JPH1031279A - Sliver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce fluctuation of characteristics, such as fog and sensitivity between manufacture batches and to enable rapid processing by incorporating at least one of specified plural compounds and at least one kind of radical scavenger. SOLUTION: The silver halide photographic sensitive material having on a support at least one silver halide emulsion layer containing >=90mol.% silver chloride and at least one kind of radical scavenger and at least one of compounds selected from among compounds (A)-(D); (A) a compound having a structure of >=3 sulfur or selenium or the like atoms combined with each other in the molecule, (B) an organic compound having at least 2 sulfur or selenium or the like atoms not combined with each other as the constituents of a hetero ring, (C) a compound represented by the formula: R11 -X11 -X12 -R12 in which each of X11 and X12 is sulfur or selenium atom or the like; and (D) at least 2 inorganic sulfur atoms or a thiosulfonic acid compound represented by the formula: R21 -SO2 S-M21 in which M21 is an aliphatic group or the like and M21 is H atom or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material which has small fluctuations in photographic characteristics such as fog and sensitivity between production batches of a silver halide emulsion and which can be rapidly processed.

[0002]

2. Description of the Related Art Silver halide photographic materials (hereinafter, also simply referred to as "photosensitive materials") have high sensitivity, and are excellent in gradation, sharpness, granularity, and color reproducibility.
It is used very often today.

[0003] In recent years, in order to finish a large number of prints in a short delivery time, rapid processing of a photosensitive material for color photographic paper has been desired. As a means for speeding up, it is known to use silver chloride or silver chlorobromide having a high silver chloride content for the silver halide emulsion to be used. For example, US Pat.
Nos. 756 and 4,225,666, and JP-A-55-26.
No. 589, No. 58-91444, No. 58-95339
Nos. 58-94340, 58-95736, 58-106538, 58-107531, 5
8-107532, 58-107533, 58
JP-A-108533, JP-A-58-125612 and the like describe the technology. With the introduction of these technologies,
Current color papers have been devised so that a high-quality image can be obtained by a development process of only several tens of seconds.

However, photosensitive materials containing silver chloride at a high concentration are known to have the disadvantages of low sensitivity and easy fogging and the disadvantage of large fluctuations in performance during storage of the photosensitive material, and various improvements have been made.

JP-A-63-301039 and JP-A-63-3
Nos. 09944, 64-86135 and 63-316
No. 039 and the like disclose a technique using inorganic sulfur. JP-A-2-256046 discloses that in a light-sensitive material having a silver halide emulsion layer having a silver chloride content of 90 mol% or more, at least one of the photographic constituent layers has at least three sulfur atoms in the molecular structure linked thereto. The solubility product of at least one polysulfide organic compound or an organic compound having at least two thioether bonds or at least one disulfide bond as a member of a heterocycle with silver ions is 1 × 10 ⁻¹⁰ or less. It is disclosed that fog is low, sensitivity over time and fluctuation of fog can be reduced by including at least one nitrogen heterocyclic compound. Besides, Japanese Patent Publication No. 62-17216,
U.S. Pat. No. 3,656,955 also discloses a technique using a polysulfide compound.

US Pat. No. 4,054,457 discloses that when a polysulfide cyclic compound having a specific thiocarbonyl group is used as a sensitizer for various silver halide emulsions,
It discloses that regardless of the pH at the time of ripening, sensitivity, minimum density and maximum density are excellent, and storage stability is also excellent.

JP-A-6-19024 and JP-A-6-1902
No. 6 discloses that, among the compounds represented by the above general formula (I), a reaction-inactive compound is used before or during precipitation of a silver halide emulsion and before spectral / chemical sensitization or spectral / chemical sensitization. It is disclosed that the addition to the inside can improve the immediate fog and the rise of the fog after aging. Further, JP-A-6-1
No. 9037 discloses that the effect can be enhanced by adding these compounds as a solid dispersion. European Patent 627,657 discloses a technique using a disulfide compound having a water-soluble group, and JP-A-6-35147 discloses a silver chloride emulsion containing a 1: 1 mixture of a diaminodisulfide and a sulfinate compound.
It is disclosed that the inclusion in a weight ratio of １ ： 1: 20 improves the storage stability of the color photographic material and the performance fluctuation due to the temperature fluctuation during exposure. JP-A-6-2
No. 02265 discloses that after the precipitation of a silver halide emulsion,
Prior to chemical sensitization or during spectral / chemical sensitization, the compound of formula (I)
It discloses that low fog and high sensitivity can be obtained by adding a specific disulfide compound and a sulfinate or seleninate compound among the compounds represented by the following formulas.

JP-A-6-301139 discloses that at least 50% of the projected area of a silver halide grain population has a {100} major plane with an adjacent edge ratio of less than 10, and an aspect ratio of at least 2. High sensitivity and improved storage stability are obtained by incorporating any of the following photographic stabilizers A to G into a silver halide emulsion which is silver halide grains and has a silver chloride content of at least 50 mol%. Is disclosed.

A. B. Mercaptoheterocyclic nitrogen compounds containing a mercapto group bonded to a carbon atom bonded to an adjacent nitrogen atom of the heterocyclic ring system B. quaternary aromatic chalcogen azolium salts wherein the chalcogen is sulfur, selenium or tellurium B. Triazole or tetrazole with ionic hydrogen bonded to adjacent nitrogen atoms of the heterocyclic ring system B. dichalcogenide compounds comprising -XX- bonds between carbon atoms, wherein each X is divalent sulfur, selenium or tellurium —SO ₂ SM (where M is a proton or a cation)
An organic compound having a thiosulfonyl group having Second mercury salt G. Quinone compounds However, as a result of the present inventors' research, when these techniques are applied, fog reduction and sensitization effects can be obtained, but sensitivity and fog are reduced due to changes in the preparation batch of silver halide emulsion grains. It has been found that there is a drawback that the level of tends to fluctuate. As a result of the analysis of the present inventors, it has been found that when the pH or pAg at the time of forming silver halide grains fluctuates, the fluctuation of the performance increases, but the direction of the fluctuation of the pH or pAg and the direction of the fluctuation of the performance vary. The correlation is not clear,
The mechanism of this phenomenon has not been elucidated yet.

The present inventors have found that these problems can be solved by using a radical scavenger, and have completed the present invention.

JP-A-8-62768 discloses a technique of a silver halide photographic emulsion characterized by being subjected to reduction sensitization and gold / chalcogen sensitization and containing at least one kind of radical scavenger. Have been. According to the description of the gazette, this technique has a disadvantage that the sensitivity increase width is smaller in the conventional reduction sensitization method than in the hydrogen sensitization,
This is a technique of improving by including a radical scavenger. JP-A-8-76311 discloses that
A storage material having a silver halide emulsion layer having a reduction sensitized silver halide photographic emulsion and containing at least one kind of radical scavenger is used for preservation fog and latent image caused by reduction sensitization. It discloses that deterioration of intensification is improved.

It is disclosed that any of the techniques is preferably used in combination with the thiosulfonic acid compound (C) of the present invention. However, in each case, Japanese Patent Application Laid-Open No. 8-62
No. 768, page 26, left column, line 26, 2 to 1
This technique is preferably applied to silver iodobromide or silver chloroiodobromide containing 0 mol% of silver iodide, and does not disclose anything about the problem of a silver halide emulsion containing silver chloride at a high concentration. Neither was suggested.

JP-A-8-54717 discloses that sharpness is improved by using a photosensitive material containing at least one compound having a specific structure including a radical scavenger of the present invention and a silver halide emulsion having an average grain size of 0.25 μm or less. It discloses that characteristics excellent in granularity and latent image stability can be obtained. According to the description of the gazette, there is a technique of improving the deterioration of latent image stability caused by using a fine grain emulsion having a particle size of 0.25 μm or less to improve sharpness and granularity with a specific compound, and is preferably used. With respect to the composition of the silver halide emulsion, it is described that silver chlorobromide or silver chloride may be used, but it is more preferable that silver bromoiodide or silver chloroiodobromide is used. In each of the examples, a silver iodobromide cubic emulsion having an average iodine content of 2.6 mol% is used, and there is no description of the problem of a silver halide emulsion containing silver chloride at a high concentration. Not even.

JP-A-8-62767 discloses that a photosensitive material having a gelatin coating amount of 10 g / m ² or more on the emulsion layer side and containing at least one compound having a specific structure including a radical scavenger according to the present invention is disclosed. It discloses that deterioration of latent image stability and deterioration of storage stability caused by increasing gelatin are improved. Regarding the halogen composition, as in the above-mentioned JP-A-8-62768, 2
This is a technique preferably applied to silver iodobromide or silver chloroiodobromide containing 10 to 10 mol% of silver iodide, and describes any problem concerning a silver halide emulsion containing silver chloride at a high concentration. No, and no suggestion.

[0015]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which has small fluctuations in characteristics such as fog and sensitivity between production batches of a silver halide emulsion and which can be rapidly processed. Is to do.

[0016]

As a result of extensive studies by the present inventors, (1) a silver halide photograph having at least one silver halide emulsion layer having a silver chloride content of 90 mol% or more on a support. In the photosensitive material, at least one of the following (A) to
A silver halide photographic material containing a compound selected from (D) and at least one radical scavenger.

(A) a compound having a structure in which three or more sulfur, selenium, or tellurium atoms are linked in a molecule; (B) an organic compound having at least two unlinked sulfur, selenium, or tellurium atoms as members of a heterocyclic ring (C) a compound represented by the following general formula (I): R ₁₁ -X ₁₁ -X ₁₂ -R _{12 wherein} X ₁₁ and X ₁₂ each independently represent a sulfur, selenium or tellurium atom R ₁₁ and R ₁₂ represent X ₁₁ and X
Together with ₁₂ , or independently, represents a group of atoms necessary to form a cyclic group, an acyclic group or a heterocyclic group.

(D) Inorganic sulfur or a thiosulfonic acid compound represented by the following general formula (II): R ₂₁ —SO ₂ S—M _{21 wherein} R ₂₁ is an aliphatic group, an aromatic group or Represents a heterocyclic group,
M ₂₁ represents a hydrogen atom or a monovalent cation.

(2) The silver halide photographic material as described in (1), wherein a sulfinic acid and a selenic acid compound are used in combination.

(3) The silver halide photographic material as described in (1) or (2), wherein the radical scavenger is represented by the following general formula (III).

Formula (III) R ₃₁ —N (OH) —R _{32 In the} formula, R ₃₁ is an alkyl group, an alkenyl group, an aryl group,
Heterocyclic group, acyl group, sulfonyl group, sulfinyl group,
A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R ₃₂ represents the same group as indicated by the hydrogen atom or R _31. Where R
_{When 31} is an alkyl, alkenyl or aryl group,
₃₂ 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 ₃₁ and R ₃₂ may be combined with each other to form a 5- to 7-membered nitrogen-containing heterocyclic ring.

Thus, it is clear that the object of the present invention can be achieved, and the present invention has been completed.

Hereinafter, the present invention will be described in detail.

The composition of the silver halide emulsion according to the present invention is as follows:
It is characterized by containing 90 mol% or more of silver chloride,
Silver chloroiodide, silver chlorobromide containing 95 mol% or more of silver chloride;
Silver chloroiodobromide is preferred. From the viewpoint of rapid processing property and processing stability, it is preferably 97 mol% or more, more preferably 9 mol% or more.
Silver chlorobromide containing 8 to 99.9 mol% of silver chloride.

The silver halide emulsion according to the present invention preferably contains a heavy metal compound for the purpose of improving reciprocity failure. The effect differs depending on the type of heavy metal compound, but potassium hexachloroiridate (IV), potassium hexabromo (IV), hexacyanoruthenium (II
Compounds such as I) potassium and potassium hexacyanoferrate (II) tend to increase the performance variation,
This can be improved, and when a compound such as potassium pentachloronitrosylruthenate (III) or potassium hexachlororhodium (III) is contained, the effect of the present invention is greatly exhibited, which is a preferred embodiment.

Typical examples of the metal compound which can be used in the silver halide emulsion of the present invention are shown below.

(DI-1) K ₃ [Fe (CN) ₆ ] (DI-2) K ₄ [Fe (CN) ₆ ] (DI-3) K ₄ [Ru (CN) ₆ ] (DI-4) K ₂ [Ir (CN) ₆ ] (DI-5) K ₂ [Fe (CO) ₅ ] (DI-6) K ₃ [Co (CN) ₆ ] (DI-7) K ₂ [IrBr ₆ ] (DI _{-8) K 3 [RhCl 6]} (DI-9) K 2 [IrCl 6] (DI-10) K 3 [IrCl 6] (DI-11) Cs 2 [Os (NO) Cl 5] (DI-12 ) K ₂ [Ru (NO) Cl ₅ ] (DI-13) K ₂ [Fe (NO) (CN) ₅ ] (DI-14) Cs ₂ [Os (NS) Cl ₅ ] These metal complexes are halogenated. In order to include the metal complex in silver grains, the metal complex is formed before silver halide grains are formed, during silver halide grains are formed, or after silver halide grains are formed. It may be added at any location of each step during ripening. The addition amount of these compounds is more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide, and particularly preferably 5 × 10 ⁻⁴ mol.
It is preferably from 10 ^{-9 to} 5 × 10 ^-6 mol.

The grain size of the silver halide grains is not particularly limited, but is preferably in the range of 0.25 to 1.2 μm in consideration of rapid processing, sensitivity, and other photographic properties.
The particle size can be measured by various methods generally used in the technical field of the art. As a representative method, there is a “particle size analysis method” of Loveland (A.
S. T. M Symposium on Right Microscopy, 1955, pp. 94-122) or Chapter 2 of "Theory of Photographic Process" (Mies and James, 3rd Edition, published by Macmillan, 1966). I have.

The particle size distribution of the halogenated particles may be polydisperse or monodisperse. Preferably, it is a monodispersed silver halide having a coefficient of variation in particle size distribution of 0.20 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the width of the particle size distribution, and is defined as follows.

Coefficient of variation = S / R (S: standard deviation of particle size distribution, R: average particle size) The particle size referred to here is the diameter of a spherical silver halide particle, or a cubic or spherical particle. In the case of particles having shapes other than, 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 prepared by any of an acidic method, a neutral method and an ammonia method. Emulsion grains may be grown at a time or seed grains may be formed and then grown. In this case, the method for producing the seed particles and the method for 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 and a combination thereof, but the simultaneous mixing method is preferred. Furthermore, as one form of the simultaneous mixing method,
The pAg controlled double jet method described in JP-A-54-48521 can also be used. Also, JP-A-57-92523 and JP-A-57-9252.
No. 4, etc., a device for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE 2,921,164, etc. An apparatus for continuously adding a salt and a water-soluble aqueous halide solution while changing the concentration may be used. If necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The desalting method is described in US Pat. No. 4,334,012.
Ultrafiltration method for taking out a reaction mother liquor out of a reactor described in JP-B-56-501776 and U.S. Pat.
No. 556, No. 2,735,841, etc., there is a precipitation method in which desalting is carried out using a precipitating agent, but those obtained by an ultrafiltration method are particularly preferred because of their small performance fluctuation.

The silver halide grains according to the present invention may have any shape. One preferred example is $ 10
It is a cube having a 0 ° plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666;
JP-A-55-26589, JP-B-55-42737.
No., The Journal of Photographic Science (J. Photogr. Sci) 21, 39 (1973), etc., have shapes such as octahedron, tetradecahedron, and dodecahedron. Particles can be made and used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed.

Compounds having a structure in which three or more sulfur, selenium or tellurium atoms are linked in the molecule and having at least two unlinked sulfur, selenium or tellurium atoms as members of a heterocyclic ring used in the present invention. As the organic compound, compounds described in JP-A-2-256046 can be used.

In the compound represented by the above formula (I), X ₁₁ and X ₁₂ independently represent a sulfur, selenium or tellurium atom, preferably a sulfur atom.

The acyclic group represented by R ₁₁ and R ₁₂ includes a substituted or unsubstituted alkyl group (methyl, ethyl, propyl,
Butyl, benzyl and the like), an amino group (N, N-diethylamino, N, N-diphenylamino, N-butylamino and the like), an aminothiocarbonyl group, a benzoyl group and the like.

The cyclic groups represented by R ₁₁ and R ₁₂ include substituted and
Unsubstituted aryl groups (phenyl, naphthyl, etc.), substituted,
Unsubstituted heterocyclic groups (morpholino, piperazino, pyridinyl and the like) can be mentioned.

Examples of the cyclic group which R ₁₁ and R ₁₂ can form together with X ₁₁ and X ₁₂ include a dithiane ring, a dithiolane ring and a 1,2,4-dithiazolidine ring. These rings may be substituted with a substituted or unsubstituted alkyl group, carboxyl group, or the like, or a benzene ring, a naphthalene ring, or the like may be condensed.

[0041] Preferable examples of the compound represented by formula (I) is a compound having a compound or a morpholino group with substituted as R _11, R _12, an unsubstituted phenyl group, R _11, R ₁₂ is X Compounds that form a dithiane ring or a dithiolane ring with ₁₁ , ₁₂ can be given.

The inorganic sulfur that can be used in the present invention is
Although it is known to have several allotropes, any of those allotropes may be used. Among the allotropes, those which are stable at room temperature are α-sulfur belonging to orthorhombic system,
Preferably, α-sulfur is used.

The thiosulfonic acid compound represented by the general formula (II) may be a free acid or a salt thereof.

The aliphatic group represented by R ₂₁ is preferably an alkyl group having 1 to 22 carbon atoms, or an alkenyl or alkynyl group having 2 to 22 carbon atoms. More preferably, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group or alkynyl group having 3 to 5 carbon atoms is preferable. These groups may have a substituent.

Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, cyclohexyl and the like. Examples of the alkenyl group include allyl and butenyl.
Examples of the alkynyl group include propargyl and butynyl.

The aromatic group represented by R ₂₁ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 10 carbon atoms. These groups may have a substituent, and specific examples include phenyl, p
-Groups such as tolyl and naphthyl.

The heterocyclic group represented by R ₂₁ is 3 to 15
Member rings are preferred, and 5- to 6-membered rings containing a nitrogen atom are more preferred. Specific examples include pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, imidazole, benzothiazole, tellurazole,
Each ring such as oxadiazole and thiadiazole can be exemplified.

The group represented by R ₂₁ has 6 carbon atoms.
Most preferred are from 10 to 10 substituted aromatic rings. Examples of the substituent include an alkyl group (eg, methyl, ethyl, butyl, pentyl), an alkoxy group (eg, methoxy, ethoxy),
Aryl group (phenyl, naphthyl, etc.), hydroxyl group, halogen atom, aryloxy group (phenoxy, etc.), alkylthio group (methylthio, butylthio, etc.),
Arylthio group (phenylthio etc.), acyl group (acetyl, propionyl etc.), sulfonyl group (methylsulfonyl, phenylsulfonyl etc.), acylamino group (acetylamino etc.), sulfonylamino group, acyloxy group,
(A) to (A) to below which include a carboxy group, a cyano group, a sulfo group, an amino group and the like can be preferably used.
Specific examples of the compound of the group (D) are shown below, but the invention is not limited thereto.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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(A) which can be used in the present invention
The compound of the group (D) is added in a step of preparing a silver halide emulsion grain, a step of chemical sensitization, a step of preparing a coating solution at the end of the step of chemical sensitization, or the like according to the purpose. When chemical sensitization is carried out in the presence of these compounds, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻ mol per mol of silver halide. It is used in an amount of about ⁴ mol. When adding at the end of chemical sensitization,
The amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. When added to the silver halide emulsion layer in the coating solution preparation step, 1 × per mol of silver halide is used.
An amount of about 10 ^-6 to 1 × 10 ^-1 mol is preferable, and 1 × 10
^-5 to 1 × 10 ^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 to 1 × 10 ^-3 mol per 1 m ² .

The compounds (A) to (D) used in the present invention are preferably used in combination with a sulfinic acid or seleninic acid compound represented by the following general formula (IV).

Formula (IV) R ₄₁ -X ₄₁ O ₂ -M _{41 wherein} X ₄₁ represents a sulfur atom or a selenium atom. R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and M ₄₁ represents a hydrogen atom or a monovalent cation.

The compound represented by formula (IV) used in the present invention may be a free acid or a salt thereof.

X ₄₁ represents a sulfur atom or a selenium atom,
Sulfur atoms are more preferred.

The aliphatic group represented by R ₄₁ is preferably an alkyl group having 1 to 22 carbon atoms, or an alkenyl or alkynyl group having 2 to 22 carbon atoms. More preferably, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group or alkynyl group having 3 to 5 carbon atoms is preferable. These groups may have a substituent.

Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, cyclohexyl and the like. Examples of alkenyl groups include allyl, butenyl and the like. Examples of the alkynyl group include propargyl and butynyl.

The aromatic group represented by R ₄₁ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 10 carbon atoms. These groups may have a substituent, and specific examples include phenyl, p-tolyl, and naphthyl.

The heterocyclic group represented by R ₄₁ is 3 to 1
A 5-membered ring is preferable, and a 5- to 6-membered ring containing a nitrogen atom is more preferable. Specific examples include pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, imidazole, benzothiazole, tellurazole,
Each ring such as oxadiazole and thiadiazole can be exemplified.

The group represented by R ₄₁ has 6 carbon atoms.
Most preferred are from 10 to 10 substituted aromatic rings. Examples of the substituent include an alkyl group (eg, methyl, ethyl, butyl, pentyl), an alkoxy group (eg, methoxy, ethoxy),
Aryl group (phenyl, naphthyl group, etc.), hydroxyl group, halogen atom, aryloxy group (phenoxy, etc.), alkylthio group (methylthio, butylthio, etc.),
Arylthio group (phenylthio etc.), acyl group (acetyl, propionyl etc.), sulfonyl group (methylsulfonyl, phenylsulfonyl etc.), acylamino group (acetylamino etc.), sulfonylamino group, acyloxy group,
Examples thereof include a carboxy group, a cyano group, a sulfo group, and an amino group. Specific examples of the sulfinic acid and selenic acid compounds that are preferably used are shown below.

[0070]

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Next, the radical scavenger used in combination with the compounds (A) to (D) will be described.

The radical scavenger according to the present invention is defined as follows: as described in JP-A-8-62768, “0018”, at 25 ° C., 0.05 g of galvinoxyl.
mmoldm ^-3 ethanol solution and 2.5 of test compound
An ethanol solution of mmoldm- ^{3 is} mixed by the stopped flow method, and the time change of the absorbance at 430 nm is measured, and a compound that substantially discolors galvinoxyl (decreases the absorbance at 430 nm) is used. May be measured at a lower concentration).

Preferably, the discoloration rate constant of galvinoxyl determined by the above method is 0.01 mmol ⁻¹ s ⁻¹ d
m ³ or more, more preferably 0.1 mmol ⁻¹ s ⁻¹ dm ³ or more.

A method for determining the radical scavenging rate using galvinoxyl is described in the Microchemical Journal (Microchem. J.), Vol. 31, pp. 18-21 (1985). No., p.321 (1970).

[0075] In the general formula _{(III) R 31 -N (OH} ) -R 32, R 31 is one of an alkyl group (1 to 36 are preferably carbon atoms, more preferably 1 to 26, for example, methyl, ethyl , I-propyl, cyclopropyl, i-butyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl, etc.), alkenyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 26 carbon atoms)
Such as vinyl, allyl, i-propenyl, 2-
Butenyl, oleyl, etc.), an aryl group (having preferably 6 to 40, more preferably 6 to 30 carbon atoms, such as phenyl and naphthyl), a heterocyclic group (a nitrogen atom, a sulfur atom, an oxygen atom as a ring-constituting atom) A group forming a 5- to 7-membered heterocyclic ring having at least one atom or phosphorus 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-triazin-2-yl,
1,2,4-triazin-3-yl, pyridyl, pyrazinyl, pyrimidinyl, prenyl, quinolyl, imidazolyl, 1,2,4-triazol-3-yl, benzimidazol-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 such as methanesulfonyl, butanesulfonyl, benzenesulfonyl, toluenesulfonyl and the like), a sulfinyl group (preferably an alkyl or arylsulfinyl group, e.g. Methanesulfinyl, benzenesulfinyl, etc.), carbamoyl group (N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl, etc.), sulfamoyl group (N-methylsulfamoyl, N-phenylsulfamoyl, N, N-diethylsulfamoyl, N-ethyl-N-dodecylsulfamoyl and the like, an alkoxycarbonyl group (methoxycarbonyl, i-pentyloxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, Octadecyloxycarbonyl, etc.) or an aryloxycarbonyl group (phenoxycarbonyl, naphthoxycarbonyl, etc.).

R ₃₂ represents a hydrogen atom or the same group as represented by R ₃₁ . In addition, between R ₃₁ and R ₃₂ have the aforementioned limitations.

Examples of the 5- to 7-membered ring which may be formed by combining R ₃₁ and R ₃₂ include succinimide, phthalimide, triazole, urazole, hydantoin, 2-oxo-4-oxazolidinone ring and the like.

The groups represented by R ₃₁ and R ₃₂ 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.

Hereinafter, typical specific examples of the radical scavenger represented by the general formula (III) will be shown.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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For the silver halide emulsion used in the present invention, a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer can be used.

As chalcogen sensitizers, sulfur sensitizers,
A selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect, and the like, but is preferably 5 × 10 ^{-10 to} 5 × 10 ^-10 per mol of the silver halide. In the range of ^10-5 mol, preferably 5
The amount is from ^10-8 to ^310-5 mol.

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 sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, and the like.
It is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization. Preferred reduction sensitizers include thiourea dioxide, amine borane, sodium sulfite, and the like.

The silver halide emulsion may contain a known antifoggant for the purpose of preventing fog generated during the preparation of the light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Agents can be used. Examples of preferred compounds that can be used for such purposes include the compounds represented by the general formula (II) described in the lower column of page 7 of JP-A-2-14636, and more preferred specific compounds Are (IIa-1) to (IIa-8) and (IIb-1) to (IIb-1) described on page 8 of the publication.
b-7) or 1- (3-methoxyphenyl)-
Examples thereof include 5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole.

These compounds are added in the steps of preparing silver halide emulsion grains, chemical sensitization, stopping chemical sensitization, and preparing a coating solution, depending on the purpose.
When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added in the step of stopping chemical sensitization, 1 × 10 ⁻⁶ to 1 mol / mol of silver halide is used.
An amount of about 1 × 10 ⁻² mol is preferable, and 1 × 10 ^{−5 to} 5 ×
^10-3 mol is more preferred. When the silver halide emulsion layer is added to the silver halide emulsion layer in the coating solution preparation step, one silver halide emulsion layer
The amount is preferably about 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ^-9 to 1 × 10 per 1 m ²
It is preferably about ^-3 mol.

In the 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, dyes having absorption in the visible region include those described in JP-A-3-2518.
The dyes of AI-1 to 11 described in JP-A No. 40, page 308 and the dyes described in JP-A-6-3770 are preferably used.
The compounds represented by the general formulas (I), (II) and (III) described in the lower left column of the page have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and have a residual color. It is preferable because there is no contamination due to. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.

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 since the whiteness can be improved. The compound preferably used is a compound represented by the general formula described in JP-A-2-232652.
Compounds represented by II are mentioned.

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

As the spectral sensitizing dye used in the present invention, any known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 described in JP-A-3-251840, page 28, can be used. It is preferable to use -8 alone or in combination. As the green photosensitive sensitizing dye, the same publication 28
GS-1 to GS-5 described on the page are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-29 described in p.
8 is preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. And the dyes of IRS-1 to 11 described on pages 6 to 8 are preferably used.
Further, these infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizer S described in JP-A-4-285950, pp. 8-9.
S-1 to SS-9 and JP-A-5-66515, 15-1
It is preferable to use compounds S-1 to S-17 described on page 7 in combination.

The sensitizing dye used in the present invention includes: a kind of the sensitizing dye, a halogen composition of a silver halide emulsion to be applied,
Although it depends on the grain size and the like, it is preferably used in a range of 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol, more preferably 1 × 10 ^{−4 to} 7 × 10 ⁻⁴ mol per mol of silver halide.

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

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. For example, a method of dispersing in the presence of a surfactant suppressed below can be used.

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

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.

As the sensitizing dye according to the present invention, a plurality of sensitizing dyes can be used in combination as long as the effects of the present invention are not impaired. In this case, the two sensitizing dyes may be added separately or may be added after mixing in advance.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it can be used, particularly typical compounds include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength range. This is known as a cyan dye-forming coupler having a spectral absorption maximum wavelength at 600 to 750 nm.

Examples of the cyan coupler which can be preferably used include couplers represented by formulas (C-I) and (C-II) described in the lower left column of page 5 of JP-A-4-114154.

Examples of the magenta coupler which can be preferably used include those represented by formulas (MI) and (M-II) described in the upper right column of JP-A-4-114154, page 4. it can. Preferred from among the magenta couplers is a coupler represented by the general formula described in the publication, page 4, right upper column (M-I), of which, R _M of the formula (M-I) is 3 A coupler which is a lower alkyl group is particularly preferable because of its excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail depiction power, and thus are preferable.

Further, as a yellow coupler which can be preferably used, a coupler represented by formula (Y-I) described in the upper right column on page 3 of JP-A-4-114154 can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, the general formula [Y-
The coupler of the formula [1], wherein R _Y1 is an alkoxy group, or the coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone, and is therefore preferable.

When an oil-in-water type emulsion dispersion method is used to add a coupler or other organic compound, a water-insoluble high-boiling organic solvent having a boiling point of 150.degree. Alternatively, they are dissolved together with a water-soluble organic solvent, 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 simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added.

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).

Preferred compounds used as surfactants for dispersing photographic additives and adjusting the surface tension during coating contain a hydrophobic group having 8 to 30 carbon atoms and a sulfo group or a salt thereof in one molecule. To do. Specific examples include A-1 to A-11 described in JP-A-64-26854. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution after the addition are short. , Preferably within 10 hours, more preferably within 3 hours and 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.

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

In a color light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or a compound is added to a silver halide emulsion layer to prevent fog. And the like are preferably improved. It is preferable to add an ultraviolet absorber to prevent static fog or to improve the light fastness of the dye image.

Preferred examples of the ultraviolet absorber include benzotriazoles. Particularly preferred compounds are those represented by the general formula III-3 described in JP-A-1-250944 and those represented by the general formula III described in JP-A-64-66646. III
A compound represented by the general formula I described in JP-A-4-1633; a compound represented by the general formula I described in JP-A-4-16333;
And the compounds represented by the general formulas (I) and (II).

It is advantageous to use gelatin as a binder in the light-sensitive material according to the present invention. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose A hydrophilic colloid such as a derivative, a single or a synthetic hydrophilic polymer such as a copolymer 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. That is,
It is preferable to use the compounds described in 1-249054 and 61-245153. 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 fungi 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 for the light-sensitive material, any material may be used, such as paper coated with polyethylene (PE) or polyethylene terephthalate (PET), paper support made of natural pulp or synthetic pulp, and vinyl chloride. Sheet, polypropylene (P
P), PET 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. PE or PET as water-resistant resin
Or their copolymers are preferred.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by weight or more, more preferably 15% by weight, in order to improve sharpness.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or to an undercoat layer (adhesion, antistatic property, dimensional stability of the support surface). , One or more subbing layers to improve rub resistance, hardness, antihalation properties, friction properties and / or other properties).

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

In order to form a photographic image using the photosensitive material according to the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. After the image is once converted to digital information, the image may be formed on a CRT (cathode ray tube), and the image may be formed on a photosensitive material to be printed and printed, or based on the digital information. The printing may be performed by scanning while changing the intensity of the laser beam.

The silver halide emulsion of the present invention is particularly preferably applied to a light-sensitive material for forming an image for direct viewing, for example, color paper, color reversal paper, a light-sensitive material for forming a positive image, a light-sensitive material for display. And light-sensitive materials for color proofing. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

Known compounds can be used as the aromatic primary amine developing agent used in the color developing process of the color light-sensitive material.

In the present invention, the above 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 to 70 ° C. 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, it is preferable that the temperature is not too high.

Conventionally, the color development time is generally 3 minutes 30 minutes.
Although it is performed in about a second, in the present invention, it is preferably performed within 40 seconds, and more preferably within 25 seconds.

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

After the color development, the light-sensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed.
Further, as an alternative to the washing process, a stabilizing process may be performed.

The developing apparatus used for developing the photosensitive material according to the present invention may be a roller transport type in which the photosensitive material is conveyed between rollers arranged in a processing tank. It may be an endless belt system in which the processing liquid is fixed and conveyed. However, a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is conveyed, or a processing liquid is sprayed. A spray method, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is usual to run using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0131]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 In 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
The following (Solution A) and (Solution B) were pAg = 7.3, pH =
The solution was added simultaneously while controlling to 3.0, and the following (solution C) and (solution D) were simultaneously added while controlling to pAg = 8.0 and pH = 5.5. At this time, the control of pAg is described in
The pH was controlled using a sulfuric acid or sodium hydroxide aqueous solution.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added and 200 ml (Solution B) Silver nitrate 10 g Water was added and 200 ml (Solution C) Sodium chloride 102.7 g Potassium hexachloroiridium (IV) ate 4 × 10 ⁻⁸ mol potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml After desalting using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to obtain an average particle diameter of 0.40 μm.
m, a coefficient of variation of 0.08, and a monodispersed cubic emulsion EMP-101 having a silver chloride content of 99.5%.

EMP-101 was optimally chemically sensitized at 55 ° C. using the following compounds to obtain a green-sensitive silver halide emulsion Em-G101. For chemical sensitization, sodium thiosulfate was added after the silver halide emulsion reached a predetermined temperature, chloroauric acid was added, and then sensitizing dye was added 5 minutes later. At the end of the chemical sensitization, a stabilizer was added to lower the temperature.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 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 GS-1 4 × 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

[0136]

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Next, in the preparation of EMP-1, (C
Solution) and (D solution) were changed to pH 6.5 to change EMP-102, and pAg was changed to 7.7 to change EMP-102.
EMP-104 was prepared by changing to -103 and 7.6.

In the preparation of Em-G101, EMP-
Em-G102 to -G104 were prepared in the same manner except that 101 was changed to EMP-102 to 104.

In the preparation of Em-G101 to G104, only the addition of Exemplified Compound D-6 prior to the addition of sodium thiosulfate was changed to Em-G111 to -G114.
Before addition of sodium thiosulfate
Em-G121-G12
4 was added to Exemplified Compound D-6 prior to the addition of sodium thiosulfate.
And Em-G131 except that E-3 was added.
~ G134 was prepared.

(Preparation of Coated Sample) A 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 on which the emulsion layer is coated, 15 anatase-type titanium oxide having been subjected to surface treatment is applied.
Fused polyethylene, dispersed and contained at a content of weight%, was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and two layers having the following constitutions were further provided to prepare a monochromatic photosensitive material.
The coating solution was prepared as follows.

First layer coating liquid 12.14 g of magenta coupler (M-1), additive (S
T-3) 12.14 g, 10.32 g of (ST-4) and 7.9 g of a high boiling point organic solvent (DIDP), (DBP) 7.
To 9 g, 60 ml of ethyl acetate was added and dissolved, and the mixture was emulsified and dispersed in 220 ml of a 10% gelatin aqueous solution containing 12 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a magenta coupler dispersion.

This dispersion was mixed with a silver halide emulsion (containing 8.5 g of silver) prepared under the following conditions to prepare a first layer coating solution.

An aqueous gelatin solution was prepared as a coating solution for the second layer, and (H-1) and (H-2) were added as hardening agents. Surfactants (SU-2), (S
U-3) was added to adjust the surface tension. Further, an antifungal agent (F-1) was added to each layer so that the total amount was 0.04 g / m ² . Table 1 shows the layer configuration.

[0144]

[Table 1]

[0145]

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SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate succinate SU-3: di (2,2,3,3) sulfosuccinate , 4,4,
5,5-octafluoropentyl) sodium salt DIDP: di-i-decyl phthalate DBP: dibutyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s- Triazine / sodium The obtained sample was exposed by an ordinary method with an exposure time of 0.5 seconds, and then subjected to the following developing treatment. The obtained dye image was measured with a PDA-65 densitometer (manufactured by Konica Corporation). The fog density and sensitivity were determined. Sensitivity is defined as the reciprocal of the exposure required to obtain a density of 0.75.
And expressed as relative values.

The development process was as follows.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60-80 30 ° C. The composition of the developing solution is shown below.

Color developer 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 diethylenetriamine Sodium pentaacetate 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter. = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution and replenisher solution Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml 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 Optical brightener (Tinopal 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 ( Polyvinylpyrrolidone) 1.0 g Aqueous ammonia (25% ammonium hydroxide aqueous solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia. adjust.

Table 2 summarizes the results.

[0153]

[Table 2]

Among the samples 101 to 104, the sensitivity was 1.2.
The fluctuating range is twice, and fog is 0.07 on average.
8, the range fluctuated by 0.02, but in samples 111 to 114 using only Exemplified Compound D-6, the sensitivity showed a fluctuation range of 1.33 times, and the fog was 0.3% as an average value.
07, a fluctuation of 0.02 as a range. That is,
Due to the effect of D-6, the fluctuation of the performance due to the change of the conditions at the time of preparing the silver halide emulsion was increased in the sensitivity and the fluctuation was not changed in the fog, but the value was reduced. When the same evaluation is performed on a sample using only the radical scavenger E-3, the sensitivity has a fluctuation range of 1.24 times, the average value of fog is 0.08, and the range is 0.
02, and showed no significant effect in the sense of decreasing the fluctuation range.

On the other hand, in the samples 131 to 134 of the present invention, the sensitivity fluctuation was 1.08 times, and the fog was 0.055 on average.
The variation of 0.01 in the range and the effect of reducing the variation in both sensitivity and fog were shown.

Example 2 Emulsions EMP-101 to EMP-101 were prepared by variously changing the compounds (A) to (D) and radical scavengers used in the present invention.
No. 04 was subjected to chemical sensitization, a coated sample was prepared in the same manner as in Example 1, and the sensitivity and fog fluctuation were evaluated in the same manner.

The results are shown in Table 3 below.

[0158]

[Table 3]

It can be seen that the samples in which the compounds (A) to (D) were used in combination all have reduced sensitivity fluctuation width and fog fluctuation width. In the sample using the compound F-2 represented by the general formula (IV) in combination, the fluctuation range of the sensitivity is smaller,
This is a preferred embodiment of the present invention. The combined effect is as shown in D-6.
It is also evident from the table that it cannot be obtained by the combined use of E-2 and F-2, or E-3 and F-2.

Example 3 In the preparation of EMP-101 to 104 of Example 1,
Hexachloroiridium (IV) added in (C solution)
EM except for potassium silicate (Exemplified Compound DI-9) and potassium hexacyanoferrate (II) (Exemplified Compound DI-2)
P-301 to 304 were added to the exemplary compound DI-
8 was added at 4 × 10 ⁻⁹ mol, and EMP-311-314 was added.
By adding 4 × 10 ⁻⁹ mol of Exemplified Compound DI-12 to E
MP-321 to 324 were prepared. The same evaluation as in Example 1 was performed using this emulsion.

Table 4 shows the results.

[0162]

[Table 4]

In the silver halide emulsion to which no metal compound was added, the original fluctuation in sensitivity was small, and DI-9, DI-9
It can be seen that the fluctuation is large in a system to which a metal compound such as -2 is added. This indicates that the present invention is particularly useful for the problem of performance variation that occurs when using a metal compound for the purpose of improving reciprocity failure.

When a metal compound such as DI-8 or DI-12 was further used in combination, a behavior was observed in which the sensitivity fluctuation width was further reduced. Use of such compounds in combination is a preferred embodiment of the present invention.

Example 4 A 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 be coated with the emulsion layer, a molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed in a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied thereon to prepare a multilayer photosensitive material. The coating solution was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 0.34 g, 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and high-boiling organic solvent (DNP)
To 1.67 g, 60 ml of ethyl acetate was added to dissolve, and 20
A 10% aqueous gelatin solution containing 7 ml of a 10% surfactant (SU-1) was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with the following blue-sensitive silver halide emulsion to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 5 and 6, respectively.

(H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension.
The total amount of the fungicide (F-1) was 0.04 g / m ² in each layer.
Was added so that

[0169]

[Table 5]

[0170]

[Table 6]

DNP: dinonyl phthalate DOP: dioctyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2, 5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A: pt-octylphenol

[0172]

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[0173]

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[0174]

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(Preparation of Blue-Sensitive Emulsion) EMP of Example 1
In the preparation of -101 to 104, a monodispersed cubic emulsion EMP-401 having an average particle size of 0.71 µm, a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was changed by changing the mixing time of the liquids. 404 was obtained.

Green-sensitive emulsions Em-G101 to G of Example 1
104, in the preparation of Em-G131-G134,
Chemical sensitization was carried out in the same manner except that MP-101 to 104 were changed to EMP-401 to 404, and the additives were changed as described below, to obtain a blue-sensitive halide emulsion Em-B40.
Nos. 1 to B404 and Em-B431 to B434 were obtained (emulsion No. corresponded to that of the green-sensitive emulsion).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 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 BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

[0178]

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(Preparation of Red-Sensitive Emulsion) EMP of Example 1
In the preparation of -101 to 104, a monodisperse cubic emulsion EMP-405 having an average particle diameter of 0.40 µm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% was changed by changing the mixing time of the liquids. 408 were obtained.

Green-sensitive emulsions Em-G101 to G of Example 1
104, in the preparation of Em-G131-G134,
MP-101 to 104 were changed to EMP-405 to 408, and the additives were changed as follows to perform chemical sensitization at 60 ° C. to obtain a red-sensitive halogenated emulsion Em-R401 to R-E.
404 and Em-R431 to R434 were obtained (Emulsion No.
Corresponded to that of the green-sensitive emulsion).

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 Additive SS-1 2 × 10 ^-3 mol / mol AgX

[0182]

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As the green photosensitive emulsion, the Em-
G101 to G104 and Em-G131 to G134 were used. Blue, green and red-sensitive emulsions were prepared as emulsion Nos. The tenth series is 1
Samples 411 and 43 were divided into groups of 0 and 30.
Sample No. 1 was prepared in the group having the highest sensitivity, and Samples 412 and 432 were prepared (Sample No. was assigned so that the numerical value in the order of 10 corresponds to the emulsion).

The printing conditions were adjusted for the samples 411 and 431 and printing was performed through the developed Konica Color LV-400 to produce color prints. As a result, color prints showing excellent color reproducibility were obtained.

Next, when the samples 412 and 432 were printed under the conditions of the corresponding samples, the prints of the samples 412 and 432 were dark, but the difference in density was clear. By adjusting the exposure conditions of the prints, the image quality was improved in both cases, but a color print with excellent image quality could be obtained with the sample 432, but only a print with poor highlighting was obtained with the sample 412.

[0186]

According to the present invention, it is possible to supply a silver halide photographic light-sensitive material which has a small variation in characteristics such as fog and sensitivity between production batches of a silver halide emulsion and can be processed quickly. Color prints could be obtained stably.

Claims (3)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer having a silver chloride content of 90 mol% or more on a support, comprising at least one of the following (A) to (D): A silver halide photographic material comprising a compound selected and at least one radical scavenger. (A) a compound having a structure in which three or more sulfur, selenium or tellurium atoms are linked in a molecule (B) an organic compound having at least two unlinked sulfur, selenium or tellurium atoms as members of a heterocyclic ring (C) A compound represented by the following general formula (I): wherein R ₁₁ -X ₁₁ -X ₁₂ -R _{12 wherein} X ₁₁ and X ₁₂ each independently represent a sulfur, selenium or tellurium atom; R ₁₁ and R ₁₂ each represent an atomic group necessary for forming a cyclic group, an acyclic group, or a heterocyclic group together with X ₁₁ and X ₁₂ , or independently. ] (D) an inorganic sulfur or the following general formula thiosulfonic acid compound represented by (II) the general formula (II) R ₂₁ -SO ₂ of S-M ₂₁ [wherein, R ₂₁ represents an aliphatic group, an aromatic group or a heterocyclic M ₂₁ represents a hydrogen atom or a monovalent cation. ] 2. The silver halide photographic material according to claim 1, wherein a sulfinic acid or selenic acid compound is used in combination. 3. The silver halide photographic material according to claim 1, wherein the radical scavenger is represented by the following general formula (III). Formula (III): R ₃₁ —N (OH) —R ₃₂ wherein R ₃₁ 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;
₃₂ represents the same group as indicated by the hydrogen atom or R _31. However, when R ₃₁ is an alkyl group, an alkenyl group or an aryl group, R ₃₂ 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 ₃₁ and R ₃₂ may be combined with each other to form a 5- to 7-membered nitrogen-containing heterocyclic ring. ]