JP2597440B2 - Silver halide photographic material - Google Patents

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 material, and more particularly, to a silver halide photographic material having high sensitivity and high contrast to high-intensity red light exposure, low fog, and excellent stability over time of an emulsion. It relates to a silver photographic light-sensitive material.

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2. Description of the Related Art With the development of rapid information transmission systems in recent years, silver halide photographic materials are required to have higher and higher sensitivity. For example, a high-speed photo-typesetting system that immediately displays information output from a computer as characters and graphics by a cathode ray tube,
Press facsimile for quickly sending newspaper manuscripts to remote locations.

[0003] As the characteristics required for the silver halide photographic light-sensitive material of such applications, a cathode ray tube (CRT), argon or helium - gas laser, such as neon, ^10-2 with a light source such as a light emitting diode (LED) ⁴ High sensitivity to so-called high-intensity short-time exposure of less than
Further, characteristics such as high contrast and high resolution are required. Among these light sources, the argon laser scanner method has been the mainstream in the past, but recently a more compact and inexpensive helium-neon laser or LED is used as the light source because of the large size and expensive equipment that can obtain high output. Have been marketed by various companies, and silver halide photographic materials having high sensitivity to such light sources have been desired.

It has been known to use trinuclear cyanine as a sensitizing dye for such a red light source. These have a spectral absorption maximum around 600 to 680 nm and are extremely effective for red sensitization for helium-neon lasers and LEDs. However, these generally tend to increase fog when added in large amounts. When an antifoggant is used to suppress fog, the developability is lowered, and the sensitivity is lowered due to desorption of a dye. If chemical sensitization is considered, the sensitivity becomes insufficient, and if the amount of the dye is further increased, the fog is further increased and the quality of the dye is deteriorated due to the deterioration of the residual color of the dye. For these reasons, there has been a demand for a light-sensitive material which has little residual color of the dye, low fog, high sensitivity even at high illuminance, and high sensitivity.

It is also known that a water-soluble rhodium compound may be added to prepare a high-contrast silver halide photographic emulsion. However, a silver halide added in combination with a sensitizing dye as described above is known. When coating the emulsion on a photographic support,
The sensitivity of the emulsion may change during the period from the completion of the emulsion to coating or during coating, and thus there has been a problem in the production stability of the emulsion and the quality stability of the photosensitive material.

[0006] The consumption of silver halide photographic light-sensitive materials is steadily increasing, and processing at high temperatures and short times is increasing in order to increase the processing amount. Therefore, there is an increasing demand for photosensitive materials that have high sensitivity and low fog even in high-temperature and short-time processing, and that provide stable photographic characteristics even when processing conditions are slightly changed. I have.

[0007] A silver iodobromide emulsion which has been subjected to gold plus sulfur sensitization in order to obtain a high sensitivity emulsion at high illuminance exposure is widely known, but a photosensitive material coated with such an emulsion is relatively halogenated. In the case of processing with a film material containing a large amount of silver, the development stability is often delayed due to short-time development, and the omission of fixation is often poor. Was.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high sensitivity, high fog, low fog, high contrast,
An object of the present invention is to provide a silver halide photographic light-sensitive material having excellent stability over time of an emulsion and good processing stability.

[0009]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion comprises 50 mol% or more of silver chloride, and the water-soluble rhodium compound is contained in 1 mol of silver. 5 × ^10-9 mol or more is added,
And at least one of sensitizing dyes represented by the general formula (Chemical Formula 2) is added, and the pH at the time of completion of the emulsion is 4.8 or less. Was done.

[0010]

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In the formula, L ₁ , L ₂ and L ₃ represent a methine group, and A represents NR ₄ , O or S. Z ₁ and Z ₂
May be the same or different and each represents a nonmetallic atomic group necessary to complete a thiazole nucleus, an oxazole nucleus or a selenazole nucleus. R ₁ , R ₂ and R ₃ each represent an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms substituted with an acid or an acid salt, and R ₄ represents an alkyl group having 1 to ₄ carbon atoms or Represents an alkyl group or an aryl group having 1 to 4 carbon atoms substituted with an acid or an acid salt (for example, a phenyl group or a naphthyl group). Specific examples of the sensitizing dye represented by Chemical Formula 2 are listed below, but the sensitizing dye used in the present invention is not limited thereto.

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These sensitizing dyes can be added to the silver halide emulsion as a solution of a single or mixed solvent such as methanol, ethanol, isopropanol, pyridine, dimethylformamide and water. It can also be added to the emulsion using ultrasonic dispersion.
Further, U.S. Pat. Nos. 3,482,981 and 3,5
No. 85,195, No. 3,469,987, No. 3,
Nos. 649,286, 3,485,634, 3,334,605 and 2,912,343 can also be used. These sensitizing dyes can be added to the silver halide photographic emulsion at any time during the emulsion production. The amount of addition depends on the type of sensitizing dye or the type of silver halide emulsion, but is usually 0.01 to 1 kg in terms of silver nitrate.
It can be used in the range of 10 to 10 g.

Examples of the water-soluble rhodium compound used in the present invention include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate and the like, and preferably a water-soluble trivalent rhodium compound. The amount of these water-soluble rhodium compound is per mol of silver halide 5.0 × 10 ^-9 mol or more, preferably 1 × 10 ^-6 mol 2 × 10 ^{over 8} mol. When the amount of these water-soluble rhodium compounds is small, the tone of the silver halide photographic light-sensitive material becomes soft and high contrast cannot be obtained. The water-soluble rhodium compound used in the present invention may be added during the physical ripening or the chemical ripening of the emulsion, but is preferably added during the physical ripening.

In the present invention, it is preferable to add an acid in order to make the pH of the emulsion 4.8 or less. The acid for adjusting the pH used in the present invention may be either an organic acid such as acetic acid, citric acid, phthalic acid or salicylic acid, or an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or perchloric acid.

The silver halide emulsion used in the present invention is:
Either silver chloride, silver chlorobromide or silver chloroiodobromide, of which 50 mol% of the halogen composition contains silver chloride grains. If the content of silver chloride is further reduced, the development progress and the fixing speed are delayed, which is not suitable for rapid processing. The higher the silver chloride content, the better, and preferably 70 mol% or more.

The silver halide emulsion of the present invention is chemically sensitized by sulfur plus gold sensitization. As the sulfur sensitizer used in the present invention, in addition to the sulfur compound contained in gelatin,
Various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used. The gold sensitizer used in the present invention is various gold salts, for example, chloroauric acid, trichloroauric acid, thiocyanatoauric acid and the like.

In the emulsion used in the present invention, a metal salt such as iridium can be used during physical ripening or chemical ripening of silver halide. The photographic emulsion used in the present invention can be sensitized using a quaternary ammonium salt, a thioether compound, a polyethylene oxide derivative, a diketone, or the like. These methods are described in U.S. Pat.
No. 708, 162, No. 3, 046, 132, No. 3, 0
No. 46, 133, No. 3, 046, 134, No. 3, 04
No. 6,135, British Patent No. 939, 357 and the like.

Various hydrophilic colloids are used in the photographic light-sensitive material of the present invention. Examples of the hydrophilic colloid used as a vector for a photographic emulsion and / or another photographic component layer include gelatin, colloidal albumin and casein. , Carboxymethylcellulose, cellulose derivatives such as hydroxyethylcellulose, sugar derivatives such as agar, sodium alginate and starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylamide or derivatives thereof, partial hydrolysates, etc. Is raised. If necessary, a compatible mixture of two or more of these colloids is used. Among these, gelatin is most commonly used, and gelatin can be partially or entirely replaced with a synthetic high-molecular substance. In addition, a so-called gelatin derivative, that is, an amino group as a functional group contained in a molecule, The imino, hydroxy, and carboxyl groups treated and modified with a reagent having one group capable of reacting with them may be used by replacing the graft polymer with the molecular chain of another polymer substance. .

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chloric acid (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-
Triacryloyl-hexahydro-S-triazine,
1,3-vinylsulfonyl-2-propanol, etc.),
Active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-S-triazine), mucohalic acids (e.g., mucochloric acid, mucophenoxycycloic acid), and the like can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a surfactant for various purposes such as a coating aid, antistatic, improvement of slipperiness, emulsification dispersion, and prevention of adhesion.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl alcohol ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glyoxide-lyl derivatives (eg, alkenyl succinic acid polyglycerides, alkylsoenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars , Nonionic surfactants such as, alkyl carboxylate, alkyl sulfonate, Le Kill benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfates, alkyl phosphate esters, N- acyl -
N-alkyltaurines, sulfosuccinates,
Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group, a phosphate group, such as sulfoalkyl polyoxyethylene alkyl phosphates: amino acids, aminoalkyl sulfonic acids, Aminoalkyl sulfates or phosphates,
Amphoteric surfactants such as alkyl betaines and amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and aliphatic or heterocyclic salts Cationic surfactants such as phosphonium or sulfonium salts can be used. Further, the physical properties of the gelatin film may be modified by adding a latex polymer or the like, or a mat may be formed by adding silica, starch powder, colloidal silica, glass powder, or the like.

The photographic emulsion layer or other hydrophilic colloid layer of the photographic material of the present invention is used for the purpose of preventing fogging during the production process of the photographic material, storage or photographic processing, or stabilizing photographic performance. And various compounds can be contained. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro-
Or a halogen-substituted compound): heterocyclic mercapto compounds, for example, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole),
Mercaptopyrimidines: the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group: thioketo compounds, for example, oxazolinethione:
Known as antifoggants or stabilizers such as azaindenes, for example, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes): benzenethiosulfonic acids: benzenesulfinic acid: and the like. Many compounds can be added.

The light-sensitive material of the present invention may contain various compounds other than those described above, for example, antistatic agents, antihalation dyes, plasticizers, developing agents, ultraviolet absorbers, fluorescent dyes, development accelerators, couplers and the like. it can.

In the photographic light-sensitive material of the present invention, all those usually used as a support for a photographic light-sensitive material can be used. For example, cellulose nitrate film,
Examples include a cellulose acetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, a laminate thereof, and paper. Baryta or α
Paper coated or laminated with an olefin polymer, especially a polymer of an α-olefin having 2 to 10 carbon atoms such as polyethylene and polypropylene, JP-B-47-1906
A support such as a plastic film or the like which improves the adhesion to other polymer substances by roughening the surface as shown in No. 8 is also suitable.

As the method for applying the hydrophilic colloid layer of the present invention, a method such as air doctor, blade coat, squeeze coat, air knife coat, reverse roll coat, cast coat, extrusion coat and the like are used. The coating amount is preferably 1 to 15 μm, more preferably 2 to 10 μm.

[0069]

【Example】

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples, and various applications can be made within the scope of the claims.

Example 1 Preparation of emulsion; an aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water at 40 ° C. and a pAg of 8.6 by a double jet method controlled at pAg 8.6; 3.25 × 10 ⁻⁶ mol) and a halogen solution containing potassium hexachlororhodate (the amount of addition was changed as shown in Tables 1 to 3 per mol of silver) to form a salt having an average particle size of 0.25 μm. A silver bromide (silver bromide 30 mol%) emulsion was prepared, and a potassium iodide (0.1 mol% with respect to silver) solution was added, and the precipitate was washed with water and dissolved again. The emulsion thus obtained was divided into 48 equal parts and subjected to sulfur + gold sensitization at 55 ° C. At this time, as shown in Table 1, 1.1.times.10.sup. ^-4 mol of the exemplified dye was added per 1 mol of silver halide, and after the dye was ripened, it was cooled to 40.degree. Thereafter, 1-phenyl-5-mercaptotetrazole, 2,4-dichloro-6-hydroxytriazine, a phenoxypolyethylene glycol-based surfactant, hydroquinone, and a water-soluble latex were added. These emulsions were adjusted to the pH shown in Table 1 to obtain finished emulsions. On a polyester film with these emulsion protective layer (gelatin 1.5g / m ^-2), silver 4.1 g / ^m-2 and so as to multilayer coating to prepare a sample. The aging of the emulsion was carried out at 37 ° C for 12 hours.
After keeping it warm for a time, it was applied in the same manner. The samples subjected to sensitometry exposure for 10 ^-4 seconds through 633nm interference filter, developed with PQ developer, fixing,
After washing with water and drying, the characteristics were determined. Table 1 shows the results. Sensitivity is determined by adding the emulsion without the water-soluble rhodium compound to pH.
The sensitivity at a density of 4.0 of each dye sample immediately after the completion of coating at 5.5 was taken as 100.

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[Table 1]

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[Table 2]

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As is clear from Tables 1 to 3, water-soluble rhodium
1 × 10 ^-8Mole or more,
Adjust the pH to 4.8 or less when the emulsion is completed and apply
High sensitivity, low fog, high contrast and stability over time
A good emulsion is obtained.

Example 2 Emulsions were prepared in the same manner as in Example 1 and the dyes shown in Tables 4 to 6 were added. A sample was prepared and processed in the same manner as in Example 1. For comparison, the sensitizing dye represented by Chemical Formula 46 was used. The results are shown in Tables 4 to 6. The sensitivity was set at 100 at the emulsion concentration of 4.0 immediately after the finished pH of each sample was 5.5 as in Table 1.

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[Table 4]

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[Table 5]

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[Table 6]

As is clear from Tables 4 to 6, a water-soluble rhodium compound was added using the present sensitizing dye, and the pH at the time when the emulsion was completed was adjusted to 4.8 or less. An emulsion having low contrast and good stability over time can be obtained.

[0082]

As will be understood from the examples, a silver halide photographic material having a high sensitivity and a high contrast with respect to a high illuminance light source of red light and a good stability of the emulsion over time can be obtained.

Continuation of the front page (56) References JP-A-63-115159 (JP, A) JP-A-62-215272 (JP, A) JP-A-62-242932 (JP, A) JP-A-62-265647 (JP) , A) JP-B-49-13331 (JP, B2) JP-B 52-25331 (JP, B2)

Claims (1)

(57) [Claims] 1. A water-soluble rhodium compound in a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein said silver halide emulsion comprises at least 50 mol% of silver chloride. Is added in an amount of 5 × 10 ⁻⁹ mol or more per mol of silver, and at least one of the sensitizing dyes represented by the general formula (1) is added.
A silver halide photographic light-sensitive material, wherein H is 4.8 or less. Embedded image In the formula, L ₁ , L ₂ and L ₃ represent a methine group, and A represents N-
Represents R ₄ , O or S. Z ₁ and Z ₂ may be the same or different and each represents a non-metallic atomic group necessary for completing a thiazole nucleus, an oxazole nucleus or a selenazole nucleus. R ₁ , R ₂ and R ₃ each have 1 to 1 carbon atoms
4 represents an alkyl group having 1 to 4 carbon atoms substituted by an alkyl group or an acid or an acid salt, and R ₄ represents an alkyl group having 1 to 4 carbon atoms or a carbon atom having 1 to 4 carbon atoms substituted by an acid or an acid salt.
4 represents an alkyl group or an aryl group.