higher gradation than the sample added with the solution of methanol or ethanol, and a higher quality image can be obtained. It was confirmed that the change in performance due to the storage of the liquid was small, and it was found that this is a preferred embodiment of the present invention. Furthermore, the effect of the present invention was obtained regardless of the sensitizing dye.

Example 9 Samples 501 to 515 of Example 5 were exposed in the same manner as in Example 2, and development processing was performed by the following processing steps until the tank was filled with the color developer. , Processing using the processing liquid in the following processing steps, sensitivity, gradation,
Fog and maximum color density were evaluated.

The processing steps are shown below.

Treatment process Treatment temperature Time Replenishment amount Color development 39.0 ± 0.3 ℃ 25 seconds 40ml / m ² Bleach fixing 35.0 ± 0.5 ℃ 30 seconds 51ml / m ² stability 30-34 ℃ 90 seconds 250ml / m ² (3 tank cascade ) Drying 60 to 80 ° C 60 seconds The composition of the development processing solution is shown below. Stabilization was supplemented by the countercurrent system of stable tank 3 → 1.

Color developer tank solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 3.6 g Potassium chloride 4.5 g Potassium sulfite 0.4 g Diethylenetriamine pentaacetic acid 5.0 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline sulfate 6.0 g Potassium carbonate 25 g Add water to bring the total volume to 1 liter, and adjust to pH = 10.10 with sulfuric acid or potassium hydroxide.

Color developer replenisher Pure water 800 ml Triethanolamine 14 g N, N-diethylhydroxylamine 5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 12 g Potassium carbonate Add 35g water to make the total volume 1 liter and adjust the pH to 10.60 with sulfuric acid or potassium hydroxide.

Bleach-fixing solution Tank solution and replenishing solution Ethylenediaminetetraacetate Ammonium dihydrate 53g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 123g Ammonium sulfite (40% aqueous solution) 51g Water is added to bring the total volume to 1 liter. And adjust the pH to 5.4 with aqueous ammonia or glacial acetic acid.

Stabilizer tank solution and replenisher o-Phenylphenol 0.1g Ubitex (Ciba Geigy) 1.0g Zinc sulfate heptahydrate 0.1g Ammonium sulfite (40% aqueous solution) 5.0ml 1-Hydroxyethylidene-1,1 -Diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Add water to bring the total volume to 1 liter and adjust the pH to 7.0 with ammonia or glacial acetic acid.

[0247]

[Table 15]

In the comparative sample in which the antifoggant was added to the third layer in the ethanol solution without adjusting the dissociation degree to 0.99 or more, the reduction in the sensitivity of the red photosensitive layer and the blue photosensitive layer was stronger than that of Example 5. I understand. However, the samples added by the additive solution having the dissociation degree of 0.99 or more of the present invention have the sensitivity of the red photosensitive layer and the blue photosensitive layer equal to those of the sample to which the antifoggant is not added, and the fog is low. It can be seen that even in the processing of the present embodiment in which the replenishment amount is small and the development time is short, the adverse effect on other emulsion layers is small. It can be seen that in the comparative sample added with the additive having a dissociation degree of 0.99 or less, the sensitivity is low, the fog is high and the maximum color density is low in a short developing time. The silver halide photographic light-sensitive material of the present invention has a small replenishment amount,
It turns out that it gives an excellent image.

[0249]

The silver halide photographic light-sensitive material according to the present invention has high sensitivity, low fog, high gradation, high-quality images, and the amount of organic solvent used during production. Few.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area // G03C 1/74

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material, which is formed by adding an antifoggant as a solution having a dissociation degree of 0.99 or more. 2. A silver halide photographic light-sensitive material according to claim 1, which contains a high silver chloride emulsion. 3. The antifoggant according to claim 1 has a dissociation degree of 0.
2. The method according to claim 1, wherein the solution is formed by adding 99 or more solutions from the end of the nucleation step of the silver halide grains contained in the silver halide emulsion layer to the end of the coating solution adjusting step. Item 2. A silver halide photographic light-sensitive material according to item 2. 4. A solution in which the silver halide grains contained are high silver chloride grains having localized portions having different silver bromide contents in a part of the grains, and the antifoggant has a dissociation degree of 0.99 or more. A silver halide photographic light-sensitive material, which is formed by adding during the period from the completion of the nucleation step of the silver halide grains to the completion of the coating solution adjusting step. 5. The silver halide grains contained are high silver chloride grains containing a gold compound inside the grains, and the solution of the antifoggant has a dissociation degree of 0.99 or more. A silver halide photographic light-sensitive material, which is added and formed between the end of the forming step and the end of the coating solution adjusting step.