JP2847430B2 - Silver halide photographic material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having improved storage stability over time and good running processing stability.

[Background of the Invention]

When silver halide photographic light-sensitive materials for X-ray image diagnosis are processed using a roller transport type automatic developing machine, the total processing time from insertion of the tip of the light-sensitive material to drying and coming out is 90 seconds. It has been more than 20 years since the so-called 90-second processing that was completed in was commercialized.

In recent years, demands for speeding up are increasing, and further reduction in processing time is desired.The present applicant has disclosed a total processing time of 45 seconds in Japanese Patent Application Laid-Open No. 62-286037 or European Patent No. 0238271A. A processing method to complete is proposed.

Such movements are intended to respond to urgent cases in the medical field, and are expected to be further accelerated in the future.

On the other hand, for silver halide photographic materials for X-rays,
There is a demand for an image having a higher sharpness with a smaller X-ray exposure dose. In other words, higher sensitivity and higher sharpness are desired.

There are many known methods for sensitizing silver halide emulsions, including a chemical sensitization method and a spectral sensitization method, but it is necessary that fogging be low in addition to sensitization.

It has been reported that the occurrence of fogging of a high-sensitivity silver halide photographic material over a long period of time depends on the amounts of silver and gold or potassium ions contained in the photographic material. In addition, as a countermeasure technology against deterioration due to these factors, a technology for limiting the amount of gold applied per unit area, the amount of silver applied per unit area, and the weight ratio of the two to a specific quantity, and a specific measure for realizing it, include halogenation. Techniques for removing gold (free gold) and / or gold compounds that are not present in and on silver particles are disclosed in JP-A-1-96642, JP-A-1-96651, and JP-A-1-9665.
No. 2, etc. Japanese Patent Laid-Open Publication No. Hei.
No. 836.

Therefore, we focused on a gold sensitizer, which is one of the causes of deterioration of a high-sensitivity photosensitive material over time. Conventionally, an inorganic gold complex salt has been generally used as a gold sensitizer (for example, see US Pat. No. 2,399,083). Of these, for example, chloroauric red (chloroauric acid), potassium chloroaurate, potassium aurithiothiocyanate, auric trichloride and the like are currently generally used as suitable gold sensitizers. However, these gold salts have the disadvantage that they are prone to liberating gold or some of the liberated gold forms a stronger complex with gelatin and remains in gelatin. Therefore, performance degradation due to the gold sensitizer is considered to be a problem due to the chemical properties of the gold sensitizer.

Furthermore, even if the photosensitive material on which such a chemical sensitization method has been applied is subjected to continuous and long-term running processing by the rapid development processing method described above, photographic performance such as sensitivity, gamma, and maximum density can be processed. There has been a demand for a new technology capable of stably maintaining high performance without fluctuation.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material which is stable and has high sensitivity without fog increase even when the light-sensitive material is stored over time.

It is a second object of the present invention to provide a silver halide photographic light-sensitive material which exhibits stable high performance without fluctuation in photographic performance such as sensitivity and gamma even when running processing by rapid development. Other objects will be apparent from the following description.

[Configuration of the invention]

The object of the present invention has been found to be achieved by the following, and has led to the present invention.

That is, (1) a silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer has the following general formula [I] Wherein at least one of the compounds represented by the following general formula [II] and / or
Or a silver halide photographic light-sensitive material containing at least one of the compounds represented by the formula (III) is processed by a roller transport type automatic developing machine under conditions corresponding to the following formula A: Photosensitive material.

In the general paper [I] _{[HlAu m (L) n (X} ) p ] _q formula, L is a heterocyclic ligand 5- or 6-membered, X represents an anionic group, l is from 0 to 2 An integer, m is an integer of 1 or 2, n is an integer of 1 to 3, p is an integer of 0 to 3, and q is 1 to 2.
Represents an integer of 4.

In the formula, R ₁ represents a hydrogen atom, an alkyl group or a hydroxymethyl group, and R ₂ represents a hydrogen atom or an alkyl group.

In the formula, R ₃ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or The stands, R _4, R ₅ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkyl sulfoxy group, an alkylsulfonyl group, R ₄ and R ₅ together They may be joined to form an aromatic ring.
R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

Formula A l ^0.75 × T = 50-130 (0.7 <l <4.0) where l is the processing length when processing the photosensitive material (unit:
m), and T represents the time (Sec) required to pass through l.

 Hereinafter, the present invention will be described in detail.

In the above general formula [I], the anion group represented by X includes a halogen ion (for example, fluorine, chlorine, bromine,
(Iodine ion) groups such as perchlorate ion, borohydrofluoric acid ion, sulfate ion, nitrate ion and thiocyanate ion.

As the 5- or 6-membered heterocyclic ligand represented by L,
Anionic, cationic or neutral monocyclic group,
It is selected from those represented by the following general formula [L ₁ ] or [L ₂ ].

In the general formulas (L ₁ ) and (L ₂ ), Y ₁ and Y ₂ are each
Represents an oxygen atom, a sulfur atom, a selenium atom or = NR ₁ group, Z
₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are each ＣC (R ₃ ) —, ＣC ＝ W, NRNR ₁ , —N ＝, a group, an oxygen atom, a sulfur atom or a selenium atom, and at least one of Z _{1 to} Z ₄ is a ＣC ＝ W group or ＝. Represents a CHSH group. W represents an oxygen atom, a sulfur atom, a selenium atom or an NR ₁ group. R ₁ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₂
And R ₃ are 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, a heterocyclic oxy group, a heterocyclic thio group, and an amino group, respectively. , Phosphonyl group, carboxyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, sulfo group, imide group, carbamoyl group, sulfamoyl group, acyl group, cyano group, acyloxy group, carbamoyloxy group, silyloxy group, ureido group, sulfamoylamino group, nitro group, sulfonyl group, sulfinyl group , Acylamino group,
Each group represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, or the like.

In the general formulas [I], [L ₁ ] and [L ₂ ], Y ₁ , Z ₁ ,
Specific examples of the 5-membered heterocyclic group formed by Z ₂ , Z ₃ and Z ₄ include pyrroles (for example, groups such as 2 (1H) -pyrroline, 2-pyrrolidinium, 2 (3H) -pyrroline, and pyronium). , Imidazoles (eg, 2 (3H) -imidazoline, 2-imidazolinium, 2 (3H) -imidazoline,
Groups such as imidazolium), oxazoles (for example, 2
(3H) -oxazolidine, 2-oxazolinium, 2
(3H) -oxazoline, groups such as oxazolium), isoxazoles (for example, 3 (2H) -isoxazoline,
Groups such as 3-isoxazolium), thiazoles (for example, 2 (3H) -thiazolidine, 2-thiazolium, 2 (3
H) -thiazoline, thiazolium, etc.), isothiazole (eg, 3 (2H) -isothiazoline, 3-isothiazolium, etc.), selenazole (eg, 2 (3H)
-Groups such as selenazolidine, selenazolium, etc.) and oxazolidines (for example, groups such as 2-thio-oxazolidine-2,4-dione, 2,4-oxazolidinedione, oxazolidine-4-one, 2-oxazoline-4-one). , Thiazolidine-based (for example, 2-thio-thiazoline-2,4-dione, 2,4-thiazolidinedione, thiazolidine-4-
Groups such as on, 2-thiazolin-4-one, etc.), imidazolidine-based (for example, 2-thio-imidazolidine-2,4-dione, 2,4-imidazolidinedione, isothiazolidine-).
Groups such as 4-one, 2-imidazolidin-4-one, etc.),
Selenazolidine-based (eg, 2-thio-selenazolidine-
Groups such as 2,4-dione, 2,4-selenazolidinedione, selenazolidine-4-one, and 2-selenazolin-4-one)
And the like.

In the general formulas [I], [L ₁ ] and [L ₂ ], Y ₂ , Z
Specific examples of the 6-membered heterocyclic group formed by ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ include pyridine-based (for example, 1,2-dihydro-2-pyridylidene, 2-pyridinium, tetrahydropyridine-
Groups such as 2,4-dione, tetrahydropyridine-2,6-dione), pyrimidines (for example, tetrahydropyrimidine-
2,4-dione, tetrahydropyrimidine-2,6-dione,
Hexahydropyridine-2,4,6-trione, 2-thio-
Groups such as hexahydropyridine-2,4,6-trione), pyrazoline (pyrazolin-5-one, pyrazolidin-3,
Groups such as 5-dione).

In the groups substituted on these rings, examples of the alkyl group represented by R ₁ , R ₂ and R ₃ include methyl, ethyl,
Propyl, amyl, 2-ethylhexyl, dodecyl, 2
Linear or branched unsubstituted groups such as hexyldecyl and octadecyl, cyclic groups such as cyclopentyl and cyclohexyl, or 2-carboxyethyl, 2-hydroxyethyl, 2-methanesulfonylaminoethyl, 2-methoxyethyl, Substituted groups such as-(2-methoxyethoxy) ethyl, 2-methanesulfonylethyl, 3-sulfopropyl, trifluoromethyl and the like are exemplified, and examples of the aryl group include phenyl, 4-t-butylphenyl,
4-di-t-aminophenyl, 4-nitrophenyl, 3
-Nitrophenyl, 4-methanesulfonylphenyl, 3
Substituted or unsubstituted groups such as -methanesulfonylaminophenyl, 2,4,6-trichlorophenyl, 4-trifluorophenyl, 2-methoxyphenyl, 2-acetylaminophenyl, 2- (2-ethylureido) phenyl Examples of the heterocyclic group include, for example, 2-pyridine, 2-furyl, 2-pyrimidi, 2-thienyl, 5-nitro-2-
Examples include substituted and unsubstituted groups such as thienyl, 4-methyl-2-thiazolyl, and 1-pyridinyl.

The halogen atom R ₂ and R ₃ represents, for example, fluorine, chlorine, bromine, iodine atom, the alkoxy groups such as methoxy, ethoxy, propoxy, 2-methoxyethoxy, 2-methylthioethoxy, 2-methane Substituted and unsubstituted groups such as sulfonylethoxy and 2-dodecyloxy are exemplified.Examples of the aryloxy group include substituted and unsubstituted groups such as phenoxy, 2-methylphenoxy and 4-t-butylphenoxy, Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyloxy groups, and examples of the acyloxy group include acetoxy and butanoyloxy. Examples of the carbamoyloxy group include a methylcarbamoyloxy group and a phenylhalbamoyloxy group Examples of each group include silyloxy groups such as trimethylsilyloxy and dibutylmethylsilyloxy.Examples of the alkylthio group include methylthio, octylthio, tetradecylthio, octadecylthio, and 3-phenoxypropylthio. There are substituted and unsubstituted groups such as 3- (4-t-butylphenoxy) propylthio, and the arylthio group includes, for example, phenylthio, 2-butoxy-5-t-
Examples include octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, and 4-tetradecanamidophenylthio, and examples of the heterocyclic thio group include 2-benzothiazolylthio, 2,4- Examples of each group include diphenoxy-1,3,5-triazole-6-thio and 2-pyridylthio, and examples of the acylamino group include groups such as acetamido, butanamide, and benzamide, and examples of the amino group include: Amino, anilino, 2-hydroxyanilino, 2-mercaptoanilino, N-acetylanilino, methylamino, N,
There are various groups such as N-diethylamino, and examples of the ureido group include groups such as 2-phenylureido, 2-methylureide, and 2,2-dibutylureide.Sulfamoylamino groups include, for example, N , N-dipropylsulfamoylamino and N-methyl-N-decylsulfamoylamino groups. Examples of the sulfonamide group include methanesulfonamide, butanesulfonamide, hexanesulfonamide, and benzenesulfonamide. , P-toluenesulfonamide, 2-methylthio-5-hydroxybenzenesulfonamide and the like. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and butoxycarbonylamino groups, and aryloxy As the carbonylamino group, for example, phenoxy Examples of the carbamoyl group include N-ethylcarbamoyl, N, N-dibutylcarbamoyl, and N- (2
-Methoxysilethyl) carbamoyl, N, N-dimethylcarbamoyl and the like. Examples of the sulfamoyl group include N-ethylsulfamoyl, N, N-dipropylsulfamoyl, and N, N-dimethylsulfamo. Moyl and the like, and examples of the sulfonyl group include, for example, methanesulfonyl, butanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, and the like.Examples of the sulfinyl group include ethanesulfinyl, 3-
There are groups such as phenoxypropylsulfinyl, and the phosphonyl group includes, for example, each group such as phenoxyphosphonyl, ethoxyphosphonyl, and phenylphosphonyl.The alkoxycarbonyl group includes, for example, methoxycarbonyl, butoxycarbonyl, and the like. Groups,
Examples of the aryloxycarbonyl group include groups such as phenoxycarbonyl and p-anisidyl, and examples of the acyl group include groups such as acetyl, 3-carboxypropanoyl, benzoyl, and p-mercaptobenzoyl. Examples of the imide group include groups such as N-succinimide, N-phthalimide, and 3-allylsuccinimide.

In the gold compound of the present invention represented by the general formula [I], a compound represented by the following general formula [Ia] or [Ib] is preferably used.

General formula [Ia] [Aum '(L) _n ' (X) _p '] _q General formula [Ib] Hl'Au (L) (X) In the formula, L, X and q each represent a general formula [ I]. l 'is an integer of 1 or 2, and X is 2
When it is a valence group, l 'is 2. m 'is an integer of 1 or 2, n' is an integer of 1, 2 or 3, p 'is an integer of 0 or 1, and satisfies the relationship m' + p '= n'.

Specific examples of the gold compound of the present invention represented by the general formula [I] are shown below, but the present invention is not limited thereto.

The compound of the present invention can be synthesized by a known method,
For example, Bull. Chem. Soc. Japan, 1975, 48 (3), 1024-9,
J. Inorg.nucl. Chem., Vol. 38 (1), 7-11 (1976), Tra
Chem., Vol. 2 (6), 224-227 (1977) and JP-A-1-47537.

The gold compound of the present invention is water or methanol, ethanol,
It is preferable to dissolve in a water-miscible solvent such as a fluorinated alcohol alone or in a mixed solvent, and to add it to a silver halide grain emulsion. When the compound is hardly soluble in a suitable solvent, it is preferably added in the form of a dispersion.

The gold compound of the present invention can be added at any time during the emulsion production process, but is preferably added at the start of chemical ripening, in the middle, or immediately before the end.

The amount of the gold compound used in the present invention is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 per mol of silver halide.
It is preferably from 1 mol to 1 × 10 ^-8 mol. More preferably, it is 1 × 10 ^-5 mol to 1 × 10 ^-8 mol.

At the time of chemical ripening in the present invention, other chemical sensitizers can be used in combination. For example, it is preferable to use together with a sulfur sensitizer. The sulfur sensitizer can be selected from sulfur crystals, water-soluble sulfide salts, thiosulfates, thioureas, mercapto compounds, rhodanines and the like.
Specific examples thereof are described in U.S. Pat.Nos. 1,574,944 and 2,410,689.
No. 2,278,947, 3,501,313, 3,656,955,
West German Patent 1,422,869, JP-B-49-20533, 58-
No. 28568.

Of these, thiosulfates, thioureas and rhodanines are particularly preferred.

In the present invention, other chemical sensitizers that can be used in combination, for example, U.S. Patent Nos. 3,420,670 and 3,297,447,
Selenium compounds described in U.S. Pat.
2,487,850, 2,518,698, 2,521,925, 2,52
1,926, 2,419,973, 2,694,637, 2,983,610
Amines, reducing substances such as stannous salts, U.S. Pat.Nos. 2,448,060, 2,566,245, 2,566,
No. 263 and the like, and salts of noble metals such as platinum, palladium, iridium, and rhodium.

Chemical ripening with the compounds of the present invention often gives good results when performed in the presence of silver halide solvents such as thiocyanates, thioethers and 4-substituted thioureas.

The chemical ripening with the compound of the present invention can also be carried out in the presence of a chemical sensitizing aid (chemical sensitizing modifier).

For example, compounds such as 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, guanosine, and sodium naurium p-toluenesulfinate can be used as a chemical sensitization aid (modifier).

Specific examples are U.S. Pat.Nos. 2,131,038 and 3,411,914.
No. 3,554,757, JP-A-58-126526 and "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (1966), 13
It is described on pages 8-143.

The pAg (logarithm of the reciprocal of silver ion concentration) of the emulsion during chemical ripening is preferably from 7.0 to 11.0. The pH of the emulsion is
It is preferably 4.0 to 9.0. The temperature of chemical ripening is
Preferably it is 40-90 ° C.

The gold compound of the present invention is to slowly add a sulfur sensitizer over a long period of time to transform silver sulfide clusters selectively grown and formed at specific locations on the surface of silver halide grains into effective gold-silver sulfide clusters. Can also be preferably used. A technique for selectively growing silver sulfide clusters is described in JP-A-61-93447.

 Next, the compound of the general formula [II] will be described.

R ₁ represents a hydrogen atom, a lower alkyl group (eg, a methyl group, an ethyl group, an iso-propyl group, etc.) or a hydroxymethyl group, and R ₂ represents a hydrogen atom, a lower alkyl group (eg, a methyl group, an n-butyl group, iso-amyl group). The lower alkyl group preferably has 1 to 1 carbon atoms.
5, especially 1 is good.

Next, the compound of the general formula [III] of the present invention will be described.

In the general formula [III], R ₃ represents a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, an n-octadecyl group, a 2-hydroxyethyl group, 2-carboxyethyl group, 2-cyanoethyl group, sulfobutyl group, N, N-dimethylaminoethyl group, etc., substituted or unsubstituted cyclic alkyl group (for example, cyclohexyl group, 3-methylcyclohexyl group, 2-oxocyclopentyl group, etc.) ), Substituted or unsubstituted alkenyl groups (eg, allyl group, methylallyl group, etc.), substituted or unsubstituted aralkyl groups (eg, benzyl group, p-methoxybenzyl group, o-chlorobenzyl group, p-iso-propylbenzyl group) A substituted or unsubstituted aryl group (e.g., phenyl, naphthyl, o-methylphenyl, m-nitrophenyl group, 3,4-dichlorophenyl group, etc.), heterocyclic group (2-
Imidazolyl group, 2-furyl group, 2-thiazolyl group, 2
-Pyridyl group), R ₄ and R ₅ are each a hydrogen atom, a halogen atom (eg, chlor, bromo, etc.), a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a chloromethyl group,
-Hydroxyethyl group, tert-butyl group, n-octyl group, etc.), substituted or unsubstituted cyclic alkyl group (eg, cyclohexyl group, 2-oxocyclopentyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group, 4-nitrophenyl group, 4-aminophenyl group, 3-acetamidophenyl group, etc.), cyano group, heterocyclic group (for example, 2-imidazolyl group, 2-thiazolyl group, 2-pyridyl group, etc., substituted or unsubstituted alkylthio group (eg, methylthio group, 2-cyanoethylthio group, 2-ethoxycarbonylthio group, etc.), substituted or unsubstituted arylthio group (eg, phenylthio group) , 2-carboxyphenylthio, p-methoxyphenylthio, etc.), substituted or R ₄ represents an unsubstituted alkylsulfoxy group (eg, methylsulfoxy group, 2-hydroxyethylsulfoxy group, etc.) or a substituted or unsubstituted alkylsulfonyl group (eg, methylsulfonyl group, 2-bromoethylsulfonyl group, etc.) , R ₅ is an aromatic ring (e.g. benzene ring, naphthalene ring, etc.) mutually may be bonded to form a.

R ₆ and R ₇ each represent a hydrogen atom, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, an isopropyl group,
A cyanoethyl group, a 2-n-butoxycarbonylethyl group, a 2-cyanoethyl group or the like, a substituted or unsubstituted aryl group (for example, a phenyl group, a naphthyl group, a 2-methoxyphenyl group, an m-nitrophenyl group, A 5-dichlorophenyl group, a 3-acetamidophenyl group or the like, or a substituted or unsubstituted aralkyl group (such as a benzyl group, a phenethyl group, a p-iso-propylbenzyl group, an o-chlorobenzyl group, or an m-methoxybenzyl group). Express.

Hereinafter, typical specific examples of the compounds represented by formulas [II] and [III] according to the present invention are shown, but the compounds of the present invention are not limited thereto.

(Exemplary compound) Some of the compounds of the above general formula [II] are commercially available from San-ai Sekiyu KK, and some of the compounds of the general formula [III] are also commercially available and can be easily obtained. And it can be synthesized according to the synthesis method described in French Patent 1,555,416.

The above compounds represented by the general formulas (II) and (III) are compounds also known as preservatives for silver halide photographic light-sensitive materials, for example, U.S. Pat.
No. 66343 and No. 63-256944.

The silver halide photographic light-sensitive material chemically sensitized by containing the gold compound represented by the general formula [I] according to the present invention has the general formulas [II] and [II], which are preservatives as described above.
It has not been expected that the object of the present invention will be easily achieved by using at least one compound of the formula [I].

The compounds of the general formulas (II) and (III) are incorporated in a silver halide emulsion layer chemically sensitized with at least one compound of the general formula (I) and / or a hydrophilic colloid layer adjacent to the emulsion layer. It is added and contained.

The compounds of the general formulas [II] and [III] may be used alone or in combination.

The hydrophilic colloid layer referred to in the present invention is, for example, a photosensitive silver halide emulsion layer having substantially no photosensitivity, a protective layer, an intermediate layer, an antihalation layer, an undercoat layer or an antistatic layer,
Examples include an ultraviolet absorbing layer and a development control layer.

In the case of a silver halide emulsion, the addition amount may be from 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol, preferably from 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol per mol of silver halide.

0.001 to 100 for hydrophilic colloid layers other than emulsion layers
It may be 0 mg / m ² , preferably 0.01 to 100 mg / m ² .

The compound of formulas (II) and (III) may be added at any time during the production process of the light-sensitive material, but in the case of a silver halide emulsion, at an appropriate time after completion of chemical ripening or before coating. In the case of a hydrophilic colloid layer, it may be at any time during preparation of the coating solution.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, but particularly high sensitivity is obtained. From the viewpoint, silver iodobromide is preferred.

The silver halide grains in the photographic emulsion include those that are all isotropically grown, such as cubic, octahedral, and tetrahedral, or those that are polyhedral, such as spherical, and twins with plane defects. Or a mixed type or a composite type thereof. The size of these silver halide grains is 0.1
Large particles ranging from fine particles of not more than μm to 20 μm may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22-2
Emulsion Preparation and type on page 3
s) and (RD) No. 18716 (November 1979), page 648.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described in, for example, "The theory of the photographic material" by TH James.
Process, 4th edition, published by Macmillan (1977), pp. 38-104, GFDauffin, "Photographic Emulsion Chemistry", "Photogr
aphic emulsion Chemistry ", published by Focal press (1966
), P. Glafkides, "Physics and Chemistry of Photography", Chimie et p.
hysique photographique "published by Paul Montel (1967),
VLZelikman et al., "Manufacture and coating of photographic emulsions", "Making a
nd coating photographic emulsion "prepared by the method described in Focal press (1964).

That is, solution conditions such as neutral method, acidic method, ammonia method, etc., mixing conditions such as forward mixing method, back mixing method, double jet method, controlled double jet method, and particle preparation conditions such as conversion method, core / shell method, etc. And a combination thereof.

A preferred embodiment of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

Examples of the silver halide emulsion preferably used in the present invention include, for example, JP-A-59-177535, JP-A-61-802237, and JP-A-61-802237.
And the internal high iodine type monodispersed particles disclosed in JP-A-132943, JP-A-63-49751 and Japanese Patent Application No. 63-238225. The crystal habit of the crystal may be cubic, tetradecahedral, octahedral, and the (1,1,1) plane and the (1,0,0) plane between them may be arbitrarily mixed.

The monodisperse emulsion as used herein means that at least 95% of the particles by number or weight are within ± 40% of the average particle diameter, preferably within ± 30%, when the average particle diameter is measured by a conventional method, for example. Some silver halide grains. The grain distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The crystal structure of the silver halide may be different from the silver halide composition inside and outside.

The emulsion according to a preferred embodiment of the present invention is a core / shell type monodisperse emulsion having a clear two-layer structure comprising a low iodine shell layer in a high iodine core portion.

The silver iodide content of the high iodide part is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

Methods for producing such monodispersed emulsions are known, for example, J. Pho
t.Sic.12.242 to 251 (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, UK Patent
Nos. 1,413,748 and U.S. Pat. Nos. 3,574,628 and 3,655,394.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus is particularly preferable. As a method for obtaining a core / shell emulsion, for example, British Patent No. 1.027.146, U.S. Pat. No. 3,505,068, and U.S. Pat.
No. 7, JP-A-60-14331 and the like.

The silver halide emulsion used in the present invention may be tabular grains having an aspect ratio of 4 or more and less than 30.

The advantages of the tabular grains are improved spectral sensitization efficiency, and the improvement in graininess and sharpness of the image can be obtained.For example, UK Patent 2,112,157, US Patent 4,439,520,
Nos. 433,048, 4.414,310, 4,434,226, and JP-A-58-1
13927, 58-127921, 63-138342, 63-284
Nos. 272 and 63-305343, and emulsions can be prepared by the methods described in these publications.

The emulsion described above may be either a surface latent image type for forming a latent image on the grain surface, an internal latent image type for forming a latent image inside the grain, or a type for forming a latent image on the surface and inside. Good. These emulsions may use cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or a coagulated polymer agent exemplified by G3, G8 described in JP-A-63-158644, etc. The method used is a particularly preferred desalting method.

In the emulsion according to the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (December 1978) and No. 18716.
(November 1979). The following table shows the types and locations of the compounds shown in these two research disclosures.

The present invention is applicable to all silver halide photographic materials, but is particularly suitable for high-sensitivity black-and-white photographic materials.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by a commonly used known method.

The developer may be a commonly used developer such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-
Those containing a single substance such as p-aminophenol or p-phenylenediamine or a combination of two or more thereof are used, and conventional additives can be used. When the light-sensitive material is for color, color development can be performed by a commonly used color development method.

A developer containing an aldehyde hardener can also be used in the silver halide light-sensitive material according to the present invention. For example, maleic dialdehydes such as dialdehydes or glutaraldehyde and sodium bisulfite thereof can be used. Known developers in the field of photographic materials can be used.

Next, the conditions under which the photosensitive material of the present invention is processed will be described.

L, which is the processing length when processing the light-sensitive material of the present invention,
The range is more than 0.7 and less than 4.0 (unit: m). l is 0.7
In the following cases, each processing step may be reduced and the sensitivity may be reduced. Further, when the present invention is applied to a roller-type apparatus for transporting a photosensitive material, the number of rollers to be used is reduced and transportability is deteriorated. Conversely, if l is 4.0 or more,
The transport speed becomes too high, and the film is easily scratched.

The product of l ^0.75 and T is 50 or more and 130 or less. If this value is less than 50, the sensitivity of the light-sensitive material may be reduced, or color remaining may become a problem. More preferably, the product of l ^0.75 and T is 76 or more.

On the other hand, when the product of l ^0.75 and T exceeds 130, the sensitivity hardly increases, but the graininess of the photographic image deteriorates and fog increases.

According to the above-mentioned processing conditions according to the present invention, good sensitivity can be obtained with high granularity while having high sensitivity, and poor fixing and poor washing.

When processing using an automatic developing machine, it is preferable to use a roller-conveying automatic developing machine, in which case the number of all conveying rollers, the value obtained by dividing the processing length l by the number of rollers is in the range of 0.01 to 0.04. Is preferable. The time of each processing part is preferably in the following range.

Inserting + developing + migratory 25-40% Fixing + migratory 12-25% Washing + migratory 10-25% squeeze + drying 25-45% total 100% The roller used is 12mm-60mm
The length is preferably between 30 cm and 110 cm, and various materials can be used. For example, bakelite-based materials (which may include glass powder, metal powder, and plastic powder) in the areas of development, fixing, washing, and drying are used. And rubber (neoprene, isoprene, silicone rubber, etc.). It is preferable to use water-repellent and elastic silicone rubber or the like and "Clarino" (manufactured by Kuraray Co., Ltd.), a synthetic leather having high water absorbency, for the transition portion and the squeeze portion.

The processing solution such as a developing solution and a fixing solution used in the processing can be appropriately selected depending on the photosensitive material.

1 of FIG. 1 and FIG.
2 is the last roller at the drying outlet, 3a is the developing tank, 36 is the fixing tank, 3c is the washing tank, 4 is the photosensitive material to be processed, 5 is the squeezing section, 6 is the drying section, 7 is the dry air. Shows the outlet.

〔Example〕

Hereinafter, embodiments of the present invention will be described in detail. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example-1 [Preparation of Film-1] While controlling at 60 ° C., pAg = 8.0 and pH = 2.0, 2.0 mol% of silver iodide having an average particle size of 0.28 μm by a double jet method.
A monodispersed cubic silver iodide emulsion containing A part of this emulsion was used as a core and grown as follows. That is, a solution containing the core particles and gelatin at 40 ° C., pAg 9.0, pH 9.
At 0, the ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide are added by the double jet method, and silver iodide is added.
A first coating layer containing 30 mol% was formed. And further pAg =
At 9.0, pH = 9.0, an ammoniacal silver nitrate solution and a potassium bromide solution were added by a double jet method to form a second coating layer of pure silver bromide, and a cubic monodisperse iodobromide having an average particle size of 0.63 μm. A silver emulsion (silver iodide content: 2.2 mol%) was prepared. After removing excess salts by the coagulation sedimentation method, 7 × 10 ^-6 mol of sodium thiosulfate and 7 × 10 ^-4 mol of ammonium thiocyanate were added per 1 mol of silver halide. Such a gold compound of the general formula [I] is converted to silver halide 1
Optimum gold / sulfur sensitization was performed by adding 8 × 10 ⁻⁸ mol per mol. Further, the following sensitizing dye and potassium iodide were added in an amount of 1 × 10 ⁻³ mol / mol AgX to perform optimal spectral sensitization.

After completion of the spectral sensitization, 4-hydroxy-6-
Methyl 1,3,3a, 7-tetrazaindene was added in an amount of 3 g per mol of silver halide.

Next, the following additives were added to prepare an emulsion. The amount of addition was shown per mole of silver halide.

The following compounds were added to the protective layer per 1 g of gelatin.

The emulsion layer and the protective layer have the general formula (II) according to the present invention.
And the compound of [III] were added in the amounts shown in Table 1 to obtain a coating solution.

Next, the emulsion coating solution and the protective layer solution were mixed to a thickness of 175 μm.
m was applied to one side of a blue-colored polyethylene terephthalate film which had been subjected to an undercoating treatment with a slide hopper coater.

The coated silver amount is 2.4 g / m ² on one side and the gelatin is 2.2 g / m ^{2 on} one side
Also, the protective layer is 1.1 g / m ² as gelatin weight.
At the same time.

Thus, a film comprising a monodisperse silver iodobromide emulsion was prepared.

 The following test was performed on the obtained sample.

Storage test of film A part of the sample was left to stand naturally for one day, and stored for three days in an atmosphere at a temperature of 55 ° C. and a relative humidity of 20% to prepare a sample which was forcibly deteriorated. The sample was screen KO- manufactured by Konica Corporation.
After exposure to X-rays using No. 250, it was processed in the automatic developing machine shown in FIG. 1 using a developing solution XD-SR and a fixing solution XF-SR (manufactured by Konica Co., Ltd.) under the following conditions. .

 The processing time T was 46 seconds, and the processing length was 2.74 m.

 The processing conditions were set as follows.

Temperature Replenishment amount Current image 35 ℃ 33cc / quartz 1 piece Fixed 33 ℃ 63cc / quartz 1 piece Washing Set to 20 ℃ 1.5 / min Drying 45 ℃ － The relative sensitivity in the table is sample No.1 The relative sensitivity when the sensitivity was set to 100 was shown.

Film running test Under the above-described processing conditions, each sample was exposed to a concentration of about 1.2, and 1000 pieces were continuously processed in a 4-piece size.

For each film, the relative sensitivity was determined at the 500th and 1000th sheets.

Note that the value at the start (0th sheet) is a value for one day when left naturally.

 Table 1 shows the obtained results.

As is evident from Table 1, the sample according to the present invention has no fog increase and desensitization even under severe storage conditions, and shows stable and high sensitivity with little fluctuation even in running processing.

Example 2 Using the emulsion prepared in Example 1 as an emulsion, a new emulsion was prepared as follows.

30 g of gelatin, 10.5 g of potassium bromide, thioether [HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH] in water 1
10 ml of a 0.5 wt% aqueous solution was added and dissolved. In a solution (pAg = 9.1, pH = 6.5) maintained at 63 ° C., 30 ml of a 0.88 mol silver nitrate solution and 0.88 mol of potassium iodide and potassium bromide were stirred while stirring. After simultaneously adding 30 ml of a mixed solution (molar ratio: 97.3) for 15 seconds, 600 ml of a 1 molar silver nitrate solution and 600 ml of a mixed solution composed of potassium bromide and potassium iodide at a molar ratio of 96.5: 3.5
Were added simultaneously over 70 minutes to prepare a tabular silver iodobromide emulsion. The resulting tabular silver halide grains have an average grain size.
It was 1.15 μm, 0.10 μm thick, and had a silver iodide content of 3.0 mol%. Excess salt was removed from the emulsion by a coagulation sedimentation method to obtain an emulsion.

The emulsion was subjected to gold and sulfur sensitization for optimal chemical sensitization as shown in Table 2 according to Example 1, and then 160 mg of a sensitizing dye was added per 1 mol of silver halide. Other than that, the sample No. 11 was exactly the same as the example 1.
Created ~ 26.

Table 2 shows the results of testing the obtained samples for film preservability and running processability. The development processing time was varied as shown in Table 2 by preparing the drive motor control unit of the automatic developing machine.

 Table 2 shows the obtained results.

As is clear from Table 2, according to the present invention, even when the emulsion was tabular silver halide grains, similar to the cubic emulsion, good storage stability and running processability were obtained.

〔The invention's effect〕

According to the present invention, a silver halide photographic light-sensitive material having stable and high sensitivity without fog increase during storage of the film over time was obtained.

Further, according to the present invention, it was possible to provide a silver halide photographic light-sensitive material having a small variation in photographic performance even after running processing.

[Brief description of the drawings]

FIG. 1 and FIG. 2 are configuration diagrams of an automatic developing machine used in an embodiment of the present invention.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer has the following general formula (I): Wherein the hydrophilic colloid layer contains at least one of the compounds represented by the following general formulas (II) and / or (III): A silver halide photographic light-sensitive material processed by a roller transport type automatic developing machine under the conditions corresponding to the following formula A: In the general formula [I] _{[HlAu m (L) n (X} ) p ] _q formula, L is a heterocyclic ligand 5- or 6-membered, X represents an anion group. l is an integer of 0 to 2, m is an integer of 1 or 2, n is an integer of 1 to 3, p is an integer of 0 to 3, and q is 1 to 4.
Represents an integer. In the formula, R ₁ represents a hydrogen atom, an alkyl group or a hydroxymethyl group, and R ₂ represents a hydrogen atom or an alkyl group. In the formula, R ₃ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or The stands, R _4, R ₅ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkyl sulfoxy group, an alkylsulfonyl group, R ₄ and R ₅ together They may combine to form an aromatic ring.
R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. Formula A l ^0.75 × T = 50-130 (0.7 <l <4.0) where l is the processing length when processing the photosensitive material (unit: m)
And T represents the time (Sec) required to pass through l.