JPS62265659A - Spectrally sensitized silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material ensuring high photosensitivity and contrast and causing little dye stain by using silver halide particles formed by a prescribed method in hydrophilic colloidal layers including a silver halide emulsion layer formed on a support and by spectrally sensitizing the silver halide particles with a specified compound. CONSTITUTION:Silver halide particles formed in the presence of a water soluble Rh salt and/or a water soluble Ir salt added by 1X10<-8>-5X10<-6>mol per 1mol silver halide are used in hydrophilic colloidal layers including a silver halide emulsion layer formed on a support, and the silver halide particles are spectrally sensitized with a compound represented by the formula. In the formula, Z is a group of nonmetallic atoms required to form an oxazole, benzoxazole or naphthoxazole ring, R<1> is alkyl, R<2> is a prescribed group such as alkoxycarbonylalkyl and each of R<3> and R<4> is H, Cl, F, alkyl, alkoxy, alkylsulfonyl or carboxy.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material spectrally sensitized with a novel merocyanine dye, and in particular has high green light sensitivity and high contrast halftone images. The present invention relates to a silver halide photographic light-sensitive material which can be obtained even in relatively rapid development and has extremely little dye staining after processing.

[Conventional technology]

It is known that photographic images with extremely high contrast can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is about 0.5μ
Silver halide consisting of a silver chlorobromide or silver chloroiodide emulsion with fine grains of m or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 mol% or more. A method is known in which a high-contrast halftone dot image or line image is obtained by processing a photosensitive material with an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions.

This type of silver halide light-sensitive material is known as a lithium-type silver halide photographic light-sensitive material, and normally during the photolithography process, changes in the continuous tone density of an original are recorded in a large and small area proportional to this density. It is used to convert to a set of halftone dots with . Such conversion involves using a lithium-type silver halide photographic light-sensitive material, photographing the original through a cross-line screen or a contact screen, and then using a so-called lithium-ion silver halide photographic material, which has a very low sulfite ion concentration and contains only a hydroquinone developing agent. A halftone image is formed by developing with a Lith type developer. Even when this lithium-type silver halide photographic light-sensitive material is processed with a normal developer with a high sulfite ion concentration, such as a commercially available developer for photographic paper, the gamma is only 5 to 6, which is the most Since there are many fringes that must be avoided, it is said that combination with the above-mentioned lithium type developer is essential for halftone negative/positive printing. Regarding this lithium type developer, please refer to J.A. CYUL's Journal of the Franklin Institute.
e: J, Franklin Institute
), Vol. 239, p. 221 (1945), which essentially contains only hydroquinone as a developing agent, and the concentration of sulfite ion, which acts as an antioxidant for the developing agent, is It is a low developer.

Such developers have poor shelf life (they are susceptible to auto-oxidation), so in order for platemakers to consistently obtain high-quality halftone negative or halftone positive images, they must maintain the developer's activity, which decreases over time. Although it is necessary to manage the developer to keep the strength constant, it is unavoidable that the operation becomes complicated.

Furthermore, in the lithographic development process, there are two major disadvantages: in addition to the above-mentioned developer management that keeps the activity constant, the processing speed is slow.

The trend in printing plate making in recent years has been to shorten the printing process and shorten the time, and there is an increasing demand for processing speed of plate making film.

For example, Japanese Patent Application No. 59-240147 uses a silver halide photographic light-sensitive material containing a tetrazolium salt as a technique for obtaining an extremely high contrast image suitable for plate making using a developer with high stability. A method is disclosed. This method allows the use of a stable developer with a high concentration of sulfite ions, and enables rapid processing with a development time of around 30 seconds and a drying time of 90 to 100 seconds, which was not possible with conventional lithography. be.

On the other hand, silver halide photographic materials for use in plate making are generally required to have so-called orthotype photosensitivity, which is photosensitivity in the green area.

Since a photosensitive silver halide emulsion alone has a narrow wavelength range of sensitivity, a spectral sensitizer is used for the purpose of expanding the wavelength range of sensitivity to longer wavelengths. For example, as a device that imparts sensitivity to green light,
No. 28, No. 40-392, No. 43-10251, No. 43-22884, British Patent No. 815.172, No. 9
No. 55.961, No. 955,912, No. 142,22
No. 8, U.S. Patent No. 1,942.854, U.S. Patent No. 1,950,
No. 876, No. 1,957,869, No. 2,238,2
No. 31, No. 2,521.705, No. 2,647.05
No. 9, Special Publication No. 43-2606, No. 44-3644,
No. 46-18106, No. 46-18108, No. 48
-15032, 49-33782, 54-34
No. 252, No. 58-52574, U.S. Patent No. 2.839
．． No. 403, No. 3,567.458, No. 3,625,
Examples include cyanine dyes and merocyanine dyes described in specifications such as No. 698.

[Problem that the invention seeks to solve]

These spectral enhancers not only increase the sensitivity in a specific wavelength region, but also have the following characteristics: (b) No change in photographic characteristics such as a decrease in sensitivity or an increase in capri even after the passage of time; (C)
Properties such as not causing dye staining after processing are required, but when the above-mentioned relatively rapid development is performed, the dye staining after processing becomes thicker, which is a big problem in practice.

In order to reduce dye staining, it is necessary to use a material that has little staining property against hydrophilic colloids such as gelatin, and which easily flows out into the processing solution.
A highly soluble spectral enhancer may be used, and various compounds have been proposed in the past.

However, in many cases, spectral sensitizers have a large effect on the development effect that provides the extremely high contrast required for plate making, resulting in problems such as a decrease in contrast. It was difficult to directly apply the solution to silver halide photographic materials that undergo high contrast development.

The purpose of the present invention is to solve the above-mentioned problems, to obtain extremely high contrast through rapid processing using a normal developing solution with high photosensitivity and high sulfite ion concentration, and to provide high contrast after processing. An object of the present invention is to provide a silver halide photographic material with extremely little dye staining.

[Means for solving problems]

As a result of various studies, the present inventors have developed a silver halide photographic material having a support and a hydrophilic colloid layer coated on the support, including at least one silver halide emulsion layer. The silver halide grains contained in the colloid layer are spectrally sensitized by a compound represented by the following general formula (1), and the silver halide grains contained in the silver halide emulsion layer are 1xlO- per mole of silver halide. a
It has been found that the above object can be achieved by a silver halide photographic material formed in the presence of ~5 x 10-h moles of water-soluble rhodium salt and/or iridium salt.

j(,:” Below is the general formula ([) Z represents the atomic group necessary to complete the oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus, and these nuclei have substituents on the carbon atoms. Specific examples of substituents include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), unsubstituted alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group,
butyl group, hexyl group, etc.), alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, propoxy group, butoxy group), hydroxy group, alkoxycarbonyl groups having 2 to 6 carbon atoms (e.g. methoxycarbonyl group, ethoxy carbonyl group, etc.), an alkylcarbonyloxy group having 2 to 5 carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), phenyl group, hydroxyphenyl group, and the like.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4.5-dimethyloxazole, 4-phenyloxazole, etc. as the oxazole nucleus; benzoxazole, 5-chlorobenzoxazole, etc. as the benzoxazole nucleus; 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6- Nut (1,2-
d) Nuclei such as oxazole, naphtho(2,1-d)oxazole, and naphtho(2,3-d)oxazole can be mentioned.

R1 represents an unsubstituted or substituted alkyl group.

Examples of substituents include hydroxy group, sulfo group, sulfonate group, carboxy group, halogen atom (e.g. fluorine atom, chlorine atom), unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (alkoxy group may further include sulfo group, may be substituted with a hydroxy group), an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a sulfamoyl group, an unsubstituted or substituted carbamoyl group (an alkyl group having 1 to 4 carbon atoms) (including substituted carbamoyl groups), substituted phenyl groups (examples of substituents include sulfo groups, carboxy groups, hydroxy groups, etc.), vinyl groups, and the like.

Specific examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of substituted alkyl groups include 2-hydroxyethyl and 3-hydroxypropyl groups as hydroxyalkyl groups, and 2-sulfoethyl and 3-hydroxypropyl groups as sulfoalkyl groups.
-Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2
-chloro-3-sulfopropyl group, carboxyalkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, 2,2.2-trifluoroethyl group, 2-(3-sulfopropyloxy)ethyl group, 2-(2-hydroxyethoxy)ethyl group, ethoxycarbonylethyl group, methylsulfonylethyl group, 2-sulfamoylethyl group, 2-carbamoylethyl group as sulfamoylalkyl group! , 2-N,N-dimethylcarbamoylethyl group, etc., phenethyl group, p-carboxyphenethyl group, p-sulfophenethyl group, O-sulfophenethyl group, etc. as sulfoaralkyl group, p-
Examples include hydroxyphenethyl group, allyl group, phenoxyethyl group, and the like.

R2 is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl group, or a substituent + CH2-hA or (÷2)1 combination (
Represents Mohha←. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or an alkoxy group having 1 to 8 carbon atoms, and n represents an integer value of 1 to 4.

Each of the above groups includes those having a substituent. For example, those in which the alkyl moiety of the above group is substituted with a halogen atom can also be preferably used. Examples of R2 include alkoxycarbonylalkyl groups in which each alkyl group is substituted with a halogen atom (e.g., methoxycarbonylfluoromethyl group, ethoxycarbonylfluoromethyl group, fluoroethoxycarbonylethyl group, etc.), hydroxyalkyl groups (e.g., 2-hydroxy Fluoroethyl group, 2-
hydroxyfluoropropyl group, 3-hydroxyfluoropropyl group, 2,3-dihydroxyfluoropropyl group, etc.), hydroxyalkoxyalkyl group (e.g. hydroxymethoxyfluoromethyl group, 2-(2-hydroxyfluoroethoxy)ethyl group, 2-hydroxy fluoroethoxymethyl group, etc.), carbamoyl alkyl group (
N-alkyl-substituted, N,N-dialkyl-substituted, N-hydroxyalkyl-substituted, N-alkyl-N-hydroxyalkyl-substituted, N,N-di(hydroxyalkyl)-substituted carbamoyl alkyl groups and 5- and 6-membered ring carbamoylalkyl groups of cyclic amines) (e.g. 2-carbamoylchloroethyl group, 2-N-(2-hydroxyethyl)carbamoylchloroethyl group, N-hydroxyfluoroethylcarbamoylmethyl group, N-N-di(2-
hydroxyfluoroethyl)carbamoylmethyl group, 2
-N,N-di(2-hydroxyethyl)carbamoylchloroethyl group, N,N-dimethylcarbamoylchloromethyl group, cerphorinocarbamoylchloromethyl group, piperidinocarbamoylmethyl group, etc.), hydroxyphenyl group, number of carbon atoms 7 to 9 hydroxyalkylphenyl groups (e.g. p-(2-hydroxyfluoroethyl)phenyl 5
, m-(1-hydroxyfluoroethyl)phenyl group, etc.), or substituent +CHz7A or +cu
t +TO+ C) represents II-hA. Here A
represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or a lower alkoxy group, and among these, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (for example, a methylsulfonyl group, ethylsulfonyl group, etc.),
The sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms (e.g., N-methylsulfonamide group, N-methylsulfonamide group,
, N-dimethylsulfonamide group, etc.), the alkylsulfonylamino group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms (for example, a methylsulfonylamino group, etc.), and the lower alkoxy group is preferably a carbon number Number 1 to 4 alkoxy groups (e.g. methoxy group,
ethoxy group, etc.).

n represents an integer value of 1-4.

R3 and R4 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably one with 1 to 4 carbon atoms, such as a methyl group or an ethyl group), or an alkoxy group (preferably one with 1 to 4 carbon atoms). , for example, a methoxy group, an ethoxy group), an alkylsulfonic acid group, a sulfonic acid group, a chlorine atom, a fluorine atom, or a carboxy group.

Particularly preferred compounds of the above general formula (1) are those in which R1 represents a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a sulfo group or a carboxyl group and/or a hydroxyl group. Yes, specifically sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3-sulfo-2
-Hydroxypropyl group, etc.

Next, typical examples of the compound represented by the above general formula [1] used in the present invention will be given, but it goes without saying that the compounds used in the present invention are not limited to these.

CI) -2 N) -6 (1)-70CHCoCI,S03K C)Ia (+)-24 (1] -25 CI)-31 [■]-34 (Ri-36 The above used in the present invention The compound represented by general formula (1) is disclosed in Japanese Patent Publication No. 46-549, No. 46-18105
No. 46-18106, No. 46-18108, No. 47-4085, No. 5B-52574, U.S. Patent 2
, No. 839,403, No. 3,384,486, No. 3,
No. 625,698, No. 3.480.439, No. 3,
567.

It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 458 and the like.

The merocyanine dye represented by the general formula (1) used in the present invention can be added and dispersed in a silver halide emulsion by various methods, such as conventionally known methods. For example, the method of adding by dispersing with a surfactant described in the specifications of JP-B No. 49-44895 and JP-A-50-11419;
No. 24, No. 53-102732, No. 53-10273
No. 3, U.S. Patent No. 3,469,987, U.S. Patent No. 3,676
．． Examples include the method of adding as a dispersion with a hydrophilic substrate as described in the specification of No. 147, and the method of adding as a solid solution as described in the specification of East German Patent No. 143,324. In addition, the merocyanine dye may be dissolved in a water-soluble solvent such as water, ethanol, methanol, acetone, n-propanol, fluorinated alcohol, pyridine, etc. alone or in a mixture thereof and added to the emulsion. It may be added at any time during the emulsion manufacturing process, but preferably during or after chemical ripening. The amount of the merocyanine dye used in the present invention is the amount for spectral sensitization of the silver halide emulsion, for example, 10-5 to 1 mole of S halide.
2×10−2 mol, preferably lXl0−′ to 2×10
−'Mole.

The water-soluble rhodium salt used in the present invention includes:
Examples include rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc., but preferred are trivalent rhodium halogen complex compounds, such as hexachlororhodium(III) Mt+L<, its salts, and rhodium trichloride trihydrate.

The water-soluble iridium salt used in the present invention includes trivalent and tetravalent iridium salts, and preferably includes a halogen complex compound of tetravalent iridium, such as potassium hexachloroiridate (IV).

The amount of water-soluble rhodium salt and iridium salt added in the present invention is 1X10-8 to 5X1 per mole of silver halide.
If the water-soluble rhodium and iridium salts are less than 1X10-'' moles, one of the objectives of the present invention will not be sufficient.

On the other hand, if the amount is more than 5 x 10-'' moles, as is well known to those skilled in the art, the desensitizing effect of water-soluble rhodium salts and iridium salts on silver halide increases, making it difficult to obtain the desired sensitivity. become.

In the present invention, water-soluble rhodium salts and iridium salts are present during the formation of silver halide grains, but the time of formation here refers to the process of emulsification and physical ripening of silver halide, and the water-soluble rhodium salt and iridium salt are present at any time during this process. It can be added using the following method. A preferred addition time is during emulsification, and a more preferred method is to add a water-soluble rhodium salt and/or iridium salt to the halide solution. The distribution of rhodium ions and iridium ions in the silver halide emulsion is preferably uniform for each silver halide grain, and there are no particular restrictions on the distribution within one grain, and the distribution on the grain surface and inside the grain is Even if it is uniform, the distribution may be biased toward the surface or inside.

In the silver halide photographic light-sensitive material of the present invention, a hydrophilic colloid layer containing at least one silver halide emulsion layer is coated on a support and a core support, and this silver halide emulsion is directly coated on the support. Alternatively, it may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer may be further coated as a protective layer on the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, eg high and low sensitivity. In this case, the silver halide emulsion layer may have an intermediate layer of a hydrophilic colloid layer between these layers, or an intermediate layer between the silver halide emulsion layer and the protective layer. Good too.

The layer containing the compound of general formula (1) of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

In order to incorporate the compound of general formula (1) of the present invention into the silver halide emulsion layer, there is a method of adding the compound after dissolving it in appropriate water and/or an organic solvent.

The general formula (
The amount of the compound 1) is 5X10-6 per mole of silver halide contained in the silver halide photographic material of the present invention.
A range of ~5X10-' moles is preferred, more preferably 5X10
It is preferably in the range of -5 to 1X10-'' moles.

The silver halide used in the silver halide photographic material of the present invention is preferably silver chlorobromide or silver chloroiodobromide containing at least 50 mol % of silver chloride. The average particle diameter of the silver halide grains used is preferably in the range of 0.05 to 0.5 μm, more preferably 0.10 to 0.40 μm.

Regarding the monodispersity of the silver halide emulsion used in the present invention, the value is preferably 5 to 25, more preferably 8 to 2.
Adjust so that it becomes 0. The grain size of the silver halide grains used in the present invention is conveniently expressed by the principal dimension of cubic grains, and the monodispersity S is the value obtained by dividing the standard deviation of the grain size by the average grain size r, as shown in the following formula (1). It is expressed as a value multiplied by 100.

As mentioned above, the silver halide grains used in the present invention preferably have a high monodispersity of 5 to 25.

Further, as the silver halide that can be used in the present invention, for example, a type having a multilayer laminated structure of at least two layers can be used. For example, silver chloride is used in the core part, silver bromide is used in the shell part, and vice versa. Silver chloride or silver chlorobromide particles whose shell portion is silver chloride may also be used. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide used in the present invention has the general formula ('
In addition to the spectral sensitization by compounds I), enhancement can be achieved by various chemical sensitizers. As a sensitizer,
For example, activated gelatin, sulfuric acid sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium enhancers (N,N-dimethylselenourea,
selenourea, etc.) reducing exacerbators (triethylenetetramine,
(stannic chloride, etc.), such as potassium chlorooleite,
Various noble metal sensitizers represented by cacaium aurothiocyanate, potassium chlorooleate, 2-oresulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chlorooleate, sodium chloroparadite, etc. are used alone, Alternatively, two or more types can be used in combination. When using a gold sensitizer, it is preferable to use hydrophilic colloids other than gelatin, such as colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, and polyvinyl. alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, e.g. U.S. Pat. No. 2.614,9
phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Pat.
Polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in the specifications of No. 48,520 and No. 2,831,767 are used. These hydrophilic colloids may be graft polymerized to gelatin, and these hydrophilic colloids can also be applied to layers that do not contain silver halide, such as /% ration prevention layer, protective layer, intermediate layer, etc.

The support used in the present invention °ζ is, for example, Balik paper,
Polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate,
For example, polyester film such as polyethylene terephthalate, polyamide film, polypropylene film 1
1. Typical examples include polycarbonate film, polystyrene film, and the like. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

The light-sensitive material according to the present invention includes, for example, at least one silver halide emulsion layer on a support as described above.
゛ However, a hydrophilic colloid layer having an appropriate thickness, preferably 0.1 to 10 μm, particularly preferably o, n to 2 μm, is coated as a protective layer on the silver halide emulsion layer. It is particularly preferable to have

The silver halide emulsion layer and hydrophilic colloid layer used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, anti-oxidants, etc., as necessary. A staining agent, a pH adjuster, an antioxidant, an antistatic agent, a thickener, a granularity improver, a dye, a mordant, a brightener, a development speed adjuster, a matting agent, etc., within a range that does not impair the effects of the present invention. Can be used within.

Among the above-mentioned various additives, those that can be particularly preferably used in the present invention include thickeners and plasticizers, such as those described in U.S. Pat.
Publication No. 39, West German Application Publication No. 1,904.604, Japanese Patent Publication No. 48-63715, Japanese Patent Publication No. 45-154
Publication No. 62, Belgian Patent No. 762.833, U.S. Patent No. 3.767.410, Belgian Patent No. 558
．． Substances described in the specifications of No. 143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based , isocyanate-based, sulfonic acid ester-based, carbodiimide-based, muyuchloric acid-based, acyloyl-based hardeners, and ultraviolet absorbers, for example, those described in U.S. Patent No. 3.
253,921, British Patent No. 1,309.349, etc., especially 2-(2'-
hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3-tertiary butyl-5-butylphenyl) )-5-chlorobenzotriazole, 2-(2-hydroxy-3゜5
-'; -tertiary 7' tylphenyl)-5-chlorobenzotriazole, etc., and as the dye,
U.S. Patent No. 2,072,908, Narrow Area Patent No. 107.
No. 990, U.S. Pat. No. 3.048.487, U.S. Pat. It may also be included. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent No. 548.5.
No. 32, No. 1.221.980, U.S. Patent No. 2.9
92.101, Patent No. 2.956.884, French Painting Patent No. 1.395,544, Special Publication No. 4B-43
Compounds described in Publication No. 125 etc. are good, especially 0
．． Silica gel with a particle size of 5-20 μm, 0.5-20
It is preferable to develop in the presence of a compound represented by polymethyl methacrylate (11) having a particle size of μm.

The remainder is white.

In the formula c, R3'l is a 5- or 6-position nitro group, R
3+1 represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion. ] As a specific compound represented by the general formula (1[[], 5-
Examples include nitroindazole and 6-nitrointasole, but the present invention is not limited thereto in any way.

The compound represented by the general formula (III) can be developed by dissolving it in an aqueous solvent such as diethylene glycol, triethylene glycol, ethanol, jetanolamine and triethanolamine, an alkali such as sodium hydroxide, an acid such as acetic acid, etc. It may be added to the liquid or may be added as is.

The compound represented by general formula (III) is contained in a concentration range of preferably about 111 Ig to 1,000 mg, more preferably about 50 mg to 300 mg per developer.

Examples of the developing agent for the silver halide photographic light-sensitive material of the present invention, particularly for the black-and-white photographic light-sensitive material, include the following. This developing agent can be used together with the compound represented by the above-mentioned general formula (I[I).

Typical examples of +1O-(-CH=C11÷-11 type developing agents include hydroquinone, as well as catechol, pyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone,
Methylhydroquinone, 2.3-dichlorohydroquinone, 2.5-dimethylhydroquinone, 2.3-dibromohydroquinone, 2.5-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2.5-di-
p-Phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4- (2-hydroxy Benzoyl) pyrogallol, ascorbic acid sorta, etc.

Further, as the HO+CH=CII+IrNHt type developer, ortho- and para-aminophenol or aminopyrazolone are typical, and 4-aminophenol,
2-amino-6-phenylphenol, 2-amino-4
-chloro-6-phenylphenol, 4-amino-2-
Phenylphenol, 3,4-diaminophenol, 3
-Methyl-4,6-diaminophenol, 2,4-cyamylsorcinol, 2,4,6-triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminephenol, Examples include p-hydroxyphenylaminoacetic acid and 2-aminonaphthol.

Furthermore, 112N +C=C-)-, NH2-type developing agents include, for example, 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N-( 4-amino-3-methylphenyl)-morpholine, p-phenylenediamine, 4-amino-N,N
-dimethyl-3-hydroxyaniline, N, N, N, N
-tetramethylparaphenylenediamine, 4-amino-
N-ethyl-N=(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-(β-methoxy ethyl)-3-methyl-aniline, 4
-amino-3-methyl-N-ethyl-N(β-methylsulfonamidoethyl)-aniline, 4-amino-N-butyl-N-n-sulfobutylaniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl,
Examples include 1,2°3,4-tetrahydroquinone and 9-aminoylolidine.

Petrocyclic type developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl-4-dimethyl-3-pyrazolidone. -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Pyrazolidones, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2
- birapurin, l-phenyl-3-methyl-4-amino-5-pyrazolone, 5-aminouracil and the like.

Other books include The Theory of the Photographic Ink Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
Developers such as those described in vol. 73, p. 3.100 (1951) of Can Chemical 5ociety) can be effectively used in the silver halide photographic light-sensitive material of the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as potassium sulfite or ammonium sulfite is used as a preservative in the developer used for processing the photosensitive material of the present invention, the effects of the present invention will not be impaired, and the effects of the present invention will not be impaired. This can be cited as one feature.

Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, it is necessary to adjust the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers, and provide a buffer function, as well as inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, and ethylenediaminetetraacetic acid, etc. Metal ion scavenger, methanol, ethanol, benzyl alcohol, development accelerator such as polyalkylene oxide, sodium alkylaryl sulfonate, natural saponin,
It is optional to add surfactants such as saccharides or alkyl esters of the aforementioned compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, and ionic strength regulators such as sodium sulfate.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamines mentioned above include triethanolamine jetanolamine, ethanolamine trimethylamine 2-diethylamino-1-ethanol 2-methylamino-niethanol 3-diethylamino-1-propanediol 3-diethylamino-1-propanol 5- Amino-1-Pentanol Diethylamine Methylamine Triethylamine Dipropylamine Di-isopropylamine 3.3'-Diaminodipropylamine 3-Dimethylamino-1-propatolhydantoic acid Allylamine Ethylamine Dimethylamine Ethylene diamine 2-Dimethylaminoethanol 2-ethyl Aminoethanol 2-(2-aminoethylamino)ethanoltetramethylammonium acetatecholinecholine chloridehydroxylamine sulfate 2-((2-aminoethylamino)-ethylaminoco-ethanolaminoguanidine sulfate 6-aminohexanoic acid 3-amino-1- Propatool 1-Dimethylamino-2-Propatool 2-Hydroxy-4-thiadodecyltrimethylammonium (pta) Pyridine Glycine 0-Aminobenzoic acid Polyethyleneimine L-(deca)-Cystine Hydrochloride Benzylamine 2-Amino-1- Ethanol 4-Amino-1-butanol 3-(dimethylamino)-1,2-propanediol 3-morpholino-1,2-propanediol 1,4-Piperazinebis(ethanesulfonic acid)3-piperidino-1
, 2-propanediol, N-piperidine ethanol, and the like.

In addition, the above glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1.4-7"tanediol,
There are 5-bentanediol and the like, but the amount is 5 to 500 g, preferably 20 to 200 g.

These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention can be developed with a developer containing the above-mentioned development inhibitor, thereby obtaining photosensitive characteristics with extremely excellent storage stability.

The pH value of the developer having the above composition is 9 to 12,
From the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11.

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably around 30°C, and the development time is generally completed within 3 minutes.
Particularly preferably within 40 seconds often brings about good results. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called early field image processing such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕

Embodiments of the present invention will be described in detail below. In addition,
As a matter of course, the present invention is not limited to the embodiments described below.

Make a silver chlorobromide emulsion using the solutions A, B, and C shown below! I! Made by I.

Solution A〉 Ossein gelatin 17 g Polyisopropylene-polyethylene oxydisuccinic acid ester sodium salt 5a110% ethanol solution Distilled water 1280 cc〈B〉 Silver nitrate 170 [g Distilled water 410 sj〈Solution C〉 Sodium chloride 40.9 g Potassium bromide 35.7 ff Polyisopropylene oxydisuccinate sodium salt l
O% ethanol solution 3s1 ossein gelatin
11 g distilled water
After keeping the 4011al solution 8 at 40°C, f! AF
Sodium chloride was added so that the C value was 160 mv.

Next, solutions B and C were added by a double jet method using the mixer described in JP-A-57-92523 and JP-A-57-92524.

As shown in Table 1, addition was carried out by gradually increasing the addition flow rate over a total addition time of 80 minutes while keeping the EAg constant.

The EAg value was 311Il 5 minutes after the start of addition from 160mv.
EAg value 12Q using sodium chloride aqueous solution of /1
mv and maintained this value thereafter until the completion of mixing.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol/l aqueous sodium chloride solution.

1e Table 1. EAg values were measured using a metal silver electrode and a double junction type saturated Ag/AgC1 comparison electrode (the electrode configuration was a double junction type disclosed in JP-A-57-197534). using a junction).

Further, a variable flow rate roller tube metering pump was used to add solutions B and C.

Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system.

Also, during the addition, the pH value of the system was kept constant at 3.0.
% nitric acid aqueous solution.

When silver halide grains are formed in the presence of rhodium salts and/or iridium salts, potassium hexachlororhodate (I[[)ate and/or hexachloroiridium (rV) is added to solution C in the amounts shown in Table 2. Each particle was prepared by adding potassium acid.

After addition of liquids B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then desalted and washed with water in a conventional manner.
An aqueous solution of ossein gelatin 600II11 (containing 30 g of ossein gelatin) was added and dispersed by stirring at 55° C. for 30 minutes, and the volume was adjusted to 750 cc.

This emulsion was then subjected to gold-sulfur enhancement, and 6-methyl-4-hydroxy-1,3,3a was added as a stabilizer.

7-Chitrazaindene was added. The emulsion was divided and as shown in Table 2, the compound of general formula (1) according to the present invention or the enhancing dyes shown below for comparison ((1) - (a) ~
(f) ) was added in an amount of 3 x 10-' mol/Ag 1 mol, respectively, for dye sensitization. In addition, each emulsion contains 2 phenylene 3.5-
Di(p-methylphenyl)syn-maleic acid copolymer 2
g/1 mole of Ag, 3.5 g of Ag and 12.0 g of gelatin ff on the polyethylene terephthalate film.
/rd. At that time, gelatin ffi
Sodium 1-decyl-2-(3-isopentyl)succinate 2-sulfonate was added as a spreading agent to a concentration of 1.0 g/m at 30 mg/n (lit! Dural protection containing 25 mg/i formalin as a film agent). The layers were applied in multiple layers.

1 Comparative sensitizing dyes (1) - (d) (1) - (e) Take three pieces of each of the obtained samples, and one piece is exposed to tungsten light using a photosensitive needle and an optical wedge. A contact screen GN No. 2 (150L) manufactured by Dainippon Screen Mfg. Co., Ltd. was used for the other piece.
The shaded areas were exposed to xenon light. Further, the remaining piece was subjected to the following processing without being exposed to light.

The above sample piece was processed in an automatic developing machine with a developing tank capacity of 40j2 using a developer having the following formulation and a commercially available fixer.

[Development processing conditions]

(Process) (Temperature) (Time) Development 28℃
Fixing for 30 seconds Washing at 28"C for 20 seconds Drying at 20'C for 20 seconds [Developer composition] (3 and composition A) (U composition) When using the developer, add the above composition A and composition in 500mj of pure water! They were dissolved in the following order and used after finishing if.

For developed samples subjected to wedge exposure, draw a photographic characteristic curve and calculate the intensity at optical density 2.5 for sample N.
The relative value is calculated based on o, 1, and gamma is the optical density of 1.
The janθ values of the straight line portion from 0 to 2.5 are shown.

For those in which M4 fil shadowing was performed using a printing plate-making camera using xenon light, the quality of the formed mesh (dot quality) was evaluated.

For dot quality, for so-called 50% dots where the area of the halftone area and the clear area are equal, the state of the fringe (blur) that occurs around the halftone dot is visually judged, and the smaller fringe is evaluated as 5.
Evaluation was made on a five-point scale.

That is, "5" is excellent and '1' is extremely poor. If the 50% dot quality is less than 13", it is generally unacceptable.

In addition, for samples processed without exposure, 4 films were stacked and the residual color of the film was visually evaluated and evaluated on a 5-point scale, with "5" being colorless and "1" being a strong orange residual color. Indicated.

For general plate making, residual color below "3" is at a level that is considered a major drawback.

These results are shown in Table 3.

As shown in Table 3, the dye is sensitized by the sensitizing dye represented by general d(I) according to the present invention, and the silver halide grains are lx10-8 to 5x10-8 per mole of silver halide.
It can be seen that the samples formed in the presence of h moles of water-soluble rhodium and/or iridium salts have high relative sensitivity, are very hard, and have little residual color.

[Effects of the Invention] As mentioned above, the silver halide photographic material of the present invention has the following properties:
It has the advantage that an extremely high contrast can be obtained by rapid development using a common developing solution with high photosensitivity and high sulfite ion concentration, and there is extremely little dye staining after processing.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Takatsuki Hirate Ygo Neho Masaharu (spontaneous) August 12, 1988 Patent Application No. 109024 2, Name of invention Spectral sensitized silver halide photographic light-sensitive material 3, Amendment person case Relationship with Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. Dia Palace Niban-cho 506 FAX (03) 221-19245 Date of amendment order Self-issued (1) In the specification, "Sulfone" in the 3rd to 2nd line from the bottom of the 2nd line ``amide group,'' is corrected to ``sulfamoyl group,''

(2) "Alkylsulfonyl group" in lines 2 and 3 of page 3 is corrected to "sulfoalkyl group."

(3) “(Mofit)-÷(÷2)” on page 14, line 3.
)7 ya” r -f-CIh+ O-e CIIzf
Correct it with "A".

(4) Page 14, line 5 and page 16, lines 4-5.

"Sulfonamide group" in line 9 of the same page and lines 10 to 11 of the same page are respectively corrected to "sulfamoyl group."

(5) "(For example, N-methylsulfonamide group, N,N-dimethylsulfonamide group, etc.)" on page 16, lines 11 to 12 of the same page is replaced with "(For example, N-methylsulfamoyl 5,
N,N-dimethylsulfamole group, etc.)".

(6) "Alkylsulfonic acid group, sulfonic acid group," on page 17, lines 3 to 4, is corrected to "sulfoalkyl group, sulfo group."

(7) The structural formula of r (1)-(a)J on page 57 of the same is corrected as follows.

that's all

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a support and a hydrophilic colloid layer coated on the support and including at least one silver halide emulsion layer, wherein the hydrophilic colloid layer contains: The silver halide grains contained in the silver halide emulsion layer are spectrally sensitized with a compound represented by the following general formula [I], and the silver halide grains contained in the first silver halide emulsion layer have a concentration of 1 x 10^-^ per mole of silver halide. 8~5x
A silver halide photographic light-sensitive material, characterized in that it is formed in the presence of 10^-^6 moles of water-soluble rhodium salt and/or iridium salt. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a substituted or substituted alkyl group.R^2 is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group,
Represents a carbamoylalkyl group, hydroxyphenyl group, hydroxyalkylphenyl group, phenyl group, alkoxyalkyl group, or a substituent -(CH_2)-_nA or -(CH_2)-_nO-(CH_2)-_nA. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or an alkoxy group, and n represents an integer value of 1 to 4. R^3 and R^4 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylsulfonyl group, a sulfo group, a chlorine atom, a fluorine atom, or a carboxy group. ]