JPH0331246B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide photographic material with particularly improved image quality. Prior Art Recently, regarding silver halide photographic materials,
Requirements are becoming increasingly complex and diverse, and in particular, there is a demand for photographic materials with stable photographic performance, high sensitivity, low fog, and high image quality. In particular, in the case of X-ray photosensitive materials, etc., in order to reduce the amount of X-rays the human body is exposed to, high sensitivity, which allows more information to be obtained with a smaller amount of
There is a need for photographic materials that have high image quality and are suitable for rapid development processing that allows information to be obtained quickly. Conventionally, as a method for increasing the sensitivity of a silver halide photographic light-sensitive material, for example, a method of incorporating a compound called a sensitizer into the silver halide photographic light-sensitive material is known. For example, US Pat.
JP-A-11116, JP-A-54-155828, etc. disclose techniques for increasing sensitivity by incorporating an organic thioale compound into a silver halide photosensitive material. Other methods for increasing sensitivity include increasing the grain size of silver halide or adding a sensitizer or accelerator to the processing solution to increase the development effect and improve silver halide photography. It is known to increase the sensitivity of photosensitive materials. Furthermore, for rapid development processing of silver halide photographic light-sensitive materials, the amount of gelatin (binder) relative to silver halide in the silver halide photographic light-sensitive material may be reduced, or the developing processing solution may be treated with a high pH value.
Moreover, it is known that the development process is carried out at a high temperature of 30 to 40°C. On the other hand, it is known that the above-described methods of increasing the sensitivity of silver halide photographic materials and methods of adapting them to rapid development processing achieve their objectives, but on the other hand, they significantly deteriorate the quality of photographic images. Many reports have been made regarding methods for compensating for deterioration in the image quality (hereinafter simply referred to as image quality) of photographic images of silver halide photographic materials. For example, a method is known in which a compound called an antifoggant or a stabilizer is contained in a silver halide emulsion to suppress deterioration in image quality due to coarsening of developed silver grains. Furthermore, as a method for maintaining the physical properties of a film supporting developed silver particles and maintaining image quality, it is known to harden gelatin (binder) of a photographic light-sensitive material using a hardening agent. For example, inorganic compounds such as chromium alum, aldehyde compounds such as formaldehyde and glutaraldehyde, compounds containing active halogens such as those described in U.S. Pat. No. 3,288,755, and U.S. Pat.
Compounds with reactive ethylenically unsaturated bonds as described in U.S. Pat. No. 3,091,537, epoxy compounds as described in U.S. Pat. A method is known in which a compound is incorporated into a silver halide emulsion layer, a protective layer, etc. to harden gelatin (binder) so that it can withstand harsh processing conditions such as high-temperature rapid processing. However, at present, none of these methods has been able to sufficiently improve the image quality without impairing the photographic performance (eg, sensitivity, contrast, maximum density, etc.) of silver halide photographic materials. Therefore, silver halide photographic materials with high image quality can be obtained by using a sensitizer in the silver halide emulsion, by reducing the amount of gelatin (binder) relative to silver halide, or by performing high-temperature rapid development processing. There is a strong demand for the emergence of a technology that can obtain this. OBJECTS OF THE INVENTION The first object of the present invention is to provide a silver halide photographic material that exhibits high sensitivity and excellent image quality even when the amount of gelatin binder in the silver halide emulsion layer is reduced. A second object of the present invention is to provide a silver halide photographic material capable of producing high-quality images even when rapid development is performed under conditions of high pH and temperature. Structure of the Invention As a result of various studies to address the above-mentioned problems, the present inventors have discovered that at least one compound containing at least one compound represented by the following general formula () on a support
It has been found that the above object can be achieved with a silver halide photographic material having two photographic constituent layers. General formula () In the formula, A represents a carbonyl group or a sulfonyl group, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₂ and R ₃ each represent a hydrogen atom, a hydroxyl group, an alkyl group, -SO ₃ M (Here, M is 1
represents a valent cation), or -COOR ₄ (where R ₄ represents a monovalent cation, an aliphatic group, or an aromatic group), provided that at least one of R ₂ and R ₃ is R Represents _-COOR4 , where ₄ is a monovalent cation excluding a hydrogen atom, or an aliphatic group or an aromatic group. n represents an integer from 0 to 2. That is, according to the present invention, it has been found that the object of the present invention can be achieved by incorporating a thioether compound represented by the general formula () into at least one of the photographic constituent layers of a silver halide photographic light-sensitive material. Ta. The present invention will be explained in more detail below. In the present invention, the compound according to the present invention contained in the photographic constituent layer is a compound represented by the above general formula (), and in the general formula (),
The aliphatic group represented by R ₁ and R ₄ includes an alkyl group having 1 to 18 carbon atoms (for example, a methyl group,
n-butyl group, i-propyl group, t-butyl group,
n-dodecyl group, etc.), alkenyl groups having 2 to 18 carbon atoms (e.g. allyl group, butynyl group, octenyl group, etc.), cycloalkyl groups having 3 to 8 carbon atoms (e.g. cyclobentyl group, cyclohexyl group, etc.)
etc. These aliphatic groups may have one or more substituents, and examples of these substituents include alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.), aryl groups (e.g., phenyl groups,
tolyl group, etc.), aryloxy group (e.g., phenoxy group, etc.), amino group, dialkylamino group (e.g., dimethylamino group, diethylamino group, etc.),
Heterocyclic groups (e.g. N-morpholino group, N-piperidino group, etc.), halogen atoms (e.g. chlorine atom,
(bromine atom, iodine atom, etc.), nitro group, hydroxyl group, carboxyl group, sulfo group, alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.). Further, as the aromatic group represented by R ₁ and R ₄ , phenyl group and naphthyl group are preferable, and these aromatic groups may have one or more substituents, and these substituents include: For example, alkyl groups (e.g. methyl group, ethyl group, etc.), alkoxy groups (methoxy group, ethoxy group, etc.), hydroxyl group,
Halogen atoms (e.g. chlorine atom, bromine atom, iodine atom, etc.), acylamino groups (acetylamino group,
(benzoylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), succinimide group, carbamoyl group, nitro group, etc. In addition, the heterocyclic group represented by R ₁ is:
Preferred examples include 5- or 6-membered heterocyclic groups having at least one of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyrrolyl group, pyridinyl group, pyridyl group, thiazolyl group, morpholino group, furanyl group, etc.). . This heterocyclic group may have a substituent, and these substituents can be arbitrarily selected from among the substituents listed as substituents for the aliphatic group and aromatic group. Also, M of the -SO ₃ M group represented by R ₂ and R ₃
Examples of the monovalent cation represented by and the monovalent cation represented by R ₄ include hydrogen ions, alkali metal ions (eg, sodium ions, potassium ions), ammonium ions, and the like. Among the compounds represented by the general formula (), particularly preferred are compounds in which R ₁ is an alkyl group having 1 to 8 carbon atoms, R ₂ and R ₃ are
One of them is a carboxyl group and the other is R ₄
is the case where the aliphatic group is _-COOR4 , which is an aromatic group, and compounds in which A is a carbonyl group are preferred. Typical specific examples of the compound represented by the general formula () according to the present invention are listed below, but the present invention is not limited thereto. The compound represented by the general formula () used in the present invention is, for example, Chemical Abstracts, Vol. 35, p. 2114 (1941
), Journal of the Chemical Society 1951
It can be synthesized by the method described in 1999, pp. 2123-2125. The compound represented by the general formula () used in the present invention has the disadvantage that organic thioether compounds known as conventional sensitizers can increase photographic sensitivity, but deteriorate other photographic properties. However, it has excellent photographic performance, not only increasing sensitivity but also suppressing the occurrence of fog and preventing and improving image quality. Next, a silver halide photographic light-sensitive material having a photographic constituent layer on a support, which is used in the present invention and contains a compound represented by the general formula (), will be described in detail. In the present invention, the photographic constituent layers refer to a photosensitive silver halide emulsion layer provided on a support and auxiliary layers (e.g., protective layer, intermediate layer, undercoat layer, etc.) provided on the same side of the emulsion layer and the support. layer, antihalation layer, etc.), and the silver halide photosensitive material according to the present invention contains a compound represented by the general formula () of the present invention in at least one of these layers. The amount of the compound used in the present invention contained in the above photographic constituent layer is per mole of silver halide.
A range of 0.1 mg to 1000 mg is preferred. It is preferably used in an amount of 1 mg to 100 mg and usually dissolved in a solvent such as methanol or fluorine-containing alcohol to a concentration of 0.1 to 1%. The addition time can be determined at any step before the coating and drying steps in the manufacturing process of the photographic light-sensitive material. Further, the constituent layer containing the compound is particularly preferably a silver halide emulsion layer. Silver halides that can be applied to the silver halide photographic emulsion according to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide, and mixtures thereof. Silver iodobromide is most preferred. Gelatin is most desirable as the binder or hydrophilic colloid used in the present invention, but derivative gelatin, colloidal alpmin, agar, gum arabic, alginic acid, cellulose derivatives, acrylamide, imidized polyacrylamide, casein, vinyl It can be used in combination with polymers such as alcohol polymers, polyvinyl alcohol, polyvinylpyrrolidone, and hydrolyzed polyvinyl acetate. The silver halide photographic emulsion used in the present invention includes various known chemical sensitizers, spectral sensitizers, antifoggants, contrast enhancers, gelatin hardeners, surfactants, film property improvers, and thickeners. , a dot improver, and other additives. Examples of the various additives include chemical sensitizers such as active gelatin, water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts, and other noble metal sensitizers. Chemical sensitization can be carried out using a chemical sensitizer such as a sulfur sensitizer, a selenium sensitizer, a polyamine, a reduction sensitizer such as stannous chloride, etc. alone or in combination. There are no particular restrictions on the spectral sensitizer; for example, spectral sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or merocyanine dyes may be used alone or in combination to optically sensitize. can. These techniques are described in U.S. Patent No. 2,688,545;
Same No. 2912329, Same No. 3397060, Same No. 3615635,
British Patent No. 3628964, British Patent No. 1195302, British Patent No. 1242588, British Patent No. 1293862, West German Patent (OLS) No. 2030326, British Patent No. 2121780, Japanese Patent Publication No. 43-4936, British Patent No. 44 -It is also described in Publication No. 14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material. The silver halide photographic emulsion used in the present invention is
Other additives may be included. For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds, aldehydes, aziridines, isoxazoles, vinylsulfones, acryloyls, carbodiimides, and maleimides. Hardeners such as methane sulfonate, triazine, etc., development accelerators such as benzyl alcohol and polyoxyethylene compounds, image stabilizers such as chroman, bisphenol, and phosphite esters, waxes, and high-grade There are lubricants such as glycerides of fatty acids and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds.
Examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether maleic acid copolymer. The silver halide photographic light-sensitive material of the present invention is produced by applying a silver halide photographic emulsion to baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, etc. , polyvinyl acetal, polypropylene, a polyester film such as polyethylene terephthalate, or a support such as polystyrene by a known method. The silver halide photographic light-sensitive material of the present invention can be provided by laminating silver halide emulsion layers having different color sensitivities, like ordinary color light-sensitive materials. The above-mentioned silver halide emulsion layers having different color sensitivities can contain photographic couplers corresponding to the respective color sensitivities. That is, the blue-sensitive silver halide emulsion layer contains a yellow coupler, the green-sensitive silver halide emulsion layer contains a magenter coupler, and the red-sensitive silver halide emulsion layer contains a cyan coupler. Furthermore, the combination of each color-sensitive layer and coupler can be changed as desired. Known 2-equivalent and 4-equivalent couplers can be used in the silver halide photographic material of the present invention. As the yellow coupler, open-chain ketomethylene couplers can be used, among which benzoylacetanilide type and bivaloylacetanilide type yellow couplers are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 3265506, No. 3277155, No. 3408194, No. 3415652, No. 3447928, No. 3664841,
Special Publication No. 13576, No. 48-29432, No. 48-
No. 66834, No. 49-10736, No. 49-122335, No. 50
-28834, 50-132926, patent application 1984-145024
It is written in the number etc. As the magenta coupler, compounds such as pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, isodazolone type, and cyanoacetyl type are used. Specific examples of magenta couplers that can be used are U.S. Pat. Nos. 2,600,788 and 3,061,432.
No. 3062653, No. 3127269, No. 3127269, No. 3062653, No. 3127269, No.
3311476, 3419391, 3519429, 3558319, 3684514, 3886680,
British Patent No. 1247493, British Patent No. 1534349, West German Patent Application (OLS) No. 2156111, Belgian Patent No. 769116
No. 792525, Special Publication No. 46-60479, Japanese Patent Publication No.
No. 49-29639, No. 49-111631, No. 49-129538,
No. 50-13041, No. 50-122935, No. 51-20826
No. 52-58533, No. 52-80027, Patent Application No. 1987-
It is described in No. 98876, No. 52-101247, No. 52-104437, etc. In addition to the above, other types of couplers such as colored couplers, competing couplers, etc. can also be used. The silver halide photographic material of the present invention may be either a black-and-white photographic material or a color photographic material, and can be used for various purposes such as general use, printing, X-ray use, and radiation use. It exhibits remarkable effects as a sensitive silver iodobromide photographic material. The silver halide photographic light-sensitive material of the present invention may be exposed to short-time or flash light in addition to normal exposure, and can be photographically processed by conventional methods. The basic photographic processing steps are a developing step and a fixing step, and these two steps may be performed simultaneously. The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example-1 Silver iodobromide (3.0
100g of silver iodide (containing mol% silver iodide), 40g of gelatin
After saponin is added as a coating aid to a high-speed negative emulsion containing sulfur-sensitized and gold-sensitized
It was divided into 15 pieces, the compounds shown in Table 1 were added in the amounts shown in the table, and the mixture was coated on a polyethylene terephthalate film base. Further, a gelatin solution containing a coating aid and a hardening agent was coated as a protective layer on this silver halide emulsion layer to a thickness of 1.5 gr/m ² and dried. The sample obtained in this way
Based on the JIS method, a continuous conveyance type automatic developing machine that can perform white exposure using a KS-1 type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.), then developing, fixing, washing, and drying in an integrated manner. Processed.
The liquids used are as follows. Developer formulation (Development time: 35℃, 30 seconds) Anhydrous sodium sulfite 70g Hydroquinone 10g Boric anhydride 1g Sodium carbonate (monohydrate) 20g 1-phenyl-1,3-pyrazolidone 0.35g Sodium hydroxide 5g 5-methylbenztriazole 0.05g Potassium bromide 5g Glytaraldehyde bisulfite 15g Glacial acetic acid 8g Add water to make 1. Sensimetry was performed on each sample thus obtained, and the photographic characteristics obtained are shown in Table 1. Note that the sensitivity shown in the table is a relative sensitivity value with the sensitivity of the comparative sample (sample number -1) set as 100. Further, the image quality shown in Table 1 is determined by visual judgment of the degree of roughness of developed silver particles at a density of 0.8. In addition, 〇 indicates good condition, △ indicates normal condition, and × indicates that the condition is so bad that it cannot be used.
Those marked with two symbols indicate the interim evaluation of each symbol.

【table】 / \
H ₂ C CH ₂
(Hardening agent)

[Table] As is clear from Table 1, all the samples according to the present invention (sample numbers 2 to 11) were at a temperature of 23°C and a relative humidity of
It was found that image quality could be improved without adversely affecting photographic performance, such as sensitivity, maximum density, fog, etc., even if left for 10 days under conditions of 65% RH. Example 2 On a triacetate film base having an antihalation layer, the first layer contains 10 g of coloring agent 4-chloro-1-hydroxy-2-n-octylnaphthamide per 1 kg of negative-working silver halide emulsion, and a red color is formed. A highly sensitive silver iodobromide emulsion layer for color photography, which is color-sensitized to light, is provided to a dry film thickness of 5 μm, and a 3% aqueous gelatin solution is applied as a second layer on top of this layer to a dry film thickness of 5 μm. It was applied to a thickness of 1μ. Next, as the third layer, 1 kg of negative silver halide emulsion
1-(3-carboxyphenyl)-3-(4-stearoylaminophenyl) as a color former
- A highly sensitive silver iodobromide emulsion layer for color photography containing 10 g of 5-pyrazolone and color-sensitized to green light was provided to a dry film thickness of 4 μm, and a fourth layer was formed on this layer. A yellow colloidal silver layer was applied as a layer so that the dry film thickness was 2 μm. Next, as the fifth layer, a high-sensitivity silver iodobromide emulsion layer containing 13 g of 2-dodecyloxybenzoylacetanilide as a coloring agent per 1 kg of negative-working silver halide emulsion and having color sensitization to blue light is dried. The film thickness was set to 7μ. On top of this layer, a 6th layer of 4%
An aqueous gelatin solution was applied to give a dry film thickness of 1 μm. In this manner, a sample of a multilayer internal color photographic negative film was prepared. Formalin was added as a hardening agent to the second, fourth and sixth layers of this sample per gram of gelatin.
mg each was added. Furthermore, the silver halide emulsion layers of the first, third and fifth layers contain 4-hydroxy-6-methyl-
Adding 1,3,3,a7-tetrazaindene,
Also, after adding saponin as a coating aid, the second
The compounds shown in the table were added. The sample thus obtained was stored in an atmosphere of 25° C. and 60% relative humidity for 30 days. Next, each of these samples and a comparative sample were processed with a color developer having the following formulation, and the color density was measured using a color densitometer. The photographic performance obtained from these measured values is shown in Table 2. However, R shown in the table,
G and B are obtained from the values measured through red, green, and blue color photographic densitometer filters, respectively, and the sensitivity is the red sensitivity of sample 16.
Shown as a relative value when set to 100. Color developer formulation (24℃, 5 minutes development) Benzyl alcohol 3.8ml Anhydrous sodium sulfite 2.0g N-ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 5.0g Sodium carbonate 5.0g Sodium bromide 5.0g Add water to make 1.

[Table] From the table above, the samples according to the present invention (sample numbers 17 and 18) in which the compound according to the present invention was contained in a multilayer color light-sensitive material had a photographic It was also found that the image quality could be improved without deteriorating the characteristics. Effects of the Invention The silver halide photographic light-sensitive material containing the thioether compound according to the present invention in its photographic constituent layer has the following properties:
Image quality can be improved without adversely affecting photographic characteristics.

Claims (1)

[Claims] 1. At least one compound containing at least one compound represented by the following general formula () on a support.
1. A silver halide photographic material comprising two photographic constituent layers. General formula () [In the formula, A represents a carbonyl group or a sulfonyl group, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₂ and R ₃ each represent a hydrogen atom, a hydroxyl group, an alkyl group, -SO ₃ M (here M is 1
represents a valent cation), or -COOR ₄ (where R ₄ represents a monovalent cation, aliphatic group, or aromatic group), provided that at least one of R ₂ and R ₃ is R ₄ is a monovalent cation excluding a hydrogen atom, or represents _-COOR4 , which is an aliphatic group or an aromatic group. n represents an integer from 0 to 2].