JPH11143011A - Photographic additive, silver halide photographic emulsion and photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic additive and to obtain a silver halide photographic emulsion and a photographic sensitive material having high sensitivity, hardly showing variation in fog and sensitivity during storage after chemical sensitization and variation in sensitivity during retention before the application of the emulsion. SOLUTION: The photographic additive consists of at least one of cations of alkali metals and alkaline earth metals and at least one of anions as shown below. It is added by >=0.1 mol per mol silver halide respectively during chemical aging.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic additive, a halogenated compound having a high sensitivity, which reduces fog and sensitivity fluctuation during storage over time after completion of chemical sensitization, and has a small sensitivity fluctuation when the emulsion is stagnation before coating. Silver photographic emulsions and photographic materials (hereinafter referred to as
It may simply be a light-sensitive material or a light-sensitive material. ).

[0002]

2. Description of the Related Art In recent years, rapid processing has progressed, and a large amount of photosensitive material for printing has been rapidly processed. Rapid processing is a very strong demand in the color photographic industry, and numerous improvements have been made, with new systems being developed every few years.

[0003] Acceleration of processing includes color development, bleach-fixing,
It is necessary to separately devise the time for each of the washing and drying processes. As a method of accelerating the processing, for example, WO 87-04534 discloses a method of rapidly processing a color photographic light-sensitive material using high silver chloride silver halide as a photographic emulsion. From the viewpoint, it is indicated that it is preferable to use a high silver chloride emulsion.

In the market, the number of installation points of mini-labs of the rapid processing type has been increasing year by year with the rapid development processing. Along with this, there is an increasing number of cases in which color prints are created at stores other than photo specialty stores, such as a service where a print can be handed over to a client at a resort. As a result, the amount of color paper consumed in minilabs is increasing year by year, and the sensitivity and gradation are always constant and uniform so that even people without specialized skills can easily print under the same conditions. There is a demand for a stable supply of color paper.

[0005] In order to supply stable color paper, an emulsion production batch has been expanded. However, when the emulsion production batch is expanded, the performance fluctuation due to the dispersion during the emulsion production is improved, but the storage period of the emulsion also becomes longer, and if the performance fluctuation occurs by the time of actual coating, the performance fluctuation of the color paper will eventually result. There is a problem that becomes large. In addition, in order to ensure stable photographic performance, it is necessary to change the performance of the solution before emulsion coating, that is, to stabilize the stagnation of the coating solution.

JP-A-1-124845 discloses a technique in which bromide is added in the presence of a specific sensitizing dye to improve the stagnation of a coating solution and the storage stability of a product. However, this technique is a technique for improving the stability of a coating solution and the storage stability of a light-sensitive material after coating, and has insufficient effect on performance variations occurring before an emulsion is made into a solution. Similarly, Japanese Patent Application Laid-Open No. 2-131233 discloses a technique for improving sharpness and storage stability of a product by adding potassium bromide in the presence of a specific dye. It is intended to prevent performance fluctuation due to later storage over time, and is insufficient in terms of compatibility with improvement in performance variation before the emulsion is made into a solution.

[0007] Also, Japanese Patent Application Laid-Open No. 8-194277 and the like disclose:
Although a technique using a radical scavenger for the purpose of improving production stability and storage stability is disclosed, the effect of improving the performance of a photosensitive material to which a high silver chloride emulsion is applied is insufficient and needs to be studied. Was.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a solution preparation technique having excellent storage stability of a photographic additive over time, a high sensitivity, and a small change in sensitivity and fog due to storage over time after completion of chemical ripening. Another object of the present invention is to provide a silver halide photographic emulsion and a photographic light-sensitive material having excellent stagnation of a coating solution.

[0009]

The above objects of the present invention are as follows. Consisting of at least one cation selected from alkali metals and alkaline earth metals, and at least one of the following anions, each being 0.1 mol per mol of silver halide during chemical ripening. Photographic additives characterized by being used as added above,

[0010] 2. In a silver halide photographic emulsion used for a silver halide emulsion layer, at least one cation selected from an alkali metal and an alkaline earth metal,
A silver halide photographic emulsion, wherein at least one of the following anions is added in an amount of 0.1 mol or more during the chemical ripening with respect to 1 mol of each silver halide; Citric acid, tartaric acid, SO ₄ , CH ₃ CO ₂ ,
NO ₃ , ClO ₃ , SCN

3. The silver halide photographic emulsion used for the silver halide emulsion layer is composed of 95 mol% or more of silver chloride, and an alkali metal ion is added at a molar ratio of 10 times or more to the compound represented by the following general formula (I). A silver halide photographic emulsion characterized by the following general formula (I): R ₁ —N (OH) —R ₂ wherein R ₁ is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group; Group, sulfonyl group, sulfinyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, or represents an aryloxycarbonyl group,
R ₂ represents a hydrogen atom or the same group as described for R ₁ . However, when R ₁ is an alkyl group, an alkenyl group or an aryl group, R ₂ is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₁ and R ₂ may be combined with each other to form a 5- to 7-membered nitrogen-containing heterocyclic ring. ]

4. The silver halide photographic emulsion used in the silver halide emulsion layer is composed of 95 mol% or more of silver chloride, and an alkali metal ion is added at a molar ratio of 10 times or more to the compound represented by the following general formula (II). A silver halide photographic emulsion, characterized in that

[0013]

Embedded image [Wherein, R _{21 to} R ₂₅ each represent a hydrogen atom, a halogen atom, a sulfone atom, a sulfonic acid group (including its salt), a carboxylic acid group (including its salt), an alkyl group, an alkoxy group, an alkylthio group, Cycloalkyl group, cycloalkyloxy group, alkyloxycarbonyl group, carbamoyl group, sulfonamide group, alkylsulfonamide group,
Sulfonyl group, aminosulfonyl group, sulfinyl group,
Alkylsulfinyl group, acyl group, acylamino group,
Or represents an acyloxy group. However, R _{21 to} R ₂₅ have 0 to 5 carbon atoms, and at least one is a hydroxyl group or —XR ₂₆ (R ₂₇ ), (X represents each atom of sulfur or nitrogen or oxygen; ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group or an alkylcarbonyl group, and R ₂₆ and R ₂₇ may form a ring). Further, R _{21 to} R ₂₅ may be bonded to each other to form a ring. Of the groups R _{21 to} R ₂₅ , the substituents at the ortho positions may be bonded to each other to form a 5- to 7-membered ring. However, each group of R _{21 to} R ₂₅ is not simultaneously a hydrogen atom, and R ₂₃ is a halogen atom, —O
-R _27, in the case of _{-S-R 27,} at least one of R _{21, R 25} is an alkyl group. ]

5. The silver halide photographic emulsion used in the silver halide emulsion layer is composed of 95 mol% or more of silver chloride, and an alkali metal ion is added at a molar ratio of 10 times or more to the compound represented by the following general formula (III). A silver halide photographic emulsion, characterized in that

[0015]

Embedded image [Wherein, R ₃₁ represents a halogen atom or a monovalent group;
₃₁ and X ₃₂ each represent a halogen atom, a carboxylic acid group (including its salt), a sulfonic acid group (including its salt), an alkylthio group, an acyl group, a lower alkylcarbamoyl group having 1 to 3 carbon atoms, an acylamino group, It represents an acyloxy group, an alkyloxycarbonyl group, a lower aminosulfonamide group having 1 to 3 carbon atoms, an aminosulfonyl group, an alkylsulfonyl group, an alkylsulfinyl group, or a group represented by the general formula (IV). n ₃₁ and the sum is an integer from 1 to 4 of _{n 32,} the sum of n _{31, n 32} and _{n 33} is 1
Represents an integer of 4. ]

[0016]

Embedded image [Wherein _Y 31 _{to Y 35} each represent a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, or a salt thereof a carboxylic acid group, or represents a sulfonic acid group (or a salt _thereof), the Y 31 _{to Y 35} Not all are hydrogen atoms. n ₃₁ represents an integer of 0 to 3. ]

6. The silver halide photographic emulsion used in the silver halide emulsion layer is composed of 95 mol% or more of silver chloride, and an alkali metal ion is added at a molar ratio of 10 times or more to the compound represented by the following general formula (V). the silver halide photographic emulsion, characterized in that formed by the general formula _{(V) -O- (CR 41 R} 42 -CR 43 R 44 -O) n- (n ≧ 1) [R 41 ~R 44 is hydrogen Represents an atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, which may be the same or different. The basic unit is shown in parentheses, but may or may not be cyclically formed by oxygen atoms at both ends. When a ring is formed, it may be condensed with one or more aromatic rings. In the case of the A-chain molecule, both ends are hydroxyl groups. ]

[7] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the silver halide emulsion of the silver halide photographic emulsion layer is the halogenated silver halide emulsion described in any of 2 to 6 above. A silver halide photographic material, which is a silver photographic emulsion;
Is achieved by each of

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.
The cations selected from the alkali metals or alkaline earth metals used in the present invention are Li, Na,
K, Rb, Cs and Mg, Ca, Sr, and Ba are preferred, but Na, K, and Ca are more preferred. For the anion, citric acid, tartaric acid, SO ₄ , CH ₃ CO ₂ ,
Examples include NO ₃ , ClO ₃ , and SCN, of which citric acid, tartaric acid, and CH ₃ CO ₂ are preferable. Regarding the addition of these ions, it is preferable to dissolve them in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, or dimethylformamide or water and to add them as a solution. The timing of addition is preferably during chemical ripening after silver halide grain formation.

By the addition of these ions, high sensitivity, sensitivity during storage over time after completion of chemical ripening, and little change in fog were confirmed, and the effect on the sensitivity change when the coating solution was stagnated could be confirmed. The mechanism by which these effects are obtained is not clear, but the interaction between the silver halide grains and the gelatin used as a dispersing medium during the preparation of the silver halide emulsion is not impaired by the salting-out effect of the silver halide grains. Weakens the effect. This is presumed to increase the adsorption of various additives added during the chemical ripening to silver halide grains.

Next, the compound represented by formula (I) will be described. In the general formula (I), R ₁ is an alkyl group (having preferably 1 to 36, more preferably 1 to 26 carbon atoms, for example, methyl, ethyl, i-propyl, cyclopropyl, i-butyl, cyclohexyl) , T
Octyl, decyl, dodecyl, hexadecyl, benzyl, etc.), alkenyl groups (preferably having 2 to 3 carbon atoms)
6, more preferably 2 to 26, such as vinyl,
Allyl, i-propenyl, 2-butenyl, oleyl, etc.), aryl group (preferably having 6 to 40 carbon atoms,
More preferably, those having 6 to 30, for example, phenyl and naphthyl, and a heterocyclic group (forming a 5- to 7-membered heterocyclic ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom as a ring-constituting atom) Preferably a nitrogen-containing heterocyclic ring having 1 to 4 nitrogen atoms, most preferably a 5- to 6-membered heterocyclic group having 1 to 3 nitrogen atoms, for example, 1,3,5-triazine -2-yl, 1,2,4-
Triazin-3-yl, pyridyl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,2
4-triazol-3-yl, benzimidazole-2
-Yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuranyl, morpholinyl, piperazinyl, etc.), acyl group ｛acetyl, benzoyl, pivaloyl, α- (2,4-di-t-pentylphenoxy) butyryl, myristoyl, stearoyl , Naphthoyl, 2-
Pentadecylbenzoyl, isonicotinoyl, etc., a sulfonyl group (preferably an alkyl or arylsulfonyl group, for example, methanesulfonyl, butanesulfonyl, benzenesulfonyl, toluenesulfonyl, etc.), a sulfinyl group (preferably an alkyl or arylsulfinyl group, for example, methanesulfinyl , Benzenesulfinyl, etc.), carbamoyl group (N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl and the like, sulfamoyl and the like (N-methylsulfamoyl, N-phenylsulfamoyl, N, N-diethylsulfamoyl,
N-ethyl-N-dodecylsulfamoyl, etc.), alkoxycarbonyl group (methoxycarbonyl, i-pentyloxycarbonyl, cyclohexyloxycarbonyl,
Represents a benzyloxycarbonyl, octadecyloxycarbonyl or the like or an aryloxycarbonyl group (phenoxycarbonyl, naphthoxycarbonyl or the like).

R ₂ represents a hydrogen atom or the same group as represented by R ₁ . Incidentally, between the _{R 1} and _{R 2} have the aforementioned limitations.
Examples of the 5- to 7-membered ring which may be formed by combining R ₁ and R ₂ include succinimide, phthalimide, triazole, urazole, hydantoin, 2-oxo-4-oxazolidinone ring, and the like.

The groups represented by R ₁ and R ₂ may further have a substituent, such as an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, Alkylthio group, arylthio group, amino group (including substituted amino group), acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a hydroxyamino group.

Next, the compound represented by formula (II) will be described. Examples of the alkyl group represented by R _{21 to} R ₂₅ include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a hydroxyethyl group. Examples of the alkoxy group represented by R _{21 to} R ₂₅ include a methoxy group, an ethoxy group, and a butyloxy group. Examples of the cycloalkyl group represented by R _{21 to} R ₂₅ include a cyclopentyl group, a cyclohexyl group, and an adamantyl group, and examples of the cycloalkyloxy group include a cyclopentyloxy group and a cyclohexyloxy group. Examples of the aryl group represented by R _{21 to} R ₂₅ include a phenyl group, a hydroxyphenyl group, and a tolyl group. Examples of the aryloxy group include a phenoxy group and a tolyloxy group. Examples of the alkyloxycarbonyl group represented by R _{21 to} R ₂₅ include a methoxycarbonyl group, an ethoxycarbonyl group, and a propyloxycarbonyl group. Examples of the acyloxy group include an acetyloxy group, an ethylcarbonyloxy group, and a propylcarbonyloxy group. Can be mentioned. R _{21 to} R ₂₅ may combine with each other to form a ring.

In the general formula (II), R ₂₆ and R ₂₇
Examples of the alkyl group represented by include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a hydroxyethyl group. Examples of the aryl group represented by R ₂₆ and R ₂₇ include a phenyl group, a hydroxyphenyl group, and a tolyl group. Examples of the alkylcarbonyl group represented by R ₂₆ and R ₂₇ include an acetyl group, an ethylcarbonyl group, and a butylcarbonyl group. R ₂₆ and R ₂₇ may form a ring.

Next, the compound represented by formula (III) will be described. In the formula, X ₃₁ and X ₃₂ each represent a halogen atom, a carboxylic acid group (including its salt), a sulfonic acid group (including its salt), an alkylthio group, an acyl group,
A lower alkylcarbamoyl group having 1 to 3 carbon atoms, an acylamino group, an acyloxy group, an alkyloxycarbonyl group, a lower alkylsulfonamide group having 1 to 3 carbon atoms, an aminosulfonyl group, an alkylsulfonyl group, an alkylsulfinyl group, a general formula Represents a monovalent group selected from (IV). n ₃₁ and n ₃₂ each represent an integer of 0 to 4; n ₃₃ represents an integer of 0 to 3; the sum of n ₃₁ and n ₃₂ is an integer of 1 to 4; the sum of n ₃₁ , n ₃₂ and n ₃₃ is 1 Represents an integer of ４4.

The general formula (IV) will be described.

[0028]

Embedded image _Wherein, Y 31 _{to Y 35} each represent a hydrogen atom, a halogen atom, an amino group, or a salt thereof hydroxyl groups, carboxylic acid groups, or represents a sulfonic acid group (or a salt _thereof), the Y 31 _{to Y 35} Not all hydrogen atoms. n ₃₄ represents an integer of 0 to 3.

In the compound represented by the general formula [IV] used in the present invention, examples of the halogen atom represented by X ₃₁ and X ₃₂ include a chlorine atom and a bromine atom.

When X ₃₁ and X ₃₂ each represent a monovalent group, the carboxylate is, for example, sodium carboxylate, the sulfonic acid is, for example, sodium sulfonate, and the alkylthio group is, for example, a methylthio group, an ethylthio group. However, as the acyl group, for example, formyl group, acetyl group, propionyl group, etc., as the carbamoyl group, for example, ethyl carbamoyl group, phenylcarbamoyl group, etc., as the acylamino group, for example, acetylamino group, propionylamino group, etc., an acyloxy group As, for example, an acetyloxy group, a butyryloxy group,
Examples of the alkyloxycarbonyl group include a methyloxycarbonyl group and an ethyloxycarbonyl group.Examples of the sulfonamide group include an ethylsulfonamide group.Examples of the aminosulfonyl group include a methylaminosulfonyl group and the like. is for example methylsulfonyl group, alkylsulfinyl is for example butyl sulfinyl group as group, as the general formula (V), for example, _-CH 2 _{CHOH, -CH} 2 _COOH,
—CH ₂ SO ₃ H, —CH ₂ CH ₂ CF _{3 and the} like.

Particularly preferred as X ₃₁ and X ₃₂ are a carboxylic acid group (including its salt), a sulfonic acid (including its salt), an acyl group and an alkyloxy group. When X ₃₁ or X ₃₂ represents a sulfonic acid group or a salt thereof, it is more preferable that at least two of the substituents represented by X ₃₁ and X ₃₂ are a sulfonic acid group or a salt thereof.

Next, examples of the halogen atom represented by R ₃₁ include a chlorine atom and a bromine atom. Examples of the monovalent group represented by R ₃₁ include a carboxylic acid group or a salt thereof (for example, a sodium carboxylate), a sulfonic acid group or a salt thereof (for example, a sodium sulfonic acid salt),
Hydroxyl group, cyano group, amino group, alkyl group,
(Eg, methyl group, ethyl group, butyl group, etc.) cycloalkyl group (eg, cyclohexyl group, etc.), aryl group (eg, phenyl group, tolyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), cycloalkyloxy Group (eg, cyclohexyloxyl group), aryloxy group (eg, phenoxy group, naphthoxy group, etc.), acyloxy group (eg, formyl group, acetyl group, propionyl group, butyryl group, oxalyl group, benzoyl group, etc.), aminocarbonyl group ( For example, methylaminocarbonyl group, ethylaminocarbonyl group, etc., alkyloxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group Amino group (e.g., acetylamino group, benzoylamino group, etc.), a sulfonamido group (e.g., methyl sulfonamide group, an ethyl sulfonamido group, etc.), a Hajime Tamaki (e.g. furyl group, a thiazolyl group,
Examples include an imidazoline group, a succinimide group, a benzoxazoline group, a phthalimide group, and the like, an alkylthio group (eg, a methylthio group, an ethylthio group, a propylthio group, and the like), and an arylthio group (eg, a phenylthio group, a naphthylthio group, and the like). The monovalent group represented by R ₃₁ may optionally be a substituent (eg, a hydroxyl group,
Carboxyl group).

When the monovalent group represented by R ₃₁ represents an alkyl group, the number of carbon atoms is preferably 5 or less, more preferably 3 or less. X ₃₁ , X ₃₂ and R ₃₁ can also form a condensed ring with each other, but it is preferable not to form a condensed ring in order to further enhance the effects of the present invention.

The compound represented by formula (V) will be described. R _{41 to} R ₄₄ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, and may be the same or different. The parentheses are the basic units of the repeating structure, but may or may not be cyclically formed by oxygen atoms at both ends. When a ring is formed, it may be condensed with one or more aromatic rings. In the case of a chain molecule, both ends are hydroxyl groups.

Examples of the compound forming a ring include a cyclic compound having a 9-membered ring or more.
Crown ethers.

In the present invention, the cyclic compound is preferably a crown ether fused with at least one aromatic ring. Alternatively, the aromatic ring may be substituted or unsubstituted. When substituted, examples of the substituent typically include alkyl, aryl, anilino, acylamino, alkylthio, arylthio, alkenyl, cycloalkyl, and the like.In addition, a halogen atom and cycloalkenyl, alkynyl , Heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
And the like. For these representative compounds, the following Pederson was used as a crown ether.
It was synthesized in 1967, and has been synthesized in large numbers since its unique properties were reported. These compounds are C.I. J. Peders
on, Journal of American Ch
Electronic Society, vol. 86 (249
5), 7017 to 7036 (1967); W. Go
kel, S .; H. Korzeniowski, "Mac
rocyclic polythesis ", Spri
nger-Verlag, (1982), Oda, Shono,
Edited by Tabushi, "Cran Ether Chemistry", Doujin Kagaku, (19
78), Tabushi et al., "Host Guest", Kyoritsu Shuppan, (19
79), Sasaki, Koga, "Synthetic Organic Chemistry", Vol. 1
45, (6), 571-582, (1987), and the like.

The compound (V) in the present invention can be prepared by using a water-miscible organic solvent such as methanol, ethanol, acetone or dimethylformamide or water in preparing the solution. The addition amount of the compounds of the general formulas (I) to (V)
2 × 10 ^{−4 to} 2 × 10 ⁻³ mol / mol AgX is preferred.

The specific examples of the compounds represented by formulas (I) to (V) are shown below, but the present invention is not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image _{S-1 OH-CH 2 -CH} 2 -OH S-2 OH-CH 2 -CH 2 -O-CH 2 -CH 2 -
OH

[0049]

Embedded image

[0050]

Embedded image

[0051]

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[0052]

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The above compounds of the present invention may be used in combination of several kinds as necessary, or may be used in combination with other compounds as long as the effects of the present invention are not impaired. The compound of the present invention is preferably added when preparing at least one silver halide emulsion among a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a red-sensitive silver halide emulsion. However, the addition amount is preferably at least 10 times, more preferably at least 30 times, the molar ratio of the spectral sensitizing dye added for imparting each photosensitivity.

The compound of the present invention may be added at a stage prior to the preparation of the coating solution, preferably at any time during chemical ripening. As a method for adding the compound of the present invention to a silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or dissolved in a water-soluble solvent such as pyridine, methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide, or a mixture thereof, or diluted with water. Or dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can be used during the dissolution process.

Further, the compound of the present invention can be prepared by the method described in US Pat.
No. 9,987, etc., a method of dissolving in a volatile organic solvent, and dispersing this solution in a hydrophilic colloid, and adding a dispersion to the emulsion, as described in JP-B-46-24185. A method of dispersing the compound of the present invention in a water-soluble solvent without dissolving the compound and adding the dispersion to an emulsion is also used.

The composition of the silver halide emulsion used in the present invention is characterized by having a silver chloride content of 95 mol% or more. If this condition is satisfied, silver chloroiodobromide, silver iodochloride,
Either silver chlorobromide or silver chloride or a silver chlorobromide emulsion having a localized phase having a silver bromide content of 30 mol% or more can be used.

The portion containing silver bromide at a high concentration may form a layer as a so-called core-shell emulsion,
A region having a partially different composition may be present without forming a complete layer due to epitaxy bonding to the silver halide emulsion grains. The portion where silver bromide is present in high concentration may be made in the stage of forming silver halide grains,
It may be made in a subsequent chemical ripening stage or a coating solution preparation stage. When the composition of the inside and the surface of the particle are different, the composition may be changed continuously or discontinuously.

Although it depends on the composition of the whole silver halide emulsion grains, when the content of silver bromide relative to the total silver halide is about 1 mol%, the silver bromide containing a high concentration of silver bromide The content is preferably 40 mol% or more. In order to form such a localized phase of silver bromide, a so-called conversion method may be used in which an aqueous solution of a water-soluble bromide salt such as potassium bromide is added, or a double-mixing method or a bromide prepared in advance. A method of adding silver fine particles and utilizing a recrystallization process may be used. Examples of such silver halide grains are described in JP-A-58-95736 and JP-A-58-1085.
No. 33 and particles described in JP-A-1-183647.

The silver bromide content of the portion containing a high concentration of silver bromide can be determined by the method described in the upper right column on page 22 of JP-A-1-183647. When the thus obtained silver bromide content has a certain range, the silver bromide content of the portion containing silver bromide at a high concentration in the present invention means the maximum value.

To obtain the silver halide emulsion according to the present invention, it is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred. These metal ions are
It can be added to the silver halide emulsion in the form of a salt or a complex salt.

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.

In order for the silver halide emulsion according to the present invention to contain heavy metal ions, the heavy metal compound is physically added before, during, and after the formation of silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 5 per mol of silver halide.
^-9 mol or more and 1 × 10 ⁻² mol or less are more preferable,
In particular, it is preferably from 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol.

The shape of the silver halide grains according to the present invention can be arbitrary. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666;
JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39.
(1973), etc., particles having an octahedral, tetradecahedral, dodecahedral shape or the like can be prepared and used. Further, particles having a twin plane may be used.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The particle size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0 or less. .15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation. Coefficient of variation = S / R (where, S represents the standard deviation of the particle size distribution, and R represents the average particle size.) The particle size referred to here is the diameter of a spherical silver halide particle, In the case of particles having a shape other than a cube or a sphere, the diameter represents a 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 an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., 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 a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming 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 sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. As sulfur sensitizers, thiosulfate, allyl thiocarbamide thiourea,
Allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like, but is preferably from 5 × 10 ^{−10 to} 5 × 10 −5 per mol of silver halide. The range of × 10 ⁻⁵ mol is preferable, and the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1
× 10 ⁻⁸ mol. As the chemical sensitization method for the silver halide emulsion according to the present invention, a reduction sensitization method may be used.

The silver halide emulsion according to the present invention is intended to prevent fogging that occurs during the preparation process of the silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fogging that occurs during development. And known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include JP-A-2-146.
General formula (II) described in the lower section of page 7 of JP-A No. 036
And more preferable specific compounds are (IIa-1) to (IIa-8) and (IIb-1) to (IIa-1) described on page 8 of the publication.
Examples of the compound include (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose.

When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ⁻⁵ mol per mol of silver halide is used.
It is preferably used in an amount of about 5 × 10 ⁻⁴ mol. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. More preferred. In the coating solution preparation step, when adding to the silver halide emulsion layer, 1 × 10
An amount of about ⁻⁶ mol to 1 × 10 ⁻¹ mol is preferable, and
It is more preferably from 10 ⁻⁵ mol to 1 × 10 ⁻² mol. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is from 1 × 10 ⁻⁹ mol to 1 × 10 ⁹ mol / m ^2.
An amount of about ^-3 mol is preferred.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region,
A described on page 308 of JP-A-3-251840
The dyes of I-1 to 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared-absorbing dye include general formulas (I) described in the lower left column of page 2 of JP-A-1-280750. The compounds represented by formulas (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are free from contamination by residual color. As a specific example of a preferred compound, see Japanese Patent Publication No.
Exemplary compounds (1) to (45) listed in the lower left column of page 5 to the lower left column of page 5 can be exemplified.

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, spectral sensitization was performed in a specific region of a wavelength region of 400 to 900 nm in combination 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.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compounds can be used. As the blue-sensitive sensitizing dye, JP-A-3-251840, p. BS-1 described in
8 can be used alone or in combination. As the green-sensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the publication are preferably used. As the red-sensitive sensitizing dye, RS-1 to 8 described on page 29 of the same publication are preferably used. In the case of performing image exposure from infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye must be used. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used.

The amount of the sensitizing dye to be added varies depending on the type of the sensitizing dye, the halogen composition of the silver halide emulsion to be applied, the particle size, and the like.
× 10 ⁻⁵ to 4 × 10 ⁻³ mol, more preferably 1 × 1
It is used in the range of 0 ^-4 to 1 × 10 ^-3 mol. These sensitizing dyes 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 by dissolving it in water, or adding it 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 dispersing the sensitizing dye, other than a method of mechanically pulverizing and dispersing fine particles of 1 μm or less in an aqueous system using a high-speed stirring type disperser, see JP-A-58-105141.
As described in JP-B-60-6496, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system under conditions of pH 6 to 8 and 60 to 80 ° C., and a surface tension of 38 dyne / cm described in JP-B-60-6496. For example, a method of dispersing in the presence of a surfactant suppressed below can be used.

Examples of the dispersing apparatus which can be used for preparing the dispersion include, for example, a high-speed stirring type dispersing apparatus shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, and an ultrasonic dispersing apparatus. And the like.

In using these dispersing apparatuses, a method may be adopted in which pretreatment such as dry pulverization is performed in advance and then wet dispersing is performed as described in JP-A-4-125632.

When a plurality of sensitizing dyes are used in combination, the two sensitizing dyes may be added separately or may be added after mixing in advance.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers 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 according to the present invention include:
Couplers represented by general formulas (C-I) and (C-II) described in the lower left column of page 5 of JP-A-4-114154 can be exemplified.

The magenta couplers which can be preferably used in the silver halide photographic light-sensitive material according to the present invention include those represented by the general formulas (MI) and (M-II) described in the upper right column of page 4 of JP-A-4-114154. )). Among the above magenta couplers, more preferred are couplers represented by the general formula (MI) described in the upper right column on page 4 of the same gazette.
The coupler of the above general formula (MI) in which RM is a tertiary alkyl group is excellent in light resistance and particularly preferred.

As the yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a coupler represented by the general formula (Y-I) described in the upper right column of page 3 of JP-A-4-114154 can be used. Can be used. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, a coupler in which RY1 of the general formula [Y-1] is an alkoxy group or a coupler disclosed in
The coupler represented by the general formula [I] described in JP-A-67388 can reproduce yellow having a preferable color tone, and is therefore preferable. Also, JP-A-4-81847, page 1 and 11
The compounds represented by the general formula [Y-1] described on page 17 may also be used.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material according to the present invention, the water-insoluble emulsion usually has a boiling point of 150 ° C. or higher. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination in the boiling point organic solvent, and the mixture is dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. 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 or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, and phosphates such as trioctyl phthalate,
Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferred compound as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A-1 to A described in JP-A-64-26854
-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB of JP-A-3-174150, and Amine compounds represented by the general formula A described in Japanese Unexamined Patent Publication No. Hei 64-90445, and general formulas XII and XII described in Japanese Patent Application Laid-Open No. 62-182741.
The metal complexes represented by I, XIV and XV are particularly preferred for magenta dyes. Further, a compound represented by the general formula I 'described in JP-A-1-19649 and JP-A-5-19649
The compounds represented by the general formula II described in JP-A No. 11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound (A'-1) described in the lower left column of page 10 of the same publication are disclosed. And the like. In addition, a fluorescent dye-releasing compound described in U.S. Pat. No. 4,774,187 can also be used.

The silver halide light-sensitive material according to the present invention includes:
It is preferable to add a compound that reacts with the oxidized developing agent to a layer between the photosensitive layers to prevent color turbidity, or to add a compound to the silver halide emulsion layer to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-tert-octylhydroquinone.

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or to improve the light fastness of a dye image. Preferred examples of the ultraviolet absorber include benzotriazoles. Particularly preferred compounds are those represented by the formula III-3 described in JP-A-1-250944 and JP-A-64-666.
No. 46, a compound represented by general formula III, and JP-A-63-187240 describes UV-1L to UV-L.
27L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the silver halide photographic light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, gelatin Other than these, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

As the support used in the silver halide photographic light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, A vinyl chloride sheet, polypropylene which may contain a white pigment, a polyethylene terephthalate support, baryta paper, and the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the 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 silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. 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 support was 13% by weight for improving sharpness.
The above is preferred, and more preferably 15% by weight. 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 measured by the method described in JP-A-2-28640. 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, as the coefficient of variation described in the above publication.

The center-surface average roughness (SRa) of the support
Is more preferably 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss is obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion on the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the silver halide photographic light-sensitive material according to the present invention, an image recorded on a negative is optically formed on a silver halide photographic light-sensitive material to be printed. The image may be printed and printed, or once the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and this image is formed on a silver halide photographic material to be printed. Alternatively, the image may be printed by scanning while changing the intensity of the laser beam based on digital information.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably applied to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can 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- (N-ethyl-N- (β-hydroxyethyl) amino) 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) methanesulfonamide 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 present invention, the above-mentioned color developing solution can be used in an arbitrary pH range.
It is preferably 5 to 13.0, more preferably p
H is used in the range of 9.8 to 12.0. The processing temperature for color development is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable. Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for the development 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 conveyed between rollers disposed in a processing tank, and the belt may be provided with the light-sensitive material. The processing tank may be formed in a slit shape, and the processing liquid may be supplied to the processing tank and the photosensitive material may be transported, or the processing liquid may be sprayed. Spray method,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used. When processing in large quantities, it is normal to run using an automatic developing machine, but in this case, the replenishment amount of the replenisher is preferably as small as possible. The most preferred method is to add a treating agent in the form described in JP-A-94-16935.

[0114]

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 (Preparation of red-sensitive silver halide emulsion)
(A solution) and (B)
Liquid) to 30 while controlling pAg = 7.3 and pH = 3.0.
Were added simultaneously over a period of 150 minutes, and the following (solution C) and (solution D) were simultaneously added over 150 minutes while controlling the pAg at 8.0 and the pH at 5.5. At this time, the control of pAg is described in
The control of pH was performed using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide Add water to 200 ml

(Solution B) Silver nitrate 10 g Water was added to 200 ml

[0117] The (C solution) Sodium chloride ^{_{102.7g K 2 IrCl 6 4 × 10}} -8 mol / mol _{Ag K 4 Fe (CN) 6} 2 × 10 -5 mol / mol Ag Potassium bromide 1.0g Water added 600ml

(Solution D) Silver nitrate 300 g Water was added to 600 ml

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.40 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99. A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the average particle size was 0.38 μm and the particle size distribution was the same as in EMP-1 except that the addition time of (solution A) and (solution B) and the addition time of solution (C) and solution (D) were changed. A monodisperse cubic emulsion EMP-1B having a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (100R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0122]

Embedded image

The red-sensitive silver halide emulsion (100R) differs from the red-sensitive silver halide emulsion (100R) only in that cations and anions are added as shown in Table 1 after addition of RS-1 and RS-2 during chemical ripening as shown in Table 1. Emulsions (101R) to (112R) were prepared.

[0124]

[Table 1]

(Preparation of coating sample for evaluation and sensitivity evaluation) In addition to the red-sensitive silver halide emulsion prepared by the above method, as shown in Table 1, each compound added during chemical ripening was used to prepare a coating sample. The coating samples (100) to (112) were prepared according to the following methods, including the level of the same amount added to the coating liquid of Example 1.

High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to which the emulsion layer was applied, a dissolving polyethylene containing a surface-treated anatase-type titanium oxide dispersed therein at a content of 15% by weight was laminated to prepare a reflective support. After corona discharge treatment of this reflective support,
A gelatin undercoat layer was provided, and each layer having the composition shown in Table 2 was provided.

[0127]

[Table 2]

[0128]

Embedded image

[0129]

Embedded image

Each of the samples was exposed to light wedges by a conventional method, and then subjected to a developing process in the following developing process. Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80ml Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 120ml Stabilization 30-34 ° C 60 seconds 150ml Drying 60-80 ° C 30 seconds

The composition of the developing solution is shown below. Color developing solution tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- (Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g sodium diethylenetriaminepentaacetate Salt 2.0 g 2.0 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. 10 and replenisher to pH = 10.60 To integer.

Bleach-fixing solution tank solution and replenisher diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

After the evaluation sample was processed, the density was measured using an optical densitometer (PDA-65 manufactured by Konica), and the reciprocal of the difference between the exposure amounts giving the densities 0.75 and 1.75 of the characteristic curve was defined as γ. Defined. The results are summarized in Table 1. After processing, the evaluation sample was subjected to density measurement using an optical densitometer (model PDA-65 manufactured by Konica), and the reciprocal of the exposure amount giving a density of 0.75 in the characteristic curve was defined as sensitivity. The relative sensitivities of (101) to (112) when the sensitivity obtained from the sample (100) prepared using the emulsion (100R) to which no compound was added during chemical ripening was 100, were defined as red sensitivity. The results for only the layers are summarized in Table 1. Potassium and citric acid,
When the amount of addition of sodium and acetic acid, and the combination of calcium and tartaric acid are 1 × 10 ⁻² mol / mol Ag or less, the sensitivity is equal to or slightly higher than that of the comparative sample (100). × 10 ⁻³ mol / mol Ag or more level (103), (104), (107), (10)
8), (111) and (112), a remarkable increase in sensitivity can be confirmed.

(Emulsion preservability) Immediately after preparation of the emulsion,
Samples stored in a refrigerator and the emulsion were stored in a refrigerator at 7 ° C. for 6 months, and the coated samples were subjected to light wedge exposure and color development by a conventional method, and then the density was measured. The sensitivity was expressed as a relative value with respect to the sensitivity of the sample of the emulsion stored in a refrigerator, assuming that the sensitivity of the sample applied immediately after the preparation of the emulsion was 100, and the fog was expressed as a relative value with the fog of the sample applied immediately after the preparation of the emulsion as 0.
The results are summarized in Table 1. For the comparative sample (100),
At a level where ions were added at 1 × 10 ⁻³ and 1 × 10 ⁻² mol / Ag mol, although desensitization during storage with time was slightly small,
It turns out that it is not enough. On the other hand, the level of addition of 0.1 mol / mol Ag or more indicates the sensitivity due to storage over time,
It can be seen that the fluctuation of fog is small and the effect of the present invention is obtained.

(Stagnation of Coating Solution) In evaluating the coated sample, the sample (10
Samples (100T) to (112T) prepared using a coating solution stagnated at 36 ° C. for 12 hours in addition to 0) to (112)
It was created. The sensitivity of (100T) to (112T) is evaluated based on the sensitivity of each sample of Samples (100) to (112), and the rate of change per hour of stagnation of coating liquid ΔS2 (% / h) for each sample. Calculated and summarized in Table 1.
The sensitivity variation in the stagnation is desensitized or sensitized depending on the ion species with respect to the comparative sample (100), but the ions are added at 1 × 10 ⁻³ and 1 × 10 ⁻² mol / Ag mol. At such a level, the fluctuation in sensitivity due to stagnation is large, and the influence on the production stability of the photosensitive material is large. On the other hand, at the level of addition of 0.1 mol / mol Ag or more, the sensitivity fluctuation due to the stagnation of the coating solution is small, and it can be seen that the effect of the present invention is obtained.

Example 2 (Evaluation of Solution Storage Stability) For the compound of the present invention, a solution was prepared for preparing a silver halide emulsion, and the solution stability after storage was evaluated from the rate of decrease in spectral absorption intensity. did. For compounds E-15, X-18, X-50, and S-2, a 3% solution was prepared using ethanol as a solvent, and the molar ratio to the compound was 0.5, 1, 5,
Potassium acetate powder equivalent to 10, 30, and 40 times was added, and the mixture was stirred at room temperature until complete dissolution was confirmed.

[0138]

[Table 3]

Immediately after complete dissolution, the spectral absorption spectrum was measured.
With the main peak intensity of the spectrum of each compound as 100,
The relative strength after storage at 25 ° C. for one month was evaluated. Table 4 shows the evaluation results.

[0140]

[Table 4]

In any of the compounds, when the amount of potassium acetate added was 5 or less in terms of molar ratio, the relative spectral intensity was reduced to 90 or less, and there was a problem that the storage stability of the solution remained a problem. became. On the other hand, when the amount of potassium acetate added is at a level of 10 or more in terms of molar ratio, a stable spectral intensity is shown regardless of the compound.
As the amount of potassium acetate added increases, the solution stability further increases, and the effect of the present invention can be confirmed.

Example 3 The red-sensitive silver halide emulsion prepared in Example 1 (100
R) is the compound (E-15) prepared in Example 2,
Emulsions were prepared which differed only in that the solutions containing (X-18), (X-47) and (S-2) were added after the addition of RS-1 and RS-2 during chemical ripening as shown in Table 5. And a silver halide photosensitive material (2)
00R) to (218R). The prepared sample was exposed and processed in the same manner as in Example 1, and the sensitivity was changed to Sample (100).
Is shown as a relative value when 100 is taken. The results are summarized in the table. Regardless of the compound, potassium acetate is used in a molar ratio of 10
Samples (204) to (209), (213) to (21) prepared using silver halide emulsions prepared by adding at least twice
Regarding 8), each of them was 2 compared to the comparative sample (200).
Sensitization of 0 to 30% is observed.

The storage stability of the emulsion over time after chemical ripening was evaluated in the same manner as in Example 1.
With respect to 4) to (209) and (213) to (218), the sensitivity decrease after storage with time is small, and the degree of fog increase is also small, so that the effect of improving storage stability can be confirmed. The same evaluation as in Example 1 was carried out for the coating solution stagnation property. As a result, depending on the compound, the sensitivity fluctuation due to the stagnation tended to sensitize and desensitize, but the samples (204) to (209) and (213) to In (218), it can be seen that the sensitivity fluctuation due to the stagnation of the coating liquid is small, and the production stability can be improved.

[0144]

[Table 5]

[0145]

According to the present invention, a technique for preparing a photographic additive having excellent stability over time, and a technique for preparing a photographic additive having high sensitivity and excellent storage over time after chemical ripening, and a technique for preparing a photographic additive having excellent sensitivity over time A silver halide photographic emulsion and a photographic material having excellent storage stability and improved production stability can be obtained.

Claims (7)

[Claims] 1. A chemical ripening process comprising at least one cation selected from alkali metals and alkaline earth metals and at least one of the following anions, each of which is chemically ripened per mole of silver halide. A photographic additive which is used in an amount of 0.1 mol or more. 2. A silver halide photographic emulsion used in a silver halide emulsion layer, wherein at least one cation selected from alkali metals and alkaline earth metals and at least one of the following anions are used. A silver halide photographic emulsion characterized by being added in an amount of 0.1 mol or more to 1 mol of silver halide during chemical ripening. Anions: citric acid, tartaric acid, SO ₄ , CH ₃ CO ₂ ,
NO ₃ , ClO ₃ , SCN 3. A silver halide photographic emulsion used for a silver halide emulsion layer, comprising 95 mol% or more of silver chloride, wherein an alkali metal ion is present in a molar ratio to a compound represented by the following general formula (I). A silver halide photographic emulsion characterized by being added 10 times or more in the above. Formula (I): R ₁ —N (OH) —R ₂ wherein R ₁ is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, Represents an alkoxycarbonyl group or an aryloxycarbonyl group,
R ₂ represents a hydrogen atom or the same group as described for R ₁ . However, when R ₁ is an alkyl group, an alkenyl group or an aryl group, R ₂ is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₁ and R ₂ may be combined with each other to form a 5- to 7-membered nitrogen-containing heterocyclic ring. ] 4. A silver halide photographic emulsion used in a silver halide emulsion layer, comprising 95 mol% or more of silver chloride, wherein an alkali metal ion has a molar ratio to a compound represented by the following general formula (II). A silver halide photographic emulsion characterized by being added 10 times or more in the above. Embedded image [Wherein, R _{21 to} R ₂₅ each represent a hydrogen atom, a halogen atom, a sulfone atom, a sulfonic acid group (including its salt), a carboxylic acid group (including its salt), an alkyl group, an alkoxy group, an alkylthio group, Cycloalkyl group, cycloalkyloxy group, alkyloxycarbonyl group, carbamoyl group, sulfonamide group, alkylsulfonamide group,
Sulfonyl group, aminosulfonyl group, sulfinyl group,
Alkylsulfinyl group, acyl group, acylamino group,
Or represents an acyloxy group. However, R _{21 to} R ₂₅ have 0 to 5 carbon atoms, and at least one is a hydroxyl group or —XR ₂₆ (R ₂₇ ), (X represents each atom of sulfur or nitrogen or oxygen; ₂₆ and R ₂₇ each represent a hydrogen atom, an alkyl group or an alkylcarbonyl group, and R ₂₆ and R ₂₇ may form a ring). Further, R _{21 to} R ₂₅ may be bonded to each other to form a ring. Of the groups R _{21 to} R ₂₅ , the substituents at the ortho positions may be bonded to each other to form a 5- to 7-membered ring. However, each group of R _{21 to} R ₂₅ is not simultaneously a hydrogen atom, and R ₂₃ is a halogen atom, —O
-R _27, in the case of _{-S-R 27,} at least one of R _{21, R 25} is an alkyl group. ] 5. A silver halide photographic emulsion used in a silver halide emulsion layer, comprising 95 mol% or more of silver chloride, wherein an alkali metal ion has a molar ratio to a compound represented by the following general formula (III). A silver halide photographic emulsion characterized by being added 10 times or more in the above. Embedded image [Wherein, R ₃₁ represents a halogen atom or a monovalent group;
₃₁ and X ₃₂ each represent a halogen atom, a carboxylic acid group (including its salt), a sulfonic acid group (including its salt), an alkylthio group, an acyl group, a lower alkylcarbamoyl group having 1 to 3 carbon atoms, an acylamino group, It represents an acyloxy group, an alkyloxycarbonyl group, a lower aminosulfonamide group having 1 to 3 carbon atoms, an aminosulfonyl group, an alkylsulfonyl group, an alkylsulfinyl group, or a group represented by the general formula (IV). n ₃₁ and the sum is an integer from 1 to 4 of _{n 32,} the sum of n _{31, n 32} and _{n 33} is 1
Represents an integer of 4. ] [Wherein _Y 31 _{to Y 35} each represent a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, or a salt thereof a carboxylic acid group, or represents a sulfonic acid group (or a salt _thereof), the Y 31 _{to Y 35} Not all are hydrogen atoms. n ₃₁ represents an integer of 0 to 3. ] 6. A silver halide photographic emulsion used for a silver halide emulsion layer, comprising 95 mol% or more of silver chloride, wherein an alkali metal ion is present in a molar ratio to a compound represented by the following general formula (V). A silver halide photographic emulsion characterized by being added 10 times or more in the above. Formula _{(V) -O- (CR 41 R} 42 -CR 43 R 44 -O) n- (n ≧ 1) [R 41 ~R 44 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, Or a sulfonyl group, which may be the same or different. The basic unit is shown in parentheses, but may or may not be cyclically formed by oxygen atoms at both ends. When a ring is formed, it may be condensed with one or more aromatic rings. In the case of the A-chain molecule, both ends are hydroxyl groups. ] 7. A silver halide photographic material having at least one silver halide photographic emulsion layer on a support, wherein the silver halide emulsion of the silver halide photographic emulsion layer is as defined in claim 2 A silver halide photographic material, which is the silver halide photographic emulsion described in any one of the above.