JPH0555006B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material capable of obtaining images with high sensitivity, high contrast, and high maximum density. [Prior Art] Increasing the sensitivity of a film is important in order to reduce the amount of silver used. For example, in X-ray film, it is also important for reducing exposure dose. One way to increase the sensitivity of a film is to reduce the degree of hardness of the film layer made of gelatin or the like. However, this method is not preferable because it deteriorates the graininess of the developed image and deteriorates the physical properties of the film. JP-A-57-89749 discloses thioethers (e.g.
C ₆ H ₁₃ OCOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OCOC ₆ H
A method is disclosed in which a development accelerator such as ₁₃ ) or a nitrogen-containing cyclic compound having a thioketone group is added to a silver halide emulsion or a developer. but,
If this method is used to increase sensitivity, graininess will deteriorate, and if added to a silver halide emulsion, fog will increase during storage, which is not preferable. Increasing the grain size of the silver halide emulsion also increases sensitivity, but in order to obtain both high sensitivity and the required maximum image density, more silver salt must be contained per unit area of the film. Moreover, it is undesirable because it is accompanied by deterioration of graininess and a decrease in covering power (Japanese Patent Application Laid-open No. 148051/1983). As an attempt to improve covering power while maintaining high sensitivity, techniques for adding various polymers to high-sensitivity coarse-grain silver halide emulsions have been published in British Patent No. 1048057, British Patent No. 1039471, and U.S. Patent No. 1039471.
It is described in the specifications of No. 3043697 and No. 3446618. All of these have the effect of increasing the covering power to some extent, but are not sufficient, and furthermore, they weaken the strength of the coating film, which is not preferable. Furthermore, this method is not preferable because fog changes significantly over time and uneven development is likely to occur depending on the development processing method. Further, JP-A-52-42725 and the like describe a so-called amplifier technique in which a black coupler imagewise contains an organic substance that develops color. However, this method is not preferable because the organic substances contained therein are unstable and therefore deteriorate significantly over time, and depending on the development method, uneven development is likely to occur. On the other hand, U.S. Pat. No. 2,996,382 and U.S. Pat. No. 3,178,282 disclose a technique in which surface latent image type silver halide coarse particles and silver halide fine particles having fog nuclei inside are supported in the same layer or in an adjacent layer. It is described that a silver photographic material is used to obtain photographic images with high sensitivity, high contrast, and high covering power. However, this method has the problem that fog is likely to occur during development. Furthermore, with this method, sensitivity and gradation changes are large during high-temperature processing (processing at a temperature of 30° C. or higher), and stable photographic performance cannot be obtained. As a technique for improving this problem, JP-A-60-166944 describes the use of mesoionic triazolium compounds, but this compound alone is not preferred because it causes desensitization. [Object of the Invention] The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a silver halide photographic material that provides images with high sensitivity, high contrast, and high maximum density. Another object of the present invention is to suppress the occurrence of fog and extremely increased changes in sensitivity and gradation, particularly during high-temperature rapid processing, and to suppress changes in sensitivity and gradation due to temperature variations at high temperatures. The goal is to reduce it. That is, an object of the present invention is to provide a silver halide photographic material that always provides stable photographic performance. [Structure and operation of the invention] The above object of the present invention is to provide photosensitive silver halide grains on a support, silver halide grains having internal fog stabilized by a compound having a mercapto functional group, and having a melting point. This could be achieved by using a valent silver halide photographic light-sensitive material that is 40° C. or higher and contains a polyhydric alcohol having at least two hydroxyl groups in its molecule. Furthermore, according to the present invention, not only can high-quality images and silver halide photographic materials with less processing dependence be obtained by high-temperature processing, but also low-temperature processing (generally 20°C
It was confirmed that excellent effects were exhibited with little change in sensitivity and gradation even when the development time was 2 to 20 minutes. The melting point used in the present invention is 40°C or higher,
And as a polyhydric alcohol having at least two or more hydroxyl groups in the molecule,
- 12 carbon atoms, 2 to 20 carbon atoms, and the hydroxyl groups are not conjugated in a conjugated chain, that is, it is an alcohol that cannot be oxidized, and has a melting point of 50℃ or higher and 300℃ The following are preferred. Specific examples Nos. 1 to 50 are given below, but the present invention is not limited to these specific examples. No. Compound name Melting point (℃) 1 2,3,3,4-tetramethyl-2,4-pentanediol 76 2 2,2-dimethyl-1,3-propanediol 126-128 3 2,2-dimethyl- 1,3-pentanediol 60-63 4 2,2,4-trimethyl-1,3-pentanediol 52 5 2,5-hexanediol 43-44 6 2,5-dimethyl-2,5-hexanediol 92-93 7 1,6-hexanediol 42 8 1,8-octanediol 60 9 1,9-nonanediol 45 10 1,10-decanediol 72-74 11 1,11-undecanediol 62-62.5 12 1, 12-Dodecanediol 79-79.5 13 1,13-Tridecanediol 76.4-76.6 14 1,14-Tetradecanediol 83-85 15 1,12-Octadecanediol 66-67 16 1,18-Octadecanediol 96-98 17 Cis -2,5-dimethyl-3-hexene-2,5-diol 69 18 trans-2,5-dimethyl-3-hexene-2,5-diol 77 19 2-butyne-1,4-diol 55 20 2, 5-dimethyl-3-hexyne-2,5-diol 95 21 2,4-hexadiyne-1,6-diol 111-112 22 2,6-octadiyne-1,8-diol 88.5-89.5 23 2-methyl-2 ,3,4-butanetriol 49 24 2,3,4-hexanetriol approx. 47 25 2,4-dimethyl-2,3,4-pentanetriol 99 26 2,4-dimethyl-2,3,4-hexane Triol 75 27 Pentamethylglycerin 116-117 28 2-Methyl-2-oxymethyl-1,3-propanediol 199 29 2-isopropyl-2-oxy methyl-1,3-propanediol 83 30 2,2-dihydroxymethyl - 1-Butanol 58 31 Erythritol 126 32 D-trait 88 33 L-trait 88-89 34 rac-trait 72 35 Pentaerythritol 260-265 36 1,2,3,4-pentanetetrol 106 37 2,3,4, 5-hexanetetrol 162 38 2,5-dimethyl-2,3,4 2,5-hexanetetrol 153-154 39 1,2,5,6-hexanetetrol 95 40 1,3,4,5-hexanetetrol 88 41 1,6-(erythro-3,4)-hexanetetrol 121-122 42 3-hexene-1,2,5,6-tetrol 80-82 43 3-hexene-1,2,5,6 - Tetrol 113-114.5 44 Adonitol 102 45 D-arabitol 102 46 L-arabitol 102 47 rac-arabitol 105 48 Xylitol 93-94.5 49 Mannitol 164 50 Dulcitol 188.5-189 There are no particular restrictions on the usage amounts of the above compounds No. 1 to 50. No is 1 to 100 g, preferably 5 to 50 g, per mole of silver halide. And the above compound No.1
~50 is added to the silver halide emulsion layer or a layer adjacent thereto. Preferably, it can be added to at least one or both of a photosensitive silver halide emulsion and a metal salt emulsion having fog nuclei inside, or to a mixed system of a silver halide emulsion and a metal salt emulsion having fog nuclei inside. Although the timing of addition is arbitrary, it is added between after the completion of chemical sensitization and during coating. As for the addition method, it may be directly dispersed in a hydrophilic colloid, or it may be added after being dissolved in an organic solvent such as methanol or acetone. In the present invention, "photosensitivity" means that the sensitivity of the photosensitive silver halide grains is higher than the sensitivity of the bulky metal salt grains inside. More specifically, it means having a sensitivity that is 10 times or more, more preferably 100 times or more, the sensitivity of the internal bulky metal salt particles. The sensitivity here is defined in the same way as the sensitivity shown below. As the photosensitive silver halide emulsion, a conventional silver halide emulsion such as a surface latent image type emulsion is used. Here, the surface latent image type silver halide emulsion is 1
~1/100 seconds After exposure, when developed using the surface development (A) method and internal development (B) method shown below, the surface development
It is an emulsion in which the sensitivity obtained in (A) is greater than the sensitivity obtained in internal development (B), preferably an emulsion in which the sensitivity of the former is at least twice that of the latter. Here, sensitivity is defined as follows. S=100/Eh S is the sensitivity, and Eh is the density 1/2 (Dmax +
Indicates the amount of exposure required to obtain Dmin). [Surface development (A)] Develop for 10 minutes at a temperature of 20°C in a developer with the following formulation. N-Methyl-p-aminophenol (hemisulfate) Add sodium ascorbate metaborate and potassium tetrachloride bromide water 2.5g 10g 35g 1g 1 [Internal development (B)] Red blood salt 3g/and phenosafnin 0.0126 g/
for 10 minutes at approximately 20°C in a bleach solution containing
After washing with water for 10 minutes, develop for 1 minute at 20°C in a developer with the following formulation. N-Methyl-p-aminophenol (hemisulfate) Sodium ascorbate metaborate tetrahydrate Sodium bromide calithiosulfate 2.5g 10g 35g 1g 3g 1 Specific examples of surface latent image type silver halide Silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide can be used. Here the content of silver iodide is 0.1-30 mol%, especially 0.5-10 mol%
It is preferable that it is in the range of . The average grain size is preferably larger than that of a silver halide emulsion having fog nuclei inside, and particularly preferably 0.6 μm or more. The particle size distribution may be narrow or wide. The silver halide grains in the emulsion may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc. It may have an irregular crystal form or a composite form of these crystal forms.
It may also consist of a mixture of particles of various crystalline forms. Further, tabular grains having a grain size of three times or more the grain thickness are preferably used in the present invention. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique, Paul
Montel Publishing, 1967), GFDuffin, Photographic Emulsion Chemistry, The
Focal Press, 1966), VLZelikamn et al.
Author, Making and Coating Photographic Emulsions
Coating Photographic Emulsion, The Focal
Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. The soluble salts are usually removed from the emulsion used in the present invention after precipitation or physical ripening, and the long-known Nudel water washing method in which gelatin is gelatinized may be used as a means for this purpose. Also, inorganic salts consisting of polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated A sedimentation method (floculation) using gelatin, etc.) may also be used. Note that the process of removing soluble salts may be omitted. Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, Glafkides or
Zelikman et al. or H. Frieser (ed.)
Grundlagen der Photographischen Prozesse
mit Silberhalogeniden, Akademische
Verlagsgesell-schaft, 1968) can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
Described in Nos. 2278947, 2728668, and 3656955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include US Pat. Nos. 2487850, 2419974,
Described in Nos. 2518698, 2983609, 2983610, and 2694637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in the periodic table group such as platinum, iridium, and palladium can be used.
It is described in issues such as No. 618061. Next, the silver halide grains having internal fog (hereinafter sometimes abbreviated as "internal fog particles") used in the silver halide photographic light-sensitive material of the present invention will be explained. In the present invention, internal fog particles are stabilized using compounds with mercapto functionality. Compounds having a mercapto functional group include, for example, heterocyclic nitrogen compounds having a mercapto functional group, in which the mercapto group is bonded to a carbon atom at the α-position relative to the nitrogen atom of the heterocyclic ring; , tetrazaindenes with at least one mercapto function, purines with at least one mercapto function, triazaindenes with at least one mercapto function,
Examples include pentazaindenes having at least one mercapto functional group. In the silver halide photographic light-sensitive material of the present invention, high sensitivity, high contrast, and increased covering power can be achieved by using an emulsion containing internal fogging grains together with a high-iodine photosensitive silver iodobromide emulsion. can. Here, it is preferable that the sensitivity of the emulsion containing internal fogging grains is lower than the sensitivity of the photosensitive silver halide emulsion. More specifically, the sensitivity of the emulsion containing internal fogging grains is preferably 10 times or less, more preferably 100 times or less (relative to the light-sensitive silver halide emulsion). For example, as a silver halide emulsion having internal fog nuclei used in the silver halide photographic light-sensitive material of the present invention, a test piece coated on a transparent support at a content of 2 g/m ² is not exposed to light. niD-
19 (Developer specified by Eastman Kodatsu) and 35
When developed for 2 minutes at ℃, it gave a transmission fog density of 0.5 or less (excluding the density of the support itself), and 0.5% of potassium iodide was added to D-19 without exposing the same specimen.
g/When developed with added developer at 35℃ for 2 minutes
An emulsion that provides a transmission fog density (excluding the density of the support itself) of 1.0 or more is used. Silver halide emulsions having fog nuclei inside can be prepared by various methods. Methods for fogging include irradiating with light or X-rays, chemically creating fog nuclei using reducing agents, gold compounds, or sulfur-containing compounds, and producing emulsions under conditions of low pAg and high pH. There is a way. To create fog nuclei only on the inside, there is a method in which both the interior and surface of the silver halide grain are fogged by the above method, and then the fog nuclei on the surface are bleached with a red blood salt solution, but it is more preferable. The method is to first prepare a core emulsion with fog nuclei using a low pAg, high PH method or a chemical fogging method, and then cover the core emulsion with a shell emulsion. For the preparation method of this core shell emulsion, for example, the description in US Pat. No. 3,206,313 can be referred to. Silver halide emulsions having internal fog nuclei generally preferably have a smaller average grain size than light-sensitive silver halide emulsions, ranging from 1.0 to 0.05μ.
Preferably, those with an average particle size of m, 0.6
Those with an average particle size of ~0.1 μm are more preferred, and those below 0.5 μm are particularly preferred and give good results. In addition, the internal bulky silver halide emulsions include silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide,
Any silver chloride or the like may be used. The content ratio of the photosensitive silver halide grains and the internal rounded silver halide grains of the silver halide photographic light-sensitive material of the present invention is determined by the emulsion type used (e.g.
It can be changed depending on the halogen composition), the type or purpose of the photosensitive material used, the contrast of the emulsion used, etc., but preferably 100:
1 to 1:100, particularly preferably 10:1 to 1:10. In addition, the total amount of coated silver is 0.5
~10 g/ ^m2 is preferred. Various hydrophilic colloids can be used as binders in the silver halide photographic material of the present invention. Colloids used for this purpose include hydrophilic colloids commonly used in the photographic field, such as gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, and acrylamide polymers. can be mentioned. Along with the hydrophilic colloid, a hydrophobic colloid, such as a dispersed polymerized vinyl compound, particularly one that increases the dimensional stability of the silver halide photographic light-sensitive material, can be contained. Suitable compounds of this type include water-insoluble polymers made by polymerizing vinylic monomers such as alkyl acrylates or alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates. Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted),
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),
Mercaptopyridines: The above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,
Many compounds known as stabilizers can be added, such as 3a, 7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc. An example of a compound that can be used is by K. Mees, The
The Theory of the Photographic Process
Process, 3rd edition, 1966), citing the original literature. For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474;
No. 3982947, No. 4021248, specifications or Tokkosho
The description in Publication No. 52-28660 can be referred to. Several embodiments are conceivable regarding the layer structure of the silver halide photographic light-sensitive material according to the present invention. Representative ones are shown below (1) to (5). (1) Photosensitive silver halide grains, silver halide grains with fog nuclei inside, and melting point of 40°C
A polyhydric alcohol (hereinafter simply referred to as polyhydric alcohol) which is the above and has at least two or more hydroxyl groups in the molecule is contained in the same coating composition (emulsion), and this is coated on a support. Structure, (2) First, an emulsion layer containing silver halide grains having fog nuclei inside is coated on a support, and then an emulsion layer containing photosensitive silver halide grains and polyhydric alcohol is further coated on top of this. (3) First, photosensitive silver halide grains and silver halide grains having fog nuclei inside are contained in the same coating composition (emulsion), and this is coated on a support, and then coated on this. (4) A structure in which an emulsion layer containing photosensitive silver halide grains is coated; (4) photosensitive silver halide grains, silver halide grains having fog nuclei inside, and polyhydric alcohol are coated in the same coating composition (emulsion); A structure in which an emulsion containing photosensitive silver halide grains and a silver halide grain emulsion having fog nuclei inside in a composition different from that of the lower layer is coated on top of the support. , (5) A structure in which a coating amount of gelatin containing polyhydric alcohol is applied as a protective layer to a structure obtained by removing only polyhydric alcohol from the components (1) to (4) above, etc. can. In the silver halide photographic material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be hardened with any suitable hardener. These hardening agents include mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dimethylol urea, trimethylolmelamine, glyoxal, momemethylglyoxal, 2,3-dihydroxy-1, Aldehyde compounds such as 4-dioxane, 2,3-dihydroxy-5-methyl-1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran, and glutaraldehyde: divinyl sulfone, methylene bismaleimide, 5-acetyl-1 ,3-diacryloyl-
Hexahydro-s-triazine, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-trivinylsulfonyl-hexahydro-s-triazine bis(vinylsulfonylmethyl)ether, 1,3-bis( Active vinyl compounds such as vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane: 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6-methoxy- s-triazine, 2,4-
Dichloro-6-(4-sulfoanilino)-s-triazine sodium salt, 2,4-dichloro-6-
(2-sulfoethylamino)-s-triazine,
N,N'-bis(2-chloroethylcarbamyl)
Active halogen compounds such as piperazine: bis(2,3-epoxypropyl)methylpropylammonium p-toluenesulfonate, 1,4
- Epoxy systems such as bis(2',3'-epoxypropyloxy)butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5-(γ-acetoxy-β-oxypropyl)isocyanurate Compounds: Ethyleneimine compounds such as 2,4,6-triethyleneimino-s-triazine, 1,6-hexamethylene-N,N'-bisethyleneurea, bis-β-ethyleneiminoethylthioether, 1,2 -di(methanesulfonoxy)ethane, 1,4-(methanesulfonoxy)
Examples include methanesulfonic acid ester compounds such as butane and 1,5-di(methanesulfonoxy)pentane, as well as inorganic compounds such as carbodiimide compounds, isoxazole compounds, and chromium alum. The photographic emulsion layer or other constituent layers of the silver halide photographic light-sensitive material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). ) may contain surfactants other than those of the present invention for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols non-ionic materials such as alkylamides or amides, polyethylene oxide adducts of silicone), glycidol derivatives (in other words, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Ionic surfactants, alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaltalene sulfonates, alkyl sulfates, alkyl phosphate esters, N-acyl-N-alkyl taurine Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Containing anionic surfactants, amino acids, aminoalkylsulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amphoteric surfactants such as amine oxides, alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The silver halide photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonole dyes: hemioxonol dyes and merocyanine dyes are useful. In the silver halide photographic material of the present invention,
When dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. Further, the silver halide photographic material of the present invention is
U.S. Patent No. 3411911, No. 3411912 in the photographic constituent layer
and Japanese Patent Publication No. 45-5331. Other additives may be added to the silver halide emulsion, especially those useful in photographic emulsions, such as lubricants, ring thickeners, light-absorbing dyes, and the like. In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a ring-enhancing dye. The dyes used include cyanine dyes,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. Merocyanine dyes or complex merocyanine dyes include a nucleus having a ketomethylene structure, such as a pyrazolin-5-one nucleus, a thiohydanthrin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiazolidine-2,4-dione nucleus. A 5- to 6-membered heteroartic ring nucleus such as a barbiturate nucleus can be applied. The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. of sensitizing dye per mole of silver halide
1.0×10 ^-5 to about 5×10 ^-4 mol, especially about 4×10 ^-5 to about 2×10 ^-4 of sensitizing dye per mol of silver halide
Preferably, molar concentrations are used. The silver halide emulsions of this invention include color image-forming couplers, namely aromatic amines (usually primary amines).
It may also contain a compound (hereinafter abbreviated as a coupler) that reacts with an oxidation product of a developing agent to form a dye. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. Also, colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DIR couplers).
May include. The coupler may be one in which the product of the coupling reaction is colorless. As the yellow color-forming coupler, various open-chain ketomethylene couplers can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Magenta couplers include pyrazolone compounds,
Indazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. As cyan couplers, phenolic compounds,
Naphthol compounds and the like can be used. The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above. Further, the protective layer may be a single layer or a multilayer. A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention. An example of a matting agent is a water-dispersible material such as polymethyl methacrylate with an appropriate particle size (preferably a particle size of 0.3 to 5 μm or a particle size of at least 2 times, especially 4 times or more, the thickness of the protective layer). Organic compounds such as vinyl polymers or inorganic compounds such as silver halide, barium strontium sulfate, etc. are preferably used. Smoothing agents are useful in preventing adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties related to camera compatibility during filming or projection of motion picture film; specific examples include liquid paraffin, Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, polyalkylpolysiloxanes,
Silicones such as polyarynepolysiloxane, polyalkylarylpolysiloxane, or alkylene oxide addition derivatives thereof are preferably used. The silver halide photographic material of the present invention may also be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary. Specifically, silver halide photographic materials using the silver halide photographic emulsion of the present invention include X-ray photographic materials, Lith photographic materials, black-and-white photographic materials,
Examples include color negative photosensitive materials, color reversal photosensitive materials, and color photographic paper. Various other additives may be used in the silver halide photographic material of the present invention, if necessary. Examples include dyes, development accelerators, optical brighteners, color antifoggants, and ultraviolet absorbers. Specifically, RESEARCH DISCLOSURE No. 176 No. 28-30
(RD-17643, 1978) can be used. Furthermore, in the present invention, a compound that releases iodide ions (for example, potassium iodide) can be contained in the silver halide emulsion, and a desired image can be obtained using a developer containing iodide ions. In the silver halide photographic material of the present invention, the emulsion layer and other layers are coated on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include cellulose nitrate, cellulose acetate, cellulose acetate butyrate,
Films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., papers coated with or laminated with baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers), etc. It is. The support may be colored using dyes or pigments. It may be black for the purpose of illumination. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating process is done by Tokukai Sho.
Publication No. 52-104913, Publication No. 59-18949, Publication No. 59-
The treatments described in JP 19940 and JP 59-19941 are preferred. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. In the silver halide photographic material of the present invention,
Photographic emulsion layers and other hydrophilic colloid layers can be coated on the support or on top of other layers by a variety of coating techniques. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. The present invention can be used for any photographic material that requires high sensitivity or high contrast. For example, it is used in X-ray photographic materials, lithographic photographic materials, black and white negative photographic materials, color negative photographic materials, color paper photographic materials, and the like. It can also be used for diffusion transfer light-sensitive materials and color diffusion transfer light-sensitive materials that produce positive images by dissolving undeveloped silver halide and precipitating it on an image-receiving layer close to a silver halide emulsion layer. can. For example, Research Disclosure No. 176, pages 28-30 (RD
-17643), any of the various methods and various processing solutions can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 18℃ to 50℃
Selected between 18℃ or lower temperature than 50℃
The temperature may exceed ℃. For example, developers used in black-and-white photographic processing can include known developing agents.
As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-o-aminophenol), etc. are used alone or in combination. be able to. The silver halide photographic material of the present invention may be photographically processed using a developer containing imidazoles as a silver halide solvent as described in Japanese Patent Application No. 155489/1982. In addition, the special request for
It can be processed with a developer containing a silver halide solvent and an additive such as indazole or triazole as described in No. 136267. The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" development processing is a process in which dihydroxybenzenes are usually used as a developing agent and the development process is carried out at a low sulfite ion temperature for the photographic reproduction of line images or the halftone dot photographic reproduction of halftone images. Refers to a developing process that is carried out contagiously. A method may be used in which the photosensitive material is contained in a light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution to perform development. Hydrophobic developing agents are
Research Disclosure No. 169 (RD-
16928) US Patent No. 2739890, UK Patent No. 813253
They can be incorporated into the emulsion layer by various methods, such as those described in German Patent No. 1,547,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When performing color photographic development processing, for example, a negative-positive method, a color reversal method, a silver dye bleaching method, etc. are used. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a primary aromatic amine developer, such as phenylenediamines (e.g. 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N -ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) and LFAMason
Author: Photographic Processing Chemistry, Focal Press
Press), 1966, pp. 226-229, U.S. Patent No.
Those described in No. 2193015, No. 2592364, JP-A-48-64933, etc. may be used. The color developer can also contain a PH buffer, a development inhibitor, an antifoggant, and the like. In addition, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, and antioxidants are added. It may also include. After color development, the photographic emulsion layer is bleached.
The bleaching process may be performed simultaneously with the fixing process,
It may also be done individually. Bleach agents include Fe ⁺³ ,
Compounds of polyvalent metals such as Co ⁺⁴ , Cr ⁺⁶ , and Cu ⁺² , peracids, quinones, and nitroso compounds are used. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thioether compound described in No. 65732, various additives can also be added. Exposure for the photographic emulsion used in the present invention varies depending on the state of optical sensitization, purpose of use, etc., but includes tungsten, fluorescent lamps, mercury lamps, arc lamps, xenon, sunlight, xenon flash, cathode ray tube flying spots, and lasers. light, electron beam, x-ray, x
Various types of light sources, such as a fluorescent screen for radiographing, can be used as appropriate. In addition to the normal exposure time of 1/1000 to 100 seconds,
For xenon flash, cathode ray tube, and laser light, short exposure times of 1/10 ⁴ to 1/10 ⁹ seconds can be applied. [Examples of the Invention] The present invention will be further explained below with reference to Examples.
It goes without saying that the present invention is not limited to the examples. Example 1 (1) Preparation of polydisperse emulsion A polydisperse emulsion [A] was prepared by a forward mixing method. That is, Solution A: Silver nitrate 100g Aqueous ammonia (28%) 78c.c. Add water to make 240c.c. Solution B: Ossein gelatin 8g Potassium bromide 80g Potassium iodide 1.3g Add water to make 550c.c. Solution C : Ammonia water 6 c.c. Glacial acetic acid 10 c.c. Water 34 c.c. Solution D: Glacial acetic acid 226 c.c. Add water to prepare four solutions of 400 c.c. Solution B and solution C were poured into a reaction vessel for emulsion preparation and stirred with a propeller type stirrer at a rotation speed of 300 revolutions/minute, and the reaction temperature was maintained at 55°C. Next, the solution A was divided into 1 volume: 2 volumes, and 1 volume, 100 ml, was added over 1 minute. After stirring for 10 minutes, the remaining 2 volumes of Solution A, 200ml
was added over 2 minutes, and stirring was continued for an additional 30 minutes. Then, add solution D to the solution in the reaction vessel.
The pH was adjusted to 6 to stop the reaction. In this way, polydispersed emulsion [A] was obtained. This emulsion contains 2.0 mol% silver iodide, and the average grain size is
It was 1.21 μm. Next, the above emulsion was desalted by a conventional agglomeration method, and then 60 mg of ammonium thiocyanate/1 mole of silver halide, 1 mg of chloroauric acid/1 mole of silver halide, and sodium thiosulfate were added to the desalted emulsion. Gold to sulfur sensitization was carried out by adding 2 mg/mol of silver halide and 1 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (stabilizer)/1 mol of silver halide. A silver iodobromide emulsion (a) was obtained. (2) Preparation of emulsion (b) with internal fog In a 2.5% by weight aqueous gelatin solution kept at 55°C,
Silver nitrate aqueous solution and potassium bromide aqueous solution were added simultaneously. After the addition, the temperature of the solution was maintained at 70°C, and potassium hydroxide and silver nitrate were added and aged for 20 minutes to form fog nuclei. Then add the solution to 55
After keeping the temperature at ℃ and neutralizing it by adding acetic acid, a coating was formed by simultaneously adding an aqueous solution of silver nitrate and an aqueous solution of potassium bromide, desalted by the usual flocculation method, and redispersed in an aqueous gelatin solution to obtain an average grain size. An emulsion with an internal fog having a diameter of 0.40 μm was obtained.
To this emulsion was added 120 mg of 5-mercapto-1-phenyltetrazole per mole of silver halide to obtain emulsion B having internal fog. (3) Preparation of test sample Photosensitive silver halide emulsion (a) prepared in (1) above
and emulsion (b) having internal fog prepared in (2) were mixed at a weight ratio of 2:1 and dissolved. To this, the polyhydric alcohol according to the present invention was added as shown in Table 1, and further 200 mg of nitrone/1 mole of silver halide and 1.5 g of sodium 2,4-dihydroxybenzenesulfonate/1 mole of silver halide were added.
1 mole of styrene and maleic acid copolymer
g/After adding 1 mole of silver halide, JP-A-59-
It was applied to the surface of a polyester film base that had been primed using the method described in 19941. Furthermore, a protective layer was formed by applying an aqueous gelatin solution having the following composition onto each emulsion surface. The amount of silver coated on both sides was 4.5g/ ^m2 .
The coating amount of gelatin in the protective layer was 2.6 g/m ² on both sides, and the coating amount of gelatin in the emulsion layer was 4.0 g/m ² . Composition of gelatin aqueous solution Lime-treated gelatin 70g 1.8g 1.0g 2.6g Ludotux AM 40c.c. 2,4-dichloro-6-hydroxy-1,
3,5-triazine sodium salt 1.0g (4) Test method for test sample The sample prepared above was wedge-exposed with 3.2CMS, and QX-
Using a 1200 automatic processor, develop at 31°C, 35°C, 37°C using XD-90 developer processing solution and XF fixing processing solution.
After developing each film at 90°C for 90 seconds, photographic performance was measured and the results shown in Table 1 were obtained. As comparison samples, one coated with only a tourist silver halide emulsion and one coated with only an emulsion having internal fog with similar amounts of silver and gelatin were used. In addition, the following compounds were used as polyhydric alcohol comparison compounds. Compound name Melting point (a) Ethylene glycol -12.6℃ (b) 1,4-betanediol 16℃ (c) Glycerin 18.2℃ (d) 1,2,6-hexanetriol -20℃ Sensitivity in Table 1 is "Fog value" It is the reciprocal of the exposure amount required to obtain a transmission blackening density of +1.0'', and is expressed as a relative value with the development temperature of sample 1 at 35° C. as 100. Furthermore, for gamma, the slope value of the characteristic curve between "fog value +02" and "fog +1.0" was used. Note that the fog value includes the base density. Furthermore, the compound (A) used in Example 2 of JP-A-60-166944 was used as a comparative compound. Compound (a)

[Table] As is clear from Table 1, Samples Nos. 10 to 18 using the compounds of the present invention have small changes in fog, sensitivity, and gamma due to changes in processing temperature, and have good processing temperature dependence. This means that compared to conventional silver halide photographic materials in which polyhydric alcohols functioned as sensitizers, in so-called "trigger-sensitive materials" they have a completely different function. . That is, it seems that polyhydric alcohols with low melting points quickly flow out of the film during high-temperature processing, making it impossible to satisfactorily control the "trigger effect." Example 2 In this example, the following experiment was conducted in order to confirm the stabilizing effect of a compound having a mercapto functional group. An emulsion (c) having an internal fog was obtained in the same manner as in Example 1, except that 5-mercaptotetrazole was omitted. Emulsions (a) and (b) were prepared according to Example 1, and samples were prepared using these emulsions in the same manner as in Example 1. As a polyhydric alcohol, compound No. 30 was added in an amount of 22 g per mole of silver halide. As is clear from Table 2, sample No. 21 of the present invention
It can be seen that the changes in fog, sensitivity, and gamma due to changes in processing temperature are small, and the processing temperature dependence is good, and the film is also excellent in terms of fog and maximum density.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide photographic material that provides images with high sensitivity, high contrast, and high maximum density. Furthermore, according to the present invention, a silver halide photographic material can be obtained which can suppress the occurrence of fog, particularly during high-temperature rapid processing, and the extreme increase in sensitivity and change in gradation. In other words, according to the present invention, a silver halide photographic material that always provides stable photographic performance can be obtained.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, which comprises light-sensitive silver halide grains and an internal fog layer on the support. and a polyhydric alcohol having at least two hydroxyl groups with a melting point of 40°C or higher, the silver halide grains having internal fog are stabilized by a compound having a mercapto functional group. A silver halide photographic material characterized by the following.