JPH05113617A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably obtain an image having high quality by rapid processing by incorporating specific metals and specific gold compds. into a silver halide emulsion. CONSTITUTION:The silver halide emulsion in the silver halide emulsion layers of the silver halide photographic sensitive material having at least one layer of the silver halide emulsion layers consisting of >=90mol% silver chloride on a base contains at least one kind of group VIII metals of the periodic table, group II transition metals, lead, rhenium, molybdenum, tungsten, and chromium at >=1X10<-9>mol per 1mol silver halide and contains at least one kind of the gold compds. expressed by formula I, formula II or formula III. In the formulas, L is a 5-or 6-membered heterocyclic ligand; X denotes an anion group; m denotes 0 to 2; n denotes 1 or 2; P is 1 to 3; q denotes 0 to 3; r denotes 1 to 4. R, W, V, W denote a hydrogen atom, etc.; X<-1> denotes an ion offsetting an intramolecular charge; I denotes 1 to 3; m denotes 2 or 3; n denotes the number of the ions necessary for offsetting the intramolecular charge.

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 capable of stably obtaining a high quality image by processing in a short time. In particular, the present invention relates to a silver halide photographic light-sensitive material capable of stably obtaining a photographic image having excellent gradation by high-intensity short-time exposure using a laser or the like from soft information recorded on a magnetic medium or the like.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials, especially silver halide color photographic light-sensitive materials are used very much today because of their high sensitivity and excellent gradation.

However, the development processing of a silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare the processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, and a dark room is required. There are drawbacks such as a long time from the start of operation until the first print is obtained. In order to make up for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, until now, engineers who were skilled in everything from the development of color negatives to the production of color prints have focused exclusively on a small number of large development laboratories. The method of doing has been adopted.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. Therefore, a so-called minilab, which is capable of consistently performing from color negative development to color print production in a small space such as at a photo shop, is rapidly becoming popular.

In particular, the development processing time has been remarkably shortened by using a silver halide emulsion containing a high concentration of silver chloride. However, a silver halide emulsion containing silver chloride at a high concentration has a large reciprocity law failure, and has drawbacks such as desensitization in low-intensity long-time exposure, high-intensity short-time exposure, and large gradation change. ..

Further, in the field of electronics today, due to remarkable progress in image pickup devices such as CCDs and magnetic recording media, photography is as easy as photography using silver halide so far, and immediately photographed on TV. It has made it possible to enjoy it. To obtain an image recorded on paper from such image data, a thermal transfer method,
Various methods such as ink jet method and electrophotographic method have been put to practical use, but even in these fields, the rich gradation of silver halide photographic materials is outstanding and superior to other methods. Has descriptive power. But,
When the exposure time is less than microseconds, the silver halide photographic light-sensitive material is not only a change in photographic characteristics, such as a decrease in sensitivity or a soft gradation, but it also bends at the point where a characteristic curve exists. Before and after that point, a phenomenon was observed in which the inclination changed significantly, and this phenomenon was more remarkable as the exposure time was shorter.

JP-A-51-139323, JP-A-59-171947 and the like disclose that by incorporating a Group VIII metal compound, the reciprocity law failure can be improved and the sensitivity can be increased. In addition, Japanese Patent Publication No. 49-33781, Japanese Patent Publication No. 50-23618,
52-18310, 58-15952, 59-214028, 61-6784
No. 5 and the like disclose that inclusion of a rhodium compound or an iridium compound makes it possible to improve reciprocity law failure and achieve a high contrast. Although such techniques improve the reciprocity law failure of silver halide emulsions containing a high concentration of silver chloride, they still have the drawback that sufficient sensitivity cannot be obtained, and it is sufficient to sensitize such emulsions with gold compounds. It was a situation in which high sensitivity was obtained. However, when a silver halide emulsion containing a metal compound as described above is subjected to gold sensitization with a compound such as chloroauric acid,
A phenomenon in which the latent image fluctuates greatly in a very short time after exposure and the characteristics change depending on the time from exposure to development, making it difficult to obtain a stable finish.

Japanese Unexamined Patent Publication (Kokai) No. 1-147537 discloses a technique for ripening a silver halide emulsion having a silver chloride content of 95 to 100 mol% using a specific gold compound and a sulfur sensitizer and containing iridium. It is disclosed that a silver halide emulsion having high sensitivity and high contrast can be obtained by ripening the high chloride silver halide emulsion described above using this technique. However, with this compound, with respect to latent image fluctuation immediately after exposure,
It did not have the effect of reducing this.

Further, US Pat. Nos. 5049484 and 5049485 disclose a technique in which a specific gold compound is used for ripening a silver halide emulsion. By aging a silver chloride emulsion with this compound, high sensitivity can be obtained. It also discloses that a high contrast image can be obtained. However, it does not mention or suggest any change in the characteristics of the silver halide emulsion containing a heavy metal compound due to the change in the time from exposure to development.

[0010]

OBJECT OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of stably obtaining a high quality image by processing in a short time. Further, to provide a silver halide photographic light-sensitive material capable of stably obtaining a photographic image having excellent gradation in a short time from an exposure device using a laser or the like from soft information recorded on a magnetic medium or the like. It is in.

[0011]

DETAILED DESCRIPTION OF THE INVENTION While the inventors of the present invention earnestly studied a silver halide photographic light-sensitive material using a high chloride silver halide emulsion for exposure using a laser, the object of the present invention was to
In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer consisting of 90 mol% or more of silver chloride on a support, the silver halide emulsion in the silver halide emulsion layer is a Group VIII metal of the periodic table. , Group II transition metal, at least one of lead, rhenium, molybdenum, tungsten and chromium is contained in an amount of 1 × 10 ^-9 mol or more per mol of silver halide, and the following general formula (I), general formula (IV) or The present invention has been completed by finding out that it is achieved by a silver halide photographic light-sensitive material characterized by containing at least one gold compound represented by the general formula (V).

General formula (I) [H _m Au _n (L) _p (X) _q ] _r [wherein L represents a 5-membered or 6-membered heterocyclic ligand, X
Represents an anion group. m is an integer of 0 to 2, n is an integer of 1 or 2, p is an integer of 1 to 3, q is an integer of 0 to 3, and r is an integer of 1 to 4. ] General formula (IV)

[0013]

[Chemical 3]

General formula (V)

[0015]

[Chemical 4]

[In the formula, R, V, W, and Y represent a hydrogen atom or a substitutable group, and X ⁻ represents an ion that cancels the intramolecular charge. 1 represents an integer of 1 to 3 and m represents 2 or 3.
However, m-1 represents an integer of 0 to 2, and n represents the number of ions necessary to cancel the intramolecular charge. In the above general formula (I), the anion group represented by X is a halide ion (eg, fluoride, chloride, bromide, iodide ion), perchlorate ion, borofluoride ion, sulfuric acid. Examples include groups such as ions, nitrate ions and thiocyanate ions.

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

General formula (II)

[0019]

[Chemical 5]

General formula (III)

[0021]

[Chemical 6]

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

In the general formula (III), Y ₂ each represents an oxygen atom, a sulfur atom, a selenium atom, or a ═NR ₁ group, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are each = C (R ₂ )
_{R 3, = C (R 3} ) -, = C = W, = NR1, -N = group,
Represents an oxygen atom, a sulfur atom or a selenium atom, Z ₁
To Z ₄ at least represents a = C = W group or a = CHSH group.

W represents an oxygen atom, a sulfur atom, a selenium atom or a = NR ₁ group. R ₁ is a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group, R ₂ and R ₃ are each an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, Heterocyclic oxy group, heterocyclic thio group, amino group, phosphonyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, imide group, carbamoyl group, sulfamoyl group, acyl group, cyano group, acyloxy group, carbamoyl Oxy group, silyloxy group,
It represents each group such as ureido group, sulfamoylamino group, nitro group, sulfonyl group, sulfinyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group and sulfonamide group.

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

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

In the groups substituting on these rings,
Examples of the alkyl group represented by R ₁ , R ₂ and R ₃ include straight chain / branched unsubstituted groups such as methyl, ethyl, propyl, amyl, 2-ethylhexyl, dodecyl, 2-hexyldecyl and octadecyl. , A cyclic group such as cyclopentyl, cyclohexyl, or 2-carboxyethyl, 2-hydroxylethyl, 2-methanesulfonylaminoethyl,
2-methoxyethyl, 2- (2-methoxyethoxy) ethyl,
Substituted groups such as 2-methanesulfonylethyl, 3-sulfopropyl, trifluoromethyl and the like can be mentioned.

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

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

The halogen atom represented by R ₂ and R ₃ is
For example, fluorine, chlorine, bromine, iodine atom, the alkoxy group, for example, methoxy, ethoxy, propoxy, 2-methoxyethoxy, 2-methylthioethoxy, 2-methanesulfonylethoxy, 2-dodecyloxy, etc. substitution,
Each unsubstituted group is mentioned.

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

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

Examples of the alkylthio group represented by R ₂ and R ₃ include methylthio, octylthio, tetradecylthio, octadecylthio, 3-phenoxypropylthio and 3-
There are substituted and unsubstituted groups such as (4-t-butylphenoxy) propylthio, and examples of the arylthio group include phenylthio, 2-butoxy-5-t-octylphenylthio and 3-
Examples thereof include groups such as pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, and examples of the heterocyclic thio group include 2-benzothiazolylthio and 2,4-diphenoxy-1,3. Examples include groups such as 2,5-triazole-6-thio and 2-pyridylthio.

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

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

Examples of the ureido group represented by R ₂ and R ₃ include 2-phenylureido, 2-methylureido, 2,2-dibutylureido and the like, and examples of the sulfamoylamino group include N, N. -Dipropylsulfamoylamino, N
Each group such as -methyl-N-decylsulfamoylamino and the like can be mentioned.

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

Examples of the carbamoyl group represented by R ₂ and R ₃ include N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-methoxyethyl) carbamoyl and N, N-dimethylcarbamoyl groups. Be done.

The sulfonyl group represented by R ₂ and R ₃ is
For example, each group such as methanesulfonyl, butanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc. may be mentioned, as the sulfinyl group, for example, each group such as ethanesulfinyl, 3-phenoxypropylsulfinyl, etc., and as the phosphonyl group, for example, phenoxy Each group such as phosphonyl, ethoxyphosphonyl, phenylphosphonyl and the like can be mentioned.

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

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

[0042] Formula (IV), and in the general formula (V), R, V, W, Y represents a hydrogen atom or a substitutable group, X ^- represents an ion to offset the intramolecular charge. l is 1
~ 3, m represents 2 or 3. However, m-1 represents an integer of 0 to 2, and n represents the number of ions necessary to cancel the intramolecular charge.

The substitutable groups represented by R, V, W and Y in the general formulas (IV) and (V) include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acylamino group, Alkylamino group, ureido group, amino group,
Represents an acyl group and a carboxyl group.

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

The aralkyl group includes, for example, a benzyl group, a phenethyl group and the like, the alkenyl group includes, for example, an allyl group and a 2-butenyl group, and the aryl group includes a phenyl group and a naphthyl group. These aryl groups are further substituted. It may be substituted by possible groups.

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

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

[0048] by X ^- as the ions to offset intramolecular charge, represented, halide ions (chloride, bromide etc.), perchloric acid ion, a hydroxide ion, p-
Toluene sulfonate ion etc. are mentioned.

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

[0050]

[Chemical 7]

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[Chemical 10]

[0054]

[Chemical 11]

[0055]

[Chemical 12]

[0056]

[Chemical 13]

The compound of the present invention can be synthesized by a known method, for example, Bull. Chem. Soc. Japan, 48 (3), 102.
4-9 (1975), J. Inorg. Nucl. Chem., 38 (1), 1-11 (1
076), Transition Met. Chem., 2 (6), 224-227 (197
7), Japanese Patent Laid-Open No. 1-147537, U.S. Patents 5049484, 504948
It can be synthesized according to the method described in No. 5.

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

The gold compound according to the present invention can be added at any time during the emulsion production process, but it is preferable to add it at the start of chemical ripening and during the process.

The amount of the gold compound used in the present invention varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but it is usually 1 × 10 ^-4 per mol of silver halide. It is preferably from mol to 1 × 10 ^-8 mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The silver halide emulsion according to the present invention can be gold-sensitized with the above-mentioned gold compound and used in combination with a sensitizing method using a reducing substance and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Thiosulfate as a sulfur sensitizer,
Examples thereof include allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Examples of the reduction sensitizer include ascorbic acid, sodium sulfite, thiourea dioxide and the like.

Heavy metal ions contained in the silver halide emulsion according to the present invention include Group VIII metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium and cobalt, and cadmium, zinc, mercury and the like. Group II transition metals, lead, rhenium, molybdenum,
It is each ion of tungsten and chromium. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable.

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

When the heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Of these, thiocyanate ion and cyanate ion are preferable. The thiocyanate ion may be called by changing the name depending on the coordinating atom, but is often used as a generic name. In the present invention, the names of thiocyanate ion and cyanate ion are used to mean this generic name.

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

(1) FeCl ₂
(2) FeCl ₃ (3) (NH ₄ ) Fe (SO ₄ ) ₂ (4) K ₃ [Fe (CN)
₆ ] (5) K ₄ [Fe (CN) ₆ ] (6) K ₂ [IrC
l ₆ ] (7) K ₃ [IrCl ₆ ] (8) K ₂ [PtC
l ₆ ] (9) K ₂ [Pt (SCN) ₄ ] (10) K ₂ [NiC
l ₄ ] (11) K ₂ [PdCl ₆ ] (12) K ₃ [RdC
l ₆ ] (13) CdCl ₂ (14) ZnCl ₂ (15) K ₂ [Mo (CO) ₄ (CNO) ₂ ] (16) K ₃ [Re (CNO) ₆ ] (17) K ₃ [Mo (OCN ) ₆ ] (18) K4 [Fe (CN
O) ₆ ] (19) K ₂ [W (CO) ₄ (CNO) ₂ ] (20) K ₂ [Cr (C
O) ₄ (CNO) ₂ ] (21) K ₄ [Ru (CNO) ₆ ] (22) K ₂ [Ni (C
N) ₄ ] (23) PbCl ₂ (24) K ₃ [Co (NH
₃ ) ₆ ] (25) K ₅ [Co ₂ (CNO) ₁₁ ] (26) K ₃ [Re (CN
O) ₆ ] (27) K ₄ [Os (CNO) ₆ ] (28) K ₂ [Cd (CN
O) ₄ ] (29) K ₂ [Pt (CNO) ₄ ] (30) K ₃ [IrB
r ₆ ] In order to contain a heavy metal ion in the silver halide emulsion according to the present invention, the heavy metal compound is added to the physical layer before the formation of silver halide grains, during the formation of silver halide grains, and after the formation of silver halide grains. It may be added at any place in each step during aging. For this purpose, for example, this heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, it may be dissolved together with the halide salt and added continuously during the grain formation process.

The amount of the heavy metal ions added to the silver halide emulsion is more preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and particularly preferably 1 × 10 ⁻⁸ mol, per mol of silver halide.
It is preferably from 1 mol to 1 × 10 ⁻³ mol.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is characterized by containing 90 mol or more of silver chloride, but is substantially free of silver iodide. Alternatively, silver chloride is preferred.

The halogen composition of the silver halide grains according to the present invention may be uniform from the inside to the surface of the grain, or the composition inside and outside the grain may be different. When the composition of the inside of the particle is different from that of the surface, the composition may be changed continuously or discontinuously.
Further, they may be layered and evenly overlapped with each other, or may be localized at corners of the crystal. Examples of such silver halide grains include JP-A-58-95736 and 58-108.
There are particles described in No. 533.

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

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

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The monodisperse silver halide grains preferably have a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

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

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

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

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

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

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

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. Further, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589
Issue, Japanese Patent Publication No. 55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21,
It is also possible to prepare particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron by the method described in the literature such as 39 (1973) and the like, and use them. Further, grains having twin planes may be used.

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

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it was spectrally sensitized to a specific region in the wavelength 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 according to the present invention, any known compound can be used, but as the blue-sensitive sensitizing dye, Japanese Patent Application No. 2-5 is used.
BS-1 to BS-8 described in No. 1124, pages 108 to 109 can be preferably used alone or in combination.
As the green sensitizing dye, GS-1 to 5 described on page 110 of the same specification are preferably used. Examples of the red-sensitizing sensitizing dye include RS-1 described on pages 111 to 112 of the same specification.
~ 8 are preferably used. When exposing the silver halide photographic light-sensitive material according to the present invention by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye, Japanese Patent Application No. 3-73619, IRS-1 on pages 12-14
Eleven dyes are preferably used. In addition, the same specification 14 ~ 15
The supersensitizers SS-1 to SS-9 described on the page are preferably used in combination with these dyes.

When the silver halide photographic light-sensitive material according to the present invention is exposed by using a laser, it is advantageous to use an exposure device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is the luminous flux in the case of scanning exposure with laser light. In the spatial change of the intensity of the light flux, the outer edge of the light flux is defined as the point where the light intensity becomes 1/2 of the maximum value, and the outer edge of the light flux and the line that is parallel to the scanning line and that passes through the point where the light intensity is the maximum. When the distance between two intersecting points is the diameter of the light beam, the (light beam diameter) / (scanning speed) can be considered as the exposure time per pixel. As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used.

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-4.
071, JP-A-59-11062, JP-A-63-197947, JP-A-2-74942, JP-A-2-236538, JP-B-56-14963,
Japanese Examined Patent Publication No. 56-40822, European Wide Area Patent 77410, Department of Electronics and Communication Technology Report 80, No. 244, and Movie Television Technical Journal 198
4/6 (382), pages 34-36, etc.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
AI described on pages 117 to 118 of Japanese Patent Application No. 2-51124
Dyes -1 to 11 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 can be used. It has preferable spectral characteristics, does not affect the photographic characteristics of the silver halide photographic emulsion, and is free from contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed in page 3, lower left column to page 5, lower left column of the same specification.

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

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula (YI) described on page 8 of Japanese Patent Application No. 2-234208. Can be mentioned.
Specific compounds are described on pages 9 to 11 of the same specification in YC-1 to
The thing described as YC-9 can be mentioned. Among them, YC-described on page 11 of the same specification
8 and YC-9 are preferable because they can reproduce a preferable yellow color.

As magenta couplers which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, there are described general formulas (M-I) and (M-II) described on page 12 of Japanese Patent Application No. 2-234208. ) And a coupler represented by Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are preferable because they are excellent in the reproduction of colors ranging from blue to purple and red and are excellent in the depiction of details.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Japanese Patent Application No. 2-234208, the general formula (C
Examples thereof include couplers represented by -I) and (C-II). Specific compounds are described in C of page 18 to 21 of the same specification.
Mention may be made of those described as C-1 to CC-14.

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

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

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described on page 33 of the specification of Japanese Patent Application No. 2-234208 and the compound (A 'on page 35 of the specification).
Compounds such as -1) can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.

The reflection support according to the present invention may be made of any material such as polyethylene coated paper containing white pigment, baryta paper, vinyl chloride sheet, polypropylene containing white pigment, polyethylene terephthalate support and the like. Can be used.

Of these, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support of the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the water resistant resin layer, and further, It is preferable that the content is 13% by weight or more, and 15
More preferably, it is at least wt%. The dispersity 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, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

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

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

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material according to the present invention include aminophenol and p-phenylenediamine which are widely used in various color photographic processes. A compound is used. In particular, aromatic primary amine type color developing agents are preferably used. To the color developing solution, a known developing solution component compound can be added in addition to the above color developing agent.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. The development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank,
The endless belt method may be used in which the photosensitive material is fixed to the belt and conveyed, but in particular, the processing tank may be formed in a slit shape so that the processing liquid is supplied to the processing tank and the photosensitive material is conveyed.

[0103]

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 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. Each layer having the structure shown below is coated on this reflective support to form a multilayer silver halide photographic light-sensitive material, Sample 101.
Was produced. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to 6.67 g of boiling point organic solvent (DNP) and dissolved, and this solution was dissolved in 15% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% gelatin aqueous solution containing 9.5 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions, and further 6.7 ml of AI-3 5% aqueous solution of anti-irradiation dye.
In addition, a first layer coating solution was prepared. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) is used for the second and fourth layers, and (H-) for the seventh layer.
2) was added. As a coating aid, a surfactant (SU
-2) and (SU-3) were added to adjust the surface tension.

The layer structure is as shown in the table below.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

[Chemical 14]

[0110]

[Chemical 15]

[0111]

[Chemical 16]

[0112]

[Chemical 17]

[0113]

[Chemical 18]

(Preparation of blue-sensitive silver halide emulsion) In 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C., the following (solution A) and (solution B) were taken for 30 minutes while controlling pAg = 6.5 and pH = 3.0. At the same time, and the following (solution C) and (solution D) were added to pAg =
Simultaneous addition was carried out over 180 minutes while controlling 7.3 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water added 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol Ag
X sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) were changed in the same manner as in EMP-1, except that the average particle size was 0.43.
A monodisperse cubic emulsion EMP-2 having a coefficient of variation (S / R) of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing sensitive silver halide emulsion) (solution A) and (B)
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as in EMP-1, except that the average particle size is 0.50 μm.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation (S / R) = 0.08, and a silver chloride content of 99.5 mol% was obtained.

For EMP-3, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol A
gX

[0122]

[Chemical 19]

[0123]

[Chemical 20]

Next, in the preparation of the emulsion (EMP-2), (EMP-4) was prepared in the same manner except that the exemplified compound (5) of the heavy metal compound was added to the liquid C, and the liquid C was added to the liquid C. (EMP-5) was prepared in the same manner except that the compound (6) was added. Exemplified compound (5) was added so as to be 10 ⁻⁶ mol per mol of the final silver halide, and Exemplified compound (6) was added at 10 ⁻⁸ per mol of silver halide.
It was added so as to become a mole. In the same manner as in the preparation of (Em-G1), green-sensitive emulsions (Em-G2) and (Em-G3).
Was prepared.

In the preparation of the green-sensitive emulsion, chemical ripening was carried out using the exemplified compounds (I-6) and (I-21) in place of chloroauric acid, and (EMP-2) (EMP-4) (EMP-
5) From each emulsion of green-sensitive emulsion (Em-G4) to (Em-G4)
G9) was prepared. The contents of the emulsion are shown in Table 3 below.

[0126]

[Table 3]

In the preparation of Sample 101, the green light-sensitive emulsion (Em-G1) was sequentially added (Em-G2) to (Em-G9).
Samples 102 to 109 were prepared in the same manner except that the above was changed.

Three samples each were prepared and the exposure time was set by the usual method.
After light-wedge exposure for 0.5 seconds, one sheet was subjected to the following development processing for 1 minute after exposure, one sheet for 5 minutes after exposure, and the remaining one sheet for 10 minutes after exposure.

The processing steps are shown below.

Processing step Processing temperature time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30 to 34 ° C. 90 seconds Dry 60 to 80 ° C. 60 seconds The composition of the developing solution is shown below.

Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-diphosphonate disodium 1.0 g N-ethyl-N-β methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative ) 1.0g Potassium carbonate 27g Add water to bring the total volume to 1 liter and adjust to pH = 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter and potassium carbonate. Or adjust the pH to 5.7 with glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution ) 3.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5g Add water to make the total volume 1 liter and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The green density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation). Sensitivity is density
Defined based on the reciprocal of the exposure dose that gives 0.75
Samples that have been subjected to development processing for 10 minutes are expressed as relative values with sample 101 being 100. Samples processed 3 and 10 minutes after exposure have sensitivity of 10 minutes for each sample after exposure.
The relative value was set to 0. The results are shown in Table 4 below.

[0135]

[Table 4]

Comparing Comparative Samples 101, 102 and 103, it can be seen that the use of the silver halide emulsion containing the heavy metal compound according to the present invention causes a large change in sensitivity due to a change in time from exposure to development. .. Comparative samples 101, 1
From the comparison of 04 and 107, it can be seen that this change in sensitivity does not depend on the type of gold compound used during chemical ripening, as long as a silver halide emulsion containing no heavy metal compound is used. However, the comparison between the comparative sample 102 and the invention samples 105 and 108, and the comparison sample 103 and the invention sample 10
From the comparison of Nos. 6 and 109, it can be seen that in the silver halide emulsion containing the heavy metal compound according to the present invention, the magnitude of the sensitivity change greatly depends on the selection of the gold compound.
In the sample of the present invention, the sensitivity variation is further improved even in the sample containing no heavy metal compound in which the sensitivity variation was small.

Comparing the sensitivities when processed one minute after exposure, the samples containing the exemplified compound (5) among the heavy metal compounds according to the present invention have high sensitivity and high sensitivity. It has been confirmed that it has a great effect as a technology for chemical conversion.

Next, the leaving time after exposure was adjusted to 10 minutes and the exposure time was changed to 0.01, 0.5, and 10 seconds to evaluate the change in sensitivity. The results are shown in Table 5 below. Here, the sensitivity was expressed as a relative value with 100 being the sensitivity at an exposure time of 0.5 seconds.

[0139]

[Table 5]

As the exposure time becomes longer than that of the sample having the exposure time of 0.5 seconds, the sensitivity is remarkably lowered, but the comparative samples 102 and 103 using the silver halide emulsion containing the heavy metal compound according to the present invention are the heavy metal compounds. It can be seen that the decrease in sensitivity is smaller than that of the comparative sample 101 not containing.

In the case of short-time exposure, the fluctuation range is small, but the sensitivity tends to be high, but it is found that the sensitivity fluctuation is reduced by using the silver halide emulsion containing the heavy metal compound according to the present invention. ..

Regarding these effects, it can be seen that the effects are enhanced when the gold compound according to the present invention is used.

As described above, in the technique of using a heavy metal compound, which is effective for improving the fluctuation of the sensitivity due to the change of the exposure time, the sensitivity is changed by the fluctuation of the latent image from the exposure to the development in a relatively short time. However, it is understood that this is improved by the present invention, and the sensitivity fluctuation due to the exposure time change is also improved.

(Example 2) The green light-sensitive emulsion (E) of Example 1
m-G1), (Em-G2), (Em-G3), sodium thiosulfate was added to triethylthiourea,
The gold compound was changed from chloroauric acid to comparative compound A, exemplified compound (I
-6), (I-8), (I-18), (I-19), (IV-
1), (V-1), and changed to green photosensitive emulsion (Em-G
10) to (Em-G30) were prepared. The contents of the green-sensitive emulsion are shown in Table 6 below. Samples 201 to 221 were prepared in the same manner as Sample 101, except that the green light-sensitive emulsion was changed.

[0145]

[Table 6]

[0146]

[Chemical 21]

In the same manner as in Example 1, the change in sensitivity was evaluated by changing the time from exposure to development. The results are shown in Table 7 below.

[0148]

[Table 7]

According to the comparison of the comparative samples 201, 202 and 203,
A halogenated compound containing a heavy metal compound was used in the same manner as in Example 1 regardless of changing the sulfur sensitizer from sodium thiosulfate to triethylthiourea and changing the gold compound from chloroauric acid to Comparative Compound A. It was confirmed that the sensitivity of the silver emulsion varied greatly depending on the time between exposure and development.

Then, the comparative sample 202 and the samples 205 and 20 of the present invention
8, 211, 214, 217, 220, and comparison sample 203 and the present invention sample 206, 209, 212, 215, 218, 221, according to the exposure to any of the gold compound according to the present invention It was confirmed that high sensitivity can be obtained without any change in sensitivity due to time change from development to development.

The silver halide emulsion of Example 1 (EMP-
In the preparation of 1), (EMP-6) was prepared in the same manner except that the exemplary compound (5) of the heavy metal compound was added to the solution C, and the same procedure was performed except that the exemplary compound (6) of the heavy metal compound was added to the solution C. (EMP-7) was prepared. Exemplified compound (5) was added so as to be 3 × 10 ^-6 mol per 1 mol of final silver halide, and Exemplified compound (6) was added so as to be 3 × 10 ^-8 mol per 1 mol of silver halide. Was added.

Next, the silver halide emulsion of Example 1 (EM
In the preparation of P-3), (EMP-8) was prepared in the same manner except that the exemplary compound (5) of the heavy metal compound was added to the solution C, and the exemplary compound (6) of the heavy metal compound was added to the solution C. (EMP-9) was similarly prepared. Exemplified compound (5) was added so as to be 10 ^-6 mol per 1 mol of the final silver halide, and Exemplified compound (6) was added so as to be 10 ^-8 mol per 1 mol of the silver halide.

A blue-sensitive emulsion was prepared in the same manner as in (Em-B1) of Example 1 except that the silver halide emulsion and the gold compound were replaced. Silver halide emulsion (EMP-
1), (EMP-6) and (EMP-7) are chemically aged using chloroauric acid (Em-B1) to (Em-B3),
Chemical aging was performed using the exemplified compound (I-6) to obtain (Em-
B4) to (Em-B6) and the exemplified compound (I-21) were chemically aged to prepare (Em-B7) to (Em-B9).

Similarly, in the preparation method of (Em-R1) of Example 1, as a silver halide emulsion (EMP-R1),
3), (EMP-8) and (EMP-9) were used to prepare red-sensitive emulsions (Em-R1) to (Em-R9) in the same manner except that the gold compound was used instead of the above gold compound.

A silver halide photographic light-sensitive material was prepared in the same manner as in the preparation of Sample 101 of Example 1, except that the blue-sensitive emulsion, the green-sensitive emulsion and the red-sensitive emulsion were replaced. The silver halide photographic emulsions having the same numbers of 1 to 9 were combined to prepare nine kinds of samples 222 to 230 in total ((Em-B1), (Em-G1) and (Em-G1). -R1) was used to prepare Sample 222 (this sample is the same as Sample 101.) (Em-B2), (Em-G2), and (Em-B2).
In R2), samples were prepared in order such as sample 223). This is subjected to exposure and development processing in the same manner as in Example 1, and the blue, green and red densities of the obtained dye image are measured. When the sensitivity variation due to the change with time was evaluated, it was confirmed that the effect of the present invention was obtained even in the blue-sensitive emulsion layer and the red-sensitive emulsion layer.

Example 3 The green-sensitive emulsion of Example 1 (Em
In the preparation of -G3), the chemical ripening was carried out in the same manner except that sodium thiosulfate was 3 mg per mol of silver halide and chloroauric acid was not added. It was confirmed that it was sensitized by 1.1 log H compared with.

Next, chemical ripening was performed under the above conditions to prepare an optimally ripened emulsion (Em-G31). Aging was carried out under the above conditions, and when the sensitivity was 0.8 log H lower than the sensitivity of optimum aging, the exemplified compound (I-6) of the gold compound was (Em-
G3) was added in an equimolar amount with chloroauric acid and further ripened to obtain an optimally ripened emulsion (Em-G32), and an exemplified compound (I-6 when the sensitivity was 0.5 log H lower than the optimum ripening sensitivity). ) Was added and further ripened to prepare an optimally ripened emulsion (Em-G33).

In the same manner as in Sample 101 of Example 1, except that the green-sensitive emulsion (Em-G1) was changed to (Em-G31), Sample 301 and Sample 302 were prepared using the green-sensitive emulsion (Em-G32). , Sample 303 was prepared using a green-sensitive emulsion (Em-G33).

In the same manner as in Example 1, the change in sensitivity due to the change in time between exposure and development was evaluated. The results are shown in Table 8 below.

[0160]

[Table 8]

The comparative sample 301 has the advantage that the change in sensitivity is small with respect to the change in time from exposure to development, but it is not sufficient yet and it is sensitized only with sodium thiosulfate. It had a drawback that the sensitivity was extremely low. In the present invention samples 302 and 303, the present invention sample 10
Compared with 6, the sensitivity fluctuation was smaller, and a little more sensitization was also observed, and the addition of the gold compound according to the present invention does not bring about the effect of the present invention even if it is added separately from the sulfur compound. It was confirmed to be obtained.

Example 4 In the preparation of (EMP-4) of Example 1, the heavy metal compound was replaced by the exemplified compound (1),
Silver halide emulsions (EMP-10), (EMP-11), (EM) were obtained in the same manner except that (13) and (18) were used.
P-12) was prepared. At this time, the amount of the heavy metal compound added was 10 ⁻⁷ mol per mol of silver halide. Green-sensitive emulsions (Em-G34) to (Em-G39) were prepared in the same manner except that only the silver halide emulsion was replaced in the method for preparing the green-sensitive emulsions (Em-G1) and (Em-G4). The contents of the emulsion are shown in Table 9 below.

[0163]

[Table 9]

Table 10 below shows the results of evaluation of changes in sensitivity due to time changes from exposure to development using this sample.

[0165]

[Table 10]

In the sample using the silver halide emulsion containing the heavy metal compound according to the present invention, when the gold compound according to the present invention was not used, the sensitivity change due to the time change from exposure to development was large. It was confirmed that the effect is high in the invention samples, particularly in the samples 404 and 406 using the complex-forming heavy metal compound.

Next, using this sample, the change in sensitivity when the exposure time was changed was evaluated. The results are shown in Table 11 below.

[0168]

[Table 11]

It can be seen that in the sample using the silver halide emulsion containing the heavy metal compound according to the present invention, the change in sensitivity due to the change in exposure time is small. It can be seen that the effect is particularly large when the heavy metal compound forming a complex is used, and the effect is slightly enhanced when the gold compound according to the present invention is used.

Example 5 Sample 222 prepared by combining the blue-sensitive emulsion (Em-B1), the green-sensitive emulsion (Em-G1) and the red-sensitive emulsion (Em-R1) in Example 2;
Sample 224 prepared by combining the blue-sensitive emulsion (Em-B3), the green-sensitive emulsion (Em-G3) and the red-sensitive emulsion (Em-R3) in Example 2, and the blue-sensitive emulsion (Em in Example 2). -B6) and a green-sensitive emulsion (Em-G6)
A print was prepared by laser exposure using a sample 227 prepared by combining a red-sensitive emulsion and Em-R6.

As image data, an image (portrait) of a color slide of 4 × 5 inches was digitized into a size of 80 × 80 μm per pixel by a scanner and used.

The exposure apparatus uses helium.
The cadmium laser (about 442 nm), the helium-neon laser (about 544 nm) as the green light source, and the helium-neon laser (about 633 nm) as the red light source were prepared and the optical system was assembled. The light emitted from the three lasers is modulated according to the image data and then focused into one beam,
For silver halide photographic light-sensitive materials transported at a speed of
Scanning exposure was performed at a main scanning speed of 160 m / sec at a right angle to the carrying direction. The beam diameter at this time was about 80 μm, and the exposure time per pixel was 500 nanoseconds.

When the sample 227 was used, an excellent image could be obtained, but in the case of the sample 222, the sensitivity to red light was particularly insufficient, and only an image having a low cyan density was obtained. I couldn't. In addition, when comparing the print developed immediately after exposure and the print developed 10 minutes after exposure, not only the density decrease occurs in Sample 224, but pseudo contours are generated in various places on the face, and the quality is remarkably high. Only a reduced image of was obtained. On the other hand, with sample 227 according to the present invention, an excellent image could be obtained with almost no change in density.

Next, an infrared-sensitive silver halide photographic light-sensitive material was prepared and evaluated in the same manner. (Preparation of infrared-sensitive silver halide emulsion (Em-IR1)) In the same manner as in the method for preparing the green-sensitive emulsion (Em-G6) of Example 1, except that the sensitizing dye was changed to (IRS-1). Infrared sensitive silver halide emulsion (Em-IR1)
An infrared-sensitive silver halide emulsion (Em-IS2) was prepared in the same manner except that the sensitizing dye was changed to (IRS-2).

[0175]

[Chemical formula 22]

In the preparation of Sample 101 of Example 1, the blue-sensitive silver halide emulsion was replaced with an infrared-sensitive silver halide emulsion (E
m-IR1), the green-sensitive silver halide emulsion is the infrared-sensitive silver halide emulsion (Em-IR2), and the red-sensitive silver halide emulsion is the red-sensitive silver halide emulsion of Example 2 (Em-IR1).
R6: Sample 5 in the same manner except that the heavy metal compound according to the present invention, the exemplified compound (6) is contained and is sensitized by the gold compound according to the present invention exemplified compound (I-6)).
01 was prepared.

An aluminum / gallium / indium / phosphorus semiconductor laser (about 67
0 nm), gallium-aluminum-arsenic semiconductor laser (about 780 nm), and gallium-aluminum-arsenic semiconductor laser (about 830 nm) were prepared, and the optical system was assembled. The specifications of the diameter of the light beam, the transportation speed, etc. were matched with those of the laser printer. When an image was output to the sample 501 using this apparatus, a color print with excellent image quality could be obtained. Comparison was made between the case where the development treatment was carried out immediately after exposure and the case where development was carried out after about 10 minutes, but the difference was slight, and even when used in an infrared-sensitive silver halide photographic light-sensitive material, It was confirmed that the effect was effectively obtained.

[0178]

The silver halide photographic light-sensitive material of the present invention comprises
A high silver chloride silver halide photographic emulsion is used, and a high quality image can be obtained by a very short processing time. Since the photographic characteristics rarely change due to the change in the time from exposure to development, this image is characterized by being stably obtained. Furthermore, even when a photographic image is obtained by high-intensity short-time exposure using a laser or the like from software information recorded on a magnetic medium or the like, an image having excellent gradation can be stably obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer consisting of 90 mol% or more of silver chloride on a support, wherein the silver halide emulsion in the silver halide emulsion layer has a periodic pattern. Table At least one of Group VIII metal, Group II transition metal, lead, rhenium, molybdenum, tungsten, and chromium is 1 × 10 5 per mol of silver halide.
^-9 mol or more, and the following general formula (I) and general formula (I
V) or a silver halide photographic light-sensitive material containing at least one gold compound represented by the general formula (V). In the general formula (I) _{[H m Au n (L) p} (X) q ] _r [wherein, L is a heterocyclic ligand 5- or 6-membered, X
Represents an anion group. m is an integer of 0 to 2, n is an integer of 1 or 2, p is an integer of 1 to 3, q is an integer of 0 to 3, and r is an integer of 1 to 4. ] General formula (IV) General formula (V) [In the formula, R, V, W, and Y represent a hydrogen atom or a substitutable group, and X ⁻ represents an ion that cancels the intramolecular charge. 1
Is an integer of 1 to 3 and m is 2 or 3. However, m-
1 represents an integer of 0 to 2, and n represents the number of ions necessary to cancel the intramolecular charge. ]