JPH0687143B2 - Image forming method with improved sticking marks - Google Patents

Description

TECHNICAL FIELD The present invention relates to an image forming method of a silver halide photographic light-sensitive material, and is called a bright room when used as a light-sensitive material particularly in the field of printing plate making. The present invention relates to an image forming method of a silver halide photographic light-sensitive material, which can be handled in an environment where it can be obtained, and which can obtain good return characteristics such as improved sticking marks.

[Conventional technology and its problems]

In recent years, in the field of printing and plate making, in order to save labor and improve the rationalized work environment, there has been a demand for a technique for enabling film making, which is conventionally performed in a dark room, that is, so-called reversing process work, in a bright room. Etc. have been improved.

Examples of light-sensitive materials that can be handled in a bright room include silver halide photographic light-sensitive materials that are sensitive to light sources rich in ultraviolet light, such as ultra-high pressure mercury lamps, metal halide light sources, xenon lamps and halogen lamps. These silver halide photographic light-sensitive materials can be handled under a bright general fluorescent lamp of 100 to 300 lux or under a dedicated fluorescent lamp with a small amount of ultraviolet rays.

However, it is known that a conventional light-sensitive material that can be handled in a bright room is inferior in the following performance to a light-sensitive material that can be handled in a dark room. That is, the line drawing performance (extracting character performance) when the halftone dot image and the line image as the return document are overlapped and exposed.
In addition, there is a disadvantage that when a line drawing original or halftone original is pasted and fixed on the base with a transparent tape for plate making, the mark of this tape remains (after the pasting tape), which deteriorates the finished image quality. , This improvement was desired.

[Object of the Invention]

An object of the present invention is to provide an image forming method of a silver halide photographic light-sensitive material which has good performance upon exposure by a selected light source, particularly good bleeding character quality in return characteristics as photographic performance, and which does not show a tape sticking mark. Especially.

[Structure and Action of Invention]

The object of the present invention is a tetrazolium compound and at least
390 a silver halide photographic light-sensitive material containing a silver halide grain containing 50 mol% of silver chloride and a compound having a maximum absorption on the long-wave side in the range of 50 nm or more and 300 nm or less from the maximum light-sensing wavelength of the silver halide grain. It is achieved by an image forming method of exposing with a light source having a maximum value of specific energy at ˜430 nm.

In a preferred embodiment of the present invention, the silver halide photographic light-sensitive material used in the present invention described above contains a desensitizing dye and / or an ultraviolet absorber, and the silver halide photographic light-sensitive material has a specific energy of 390 to 430 nm. It is to form an image by exposing with a light source having a maximum value of.

Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material used in the present invention contains a tetrazolium compound. As the tetrazolium compound, typically, compounds represented by the following general formulas [I] to [III] are preferably used.

General formula [I]General formula (II)General formula (III)[R in the formula₁， R₃， R_Four， R_Five， R₈， R₉， R_TenAnd R₁₁Are each
Alkyl group (eg, methyl group, ethyl group, propyl group,
Dodecyl group, etc.), allyl group, phenyl group (eg phenyl group)
Group, tolyl group, hydroxyphenyl group, carboxy group
Phenyl group, aminophenyl group, mercaptophenyl group,
Methoxyphenyl group, etc.), naphthyl group (eg α-naphthyl)
Cyl group, β-naphthyl group, hydroxynaphthyl group, cal
Boxynaphthyl group, aminonaphthyl group, etc.), and heterocycle
Groups (eg thiazolyl, benzothiazolyl, oxa
Zolyl group, pyrimidinyl group, pyridyl group, etc.)
Group, each of which is a metal chelate or complex.
It may be a group that forms a body. R₂， R₆And R₇Is it
Allyl group, phenyl group, naphthyl group, heterocyclic group,
Alkyl group (eg methyl group, ethyl group, propyl group, group
Cyl group, mercaptomethyl group, mercaptoethyl group
Etc.), hydroxyl group, alkylphenyl group, alkoxyphenyl
Group, carboxyl group or a salt thereof, carboxyalkyl group
Group (eg methoxycarbonyl group, ethoxycarbonyl group
Group), an amino group (for example, an amino group, an ethylamino group,
Anilino group, etc.), mercapto group, nitro group and hydrogen atom
Represents a group selected from, D represents a divalent aromatic group, E
Is an alkylene group, an arylene group, or an aralkylene group.
Represents a selected group, X Represents an anion, n is 1 or
Represents 2. However, when the compound forms an inner salt, n is
It is 1. Next, the cation of the tetrazolium compound used in the present invention
Although specific examples of the internal portion are shown, they can be used in the present invention.
The cation portion of the compound is not necessarily limited to these
Not of.

(1) 2- (Benzothiazol-2-yl) -3-phenyl-5-dodecyl-2H-tetrazolium (2) 2,3-Diphenyl-5- (4-t-octyloxyphenyl) -2H-tetrazolium ( 3) 2,3,5-Triphenyl-2H-tetrazolium (4) 2,3,5-Tri (p-carboxyethylphenyl)-
2H-tetrazolium (5) 2- (benzothiazol-2-yl) -3-phenyl-5- (o-chlorophenyl) -2H-tetrazolium (6) 2,3-diphenyl-2H-tetrazolium (7) 2, 3-diphenyl-5-methyl-2H-tetrazolium (8) 3- (p-hydroxyphenyl) -5-methyl-2-phenyl-2H-tetrazolium (9) 2,3-diphenyl-5-ethyl-2H-tetrazolium (10) 2,3-Diphenyl-5-n-hexyl-2H-tetrazolium (11) 5-Cyano-2,3-diphenyl-2H-tetrazolium (12) 2- (Benzothiazol-2-yl) -5- Phenyl-3- (4-tolyl) -2H-tetrazolium (13) 2- (Benzothiazol-2-yl) -5- (4-chlorophenyl) -3- (4-nitrophenyl) -2H-tetrazolium (14) ) 5-Ethoxycarbonyl-2,3-di (3-nitrophenyl) -2H-tetrazo Um (15) 5-acetyl-2,3-di (p- ethoxy Phenylalanine) -
2H-tetrazolium (16) 2,5-diphenyl-3- (p-tolyl) -2H-tetrazolium (17) 2,5-diphenyl-3- (p-iodophenyl)-
2H-tetrazolium (18) 2,3-diphenyl-5- (p-diphenyl) -2H-
Tetrazolium (19) 5- (p-bromophenyl) -2-phenyl-3-
(2,4,6-Trichlorophenyl) -2H-tetrazolium (20) 3- (p-Hydroxyphenyl) -5- (p-nitrophenyl) -2-phenyl-2H-tetrazolium (21) 5- (3, 4-dimethoxyphenyl) -3- (2-ethoxyphenyl) -2- (4-methoxyphenyl) -2H-tetrazolium (22) 5- (4-cyanophenyl) -2,3-diphenyl-
2H-tetrazolium (23) 3- (p-acetamidophenyl) -2,5-diphenyl-2H-tetrazolium (24) 5-acetyl-2,3-diphenyl-2H-tetrazolium (25) 5- (fur-2yl) ) -2,3-Diphenyl-2H-tetrazolium (26) 5- (thien-2yl) -2,3-diphenyl-2H-
Tetrazolium (27) 2,3-diphenyl-5- (pyrid-4-yl) -2H-
Tetrazolium (28) 2,3-diphenyl-5- (quinol-2yl) -2H
-Tetrazolium (29) 2,3-diphenyl-5- (benzoxazole-2
Yl) -2H-tetrazolium (30) 2,3-diphenyl-5-nitro-2H-tetrazolium (31) 2,2 ', 3,3'-tetraphenyl-5,5'-1,4-butylene-di -(2H-tetrazolium) (32) 2,2 ', 3,3'-tetraphenyl-5,5'-p-phenylene-di- (2H-tetrazolium) (33) 2- (4,5-dimethylthiazole -2yl) -3,5-diphenyl-2H-tetrazolium (34) 3,5-diphenyl-2- (triazin-2yl)-
2H-tetrazolium (35) 2- (benzothiazol-2-yl) -3- (4-methoxyphenyl) -5-phenyl-2H-tetrazolium (36) 2,3-dimethoxyphenyl-5-phenyl-2H-tetrazolium ( 37) 2,3,5-Tris (methoxyphenyl) -2H-tetrazolium (38) 2,3-Dimethylphenyl-5-phenyl-2H-tetrazolium (39) 2,3-Hydroxyethyl-5-phenyl-2H- Tetrazolium (40) 2,3-Hydroxymethyl-5-phenyl-2H-tetrazolium (41) 2,3-Cyanohydroxyphenyl-5-phenyl-2H
-Tetrazolium (42) 2,3-di (p-chlorophenyl) -5-phenyl-2H-
Tetrazolium (43) 2,3-di (hydroxyethoxyphenyl) -5-phenyl-2H-tetrazolium (44) 2,3-di (2-pyridyl) -5-phenyl-2H-tetrazolium (45) 2,3, 5-Tris (2-pyridyl) -2H-tetrazolium (46) 2,3,5-Tris (4-pyridyl) -2H-tetrazolium The tetrazolium compound contained in the light-sensitive material used in the present invention is used as a non-diffusible substance. In this case, a non-diffusible compound obtained by appropriately selecting the cation portion and the anion portion is used.

Examples of the anion moiety of the tetrazolium compound used in the present invention include halogen ions such as chloride ion, bromide ion and iodide ion, acid groups of inorganic acids such as sulfuric acid, nitric acid and perchloric acid, sulfonic acid and carboxylic acid. Acid groups of organic acids, lower alkylbenzenesulfonate anions such as p-toluenesulfonate anion, higher alkylbenzenesulfonate anions such as p-dodecylbenzenesulfonate anion, higher alkylsulfate anions such as lauryl sulfate anion, di- Diethylsulfosuccinate anion such as 2-ethylhexyl sulphosuccinate anion, polyether alcohol sulfate anion such as cetyl polyethenoxysulfate anion, higher fatty acid anion such as stearic acid anion, polyacrylic acid Examples thereof include polymers having acid radicals such as anions.

The non-diffusible tetrazolium compound according to the present invention can be synthesized by appropriately selecting the anion portion and the cation portion. The compounds according to the present invention thus synthesized are, for example, 2,3,5-triphenyl-2H-tetrazolium-dioctylsuccinate sulfonate, etc., which are each described in detail in Examples below. Soluble salt of gelatin is dispersed in gelatin, then both are mixed and dispersed in gelatin matrix, and crystals of oxidizer are purely synthesized and then dissolved in a suitable solvent (eg dimethyl sulfoxide). May be dispersed in a gelatin matrix. When the dispersion is difficult to be uniform, a method of emulsifying and dispersing with an ultrasonic wave or a suitable homogenizer such as Manton-Gaulin homogenizer may give good results. It is also possible to finely disperse it in a high boiling point solvent such as dioctyl phthalate to protect it and disperse it in the hydrophilic colloid layer.

As described above, by using a combination of a plurality of preferable compounds, in the present invention, it is possible to obtain an advantage such as a wide allowable development range, and the compounds may be used in any combination according to the purpose.

The tetrazolium compound used in the present invention is preferably contained in a hydrophilic colloid layer containing a silver halide emulsion. Specifically, it is contained in a silver halide emulsion layer and / or a layer directly or indirectly adjacent thereto. Further, the tetrazolium compound used in the present invention is, for example, by dissolving the tetrazolium compound used in the present invention in a suitable organic solvent and directly coating the outermost portion of the silver halide photographic light-sensitive material or the outermost portion during production by an overcoat method or the like. It may be incorporated into the silver halide photographic light-sensitive material of the present invention.

The tetrazolium compound used in the present invention is generally preferably 0.0001 to 10 mol, and more preferably 0.001 to 1 mol per mol of silver halide contained in the silver halide photographic light-sensitive material used in the present invention. It is suitable to be used in.

In the silver halide photographic light-sensitive material to which the image forming method of the present invention is applied, the maximum absorption is on the long-wave side of 50 nm or more and 300 nm or less from the light-sensitive maximum wavelength of the silver halide grains so that it can be handled in a bright room. Incorporate a compound that has.

The optimum maximum absorption wavelength of the above compound varies to some extent depending on various conditions of the silver halide emulsion used,
It can be easily found by measuring the spectroscopic spectrum. Such a compound may be contained in the silver halide emulsion layer, but more effectively, it is preferably contained in a layer located farther from the support than the emulsion layer, for example, a protective layer. Further, it may be contained in an intermediate layer between the silver halide emulsion layer and the protective layer. The effect of the present invention can be further enhanced by using a substance capable of immobilizing the above compound, such as a basic modulant or an acid-treated gelatin having a high isoelectric point, in the layer containing the above compound.

About 5 m
It is preferably used in the range of g to 3 g / m ² , and the optical density at the maximum absorption wavelength is preferably 0.10 or more. Further, the maximum absorption wavelength has a maximum absorption on the long-wave side in the range of 50 nm or more and 300 nm or less, and more preferably 200 nm or less long-wave. Further, for example, 50-100 nm
More preferable results can be obtained by combining two or more kinds such as a long wave compound and a 100 to 200 nm long wave compound. These compounds are represented by, for example, the following general formulas [II]-(a), (b) and (c) and specific exemplified compounds, but of course they are not limited thereto.

General formula [IV]-(a) In the formula, R ₄₁ is -OX or Wherein X and Y are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, a halogenated alkyl group or an optionally substituted alkyl group or Represents a sodium / potassium salt thereof, R ₄₂ and R ₄₃ represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or a group similar to the above-OX group, and Q is at least one. A halogen atom, a carboxy group, a sulfo group, a sulfoalkyl group, or a phenyl group substituted with a sodium / potassium salt thereof, a sulfoalkyl group, a sulfoalkoxyalkyl group, a sulfoalkylthioalkyl group, or L may be substituted. Represents a methine group. R ₄₄ represents an alkyl group, a carboxy group, an alkyloxycarbonyl group, or an acyl-substituted, sulfo-substituted, or unsubstituted amino group. m ₁ represents an integer 0, 1 or 2 and m ₂ represents an integer 0 or 1.

General formula [IV]-(b) In the formula, R ₄₅ , R ₄₆ , R ₄₈ , R ₄₉ and R ₅₀ are a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfone group or a sodium / potassium salt thereof. And R ₄₇ represents an alkyl group or a carboxyl group.

General formula [IV]-(c) In the formula, R ₅₁ and R ₅₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group or a carboxyl group, and R ₅₃ and R ₅₄ are an alkyl group substituted with a sulfonic acid group or a carboxyl group or a sulfonic acid group or It represents an aryl group substituted with a carboxyl group or a sulfonic acid group or a sodium / potassium salt thereof, and L represents a substituted or unsubstituted methine chain. M represents a sodium, potassium or hydrogen atom, and m ₃ represents 0 or 1.

Typical specific examples of the compounds represented by the general formulas [IV]-(a) (b) (c) are shown below.

In the image forming method of the present invention, a light source having a maximum specific energy at 390 to 430 nm is used as a light source for exposing the silver halide photographic light-sensitive material used in the present invention. Preferably 400-4
Exposure is performed with a light source having a maximum value at 20 nm, but any light emission type may be used as long as it meets this condition. For example, the presence or absence of a filament and the presence or absence of an electrode are not limited. Further, the light emitting gas contained in the light emitting electrode tube may be a halogen gas, a rare gas or a mixture. Further, a light emitting metal may be contained together with the gas.

In general, as a light source suitable for this purpose, an emission spectrum of a V-bulb type of an electrodeless discharge tube described later is preferable in addition to an ultra-high pressure mercury lamp and a metal halide lamp. This type of arc tube is available from FUSION in the United States and other light source manufacturers.
No. 4254363, No. 4010400, No. 3993379, No. 3950670, No. 3873
884, same 3790852, same 3787705, same 3786308, same 3645629,
Same 4536675, same 4422017, same 4415838, same 4390813, same 4383
203, 4359668, 3911318, 3872349, 3983039,
Examples thereof include those disclosed in 4042850, 4208587, 4313969, 4269581 and the like.

Further, the light source having the maximum value of the specific energy in the range of 390 to 430 nm referred to in the present invention is the light source above the ultra-high pressure mercury lamp or the metal halide lamp light source in order to obtain the above-mentioned V-sphere type emission spectrum.
It also includes a filter equipped with an absorption filter that cuts short waves of 390 nm or shorter (whether or not it cuts long waves of 430 nm or longer), and the effects of the present invention can also be obtained. This filter can be attached near the top of the light source or
There is a method in which the glass plate on the upper part of the printer (the glass plate shown in FIG. 2) is used as an absorption filter glass.

The silver halide used in the silver halide photographic light-sensitive material according to the present invention is silver chloride, silver chlorobromide, silver chloroiodobromide or the like having an arbitrary composition and containing at least 50 mol% of silver chloride. The average grain size of silver halide grains is preferably 0.025 to 0.5 μm, more preferably 0.05 to 0.30 μm.

The monodispersity of the silver halide grains according to the present invention is defined by the following formula (1), and the value is preferably 5 to 60, more preferably 8 to 30. The grain size of the silver halide grains according to the present invention is represented by the edge length of cubic grains for convenience, and the monodispersity is a value obtained by dividing the standard deviation of grain sizes by the average grain size.
Expressed as a value multiplied by 100.

The silver halide usable in the present invention may be of a type having a multi-layer laminated structure of at least two layers. For example, silver chlorobromide grains in which silver chloride is used in the core portion, silver bromide in the shell portion, conversely silver bromide in the core portion and silver chloride in the shell portion may be used. At this time, iodine can be contained in any layer within 5 mol%.

When the silver halide emulsion used in the present invention is prepared, a rhodium salt can be added to control the sensitivity or gradation. The addition of the rhodium salt is generally preferred during grain formation, but may be during chemical ripening or preparation of the emulsion coating solution.

The rhodium salt added to the silver halide emulsion used in the present invention may be a simple salt or a double salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride and the like are used.

The addition amount of the rhodium salt can be freely changed depending on the required sensitivity and gradation, but a range of 10 ^-9 mol to 10 ^-4 mol is particularly useful for 1 mol of silver.

When the rhodium salt is used, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt and gold salt may be used together. Iridium salts are often used for the purpose of improving the high illuminance property, and are contained in an amount of 10 ^-9 to 10 ^-4 mol per mol of silver.
It can be preferably used up to a molar range.

The silver halide used in the present invention can be sensitized with various chemical sensitizers. As a sensitizer,
For example, active gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, etc.), selenium sensitizers (N, N-dimethylselenourea, selenourea, etc.), reduction sensitizers (tri Ethylene tetramine,
Stannous chloride, etc.), such as potassium chloroaurite,
Potassium aurithiocyanio, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, various precious metal sensitizers typified by sodium chloroparadite, etc., respectively, Alternatively, two or more kinds can be used in combination. When a gold sensitizer is used, rodan ammon can be used as an auxiliary agent.

The effect of the present invention can be further enhanced by incorporating a desensitizing dye and / or an ultraviolet absorber in the silver halide photographic light-sensitive material of the present invention.

As the desensitizing dye, those represented by the following general formulas [V]-(a) to (e) can be preferably used.

As the ultraviolet absorber, the following general formula [V]-(f),
What is represented by (g) can be used preferably.

These compounds are disclosed in US Pat. Nos. 3,567,456 and 3,615,6.
39, same 3,579,345, same 3,615,608, same 3,598,596, same 3,598,95
5, No. 3,592,653, No. 3,582,343, Japanese Examined Patent Publication No. 40-26751, No. 40-2
It can be synthesized with reference to the specifications such as 7332, 43-13167, 45-8833, 47-8746.

General formula [V]-(a) General formula [V]-(b) [In the formula, R ₆₁ and R ₆₂ represent a hydrogen atom, a halogen atom, a cyano group or a nitro group. Further, R ₆₁ and R ₆₂ may form an aromatic ring. R ₆₃ and R ₆₄ each represent an alkyl group, a lower alkenyl group, a phenyl group or a lower hydroxyalkyl group, and when R ₆₁ and R ₆₂ are other than a hydrogen atom, they may be an aryl group, and m ₄ is 1 to 4 A positive integer for R ₆₅
Represents a lower alkyl group or a sulfonated lower alkyl group, and X ₁ represents an acid anion] General formula [V]-(c) [In the formula, R ₆₆ and R ₆₇ are each a hydrogen atom or a nitro group, R ₆₈ and R ₆₉ are a lower alkyl group, an alkyl group or a phenyl group, Z ₁ is a nitrobenzothiazole nucleus, a nitrobenzoxazole nucleus, or a nitrobenzoselenazole. Nucleus, imidazo [4,5-b] quinoxaline nucleus, 3,3-dimethyl-3H-
Pyrrolo [2,3-b] pyridine nucleus, 3,3-dialkyl-3H-
Nitroindole nucleus, thiazolo [4,5-b] quinoline nucleus, nitroquinoline nucleus, nitrothiazole nucleus, nitronaphthothiazole nucleus, nitrooxazole nucleus, nitronaphthoxazole nucleus, nitroselenazole nucleus, nitronaphthoselenazole nucleus or nitropyridine An atomic group necessary for forming a nucleus, X ₂ is an anion, and m ₅ and n are 1 or 2, respectively. However, when the compound forms an inner salt, n represents 1.] General formula [V]-(d) [In the formula, R ₇₀ , R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a nitro group, and R ₇₄ represents a hydrogen atom, an alkyl group or a nitro group. Z ₂ is a thiazole which is unsubstituted or substituted by a lower alkyl group, a phenyl group, a thienyl group, a halogen atom, an alkoxy group, a hydroxy group, a cyano group, an alkylsulfonyl group, an alkoxycarbonyl group, a phenylsulfonyl group or a trifluoromethyl group. Nuclear,
Benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
To form a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a thiazoline nucleus, a pyridine nucleus, a quinoline nucleus, an isoquinoline nucleus, a 3,3-dialkyl-3H-indole nucleus, an imidazole nucleus, a benzimidazole nucleus or a naphthimidazole nucleus. Represents the necessary atomic group, L ₁ and L ₂
Each represents a methine chain which is unsubstituted or substituted with a lower alkyl group or an aryl group, and R ₇₅ and R ₇₆ are each an unsubstituted or substituted alkyl group, an alkenyl group, an aryl group, a sulfoalkyl group or an aralkyl group, X ₂ represents an anion, and m ₆ and n each represent 1 or 2. However, when the compound forms an inner salt, n represents 1.] General formula [V]-(e) [In the formula, R ₇₇ and R ₇₉ each represent an alkyl group, and R ₇₈ represents an aryl group. L ₁ and L ₂ each represent a methine chain which is unsubstituted or substituted with a lower alkyl group or an aryl group.
Z ₃ is a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a thiazoline nucleus, a pyridine nucleus, a quinoline nucleus, 3,3 -Atomic group necessary for forming a dialkylindolenine nucleus, an imidazole nucleus, and an imidazo [4,5-b] quinoxaline nucleus, X ₂ is an anion, and m ₇ is 1 to 3
Is a positive integer, and m ₈ represents 1 or 2. ] General formula [V]-(f) [Wherein R ₈₀ represents an alkyl, hydroxyalkyl, cyanoalkyl or sulfoalkyl group, Z ₄ represents an oxazole, thiazole, benzoxazole, benzothiazole, imidazole or benzimidazole ring, and A represents a pyrrole ring or a pyrrolidine ring. Represents the necessary atomic group. ] General formula [V]-(g) [In the formula, R ₈₁ , R ₈₂ , R ₈₃ and R ₈₄ represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group or a sulfoalkyl group. R ₈₅ and R ₈₆ represent a sulfonic acid group or an alkyl sulfonic acid group] Next, specific exemplary compounds of the desensitizing dye and the ultraviolet absorber which are preferably used in the present invention are shown, but the compounds are not limited to these. Absent. (Note that some of the V-1 to V-36 exemplified below do not correspond to the general formula of the above.
Represents a paratoluenesulfonic acid group. ) Further, the silver halide emulsion used in the present invention is, for example, U.S. Patent Nos. 2,444,607, 2,716,062, and 3,512,98.
No. 2, West German application publication No. 1,189,380, No. 2,058,626
No. 2,118,411, Japanese Examined Patent Publication No. 43-4133, U.S. Pat.
No. 342,596, Japanese Patent Publication No. 47-4417, West German Application Publication No. 2,149,
No. 789, Japanese Examined Patent Publication No. 39-2825, Japanese Examined Patent Publication No. 49-13566 and the like, compounds described in each specification or publication, preferably, for example, 5,6-trimethylene-7-hydroxy-S-triazolo (1, 5-a) pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo (1,5-a) pyrimidine, 5-methyl-7
-Hydroxy-S-triazolo (1,5-a) pyrimidine, 7-hydroxy-S-triazolo (1,5-a) pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazolo (1,5 -a)
Pyrimidine, gallic acid ester (eg isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole),
Benzotriazoles (5-bromobenztriazole,
5-methylbenztriazole), benzimidazoles (6-nitrobenzimidazole) and the like can be used for stabilization.

The hydrophilic colloid which is particularly advantageously used in the present invention is gelatin, but as the hydrophilic colloid other than gelatin,
For example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives such as U.S. Pat.Nos. 2,614,928 and 2,525,753. Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in each specification, or styrene acrylate, acrylic ester as described in each specification of US Pat. Nos. 2,548,520 and 2,831,767. , A methacrylic acid, a methacrylic acid ester, or other polymerizable monomer having an ethylene group that is graft-polymerized with gelatin. These hydrophilic colloids are used in layers containing no silver halide, such as antihalation. Layer, protective layer, intermediate layer, etc. It can also be applied.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Representative examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films and the like. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

The developing agents used for developing the silver halide photographic light-sensitive material according to the present invention include the following. HO- (CH
(= CH) _n -OH type developing agents include hydroquinone, catechol, pyrogallol and its derivatives and ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dibromohydroquinone, 2 There are 5,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, sodium ascorbate and the like.

Further, as the HO- (CH = CH) _n -NH ₂ type developer, ortho and rose aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-amino- 4-chloro-6-phenylphenol, N-methyl-p-aminophenol, etc.

Furthermore, examples of H ₂ N- (CH = CH) _n -NH ₂ type developers include 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N There are-(4-amino-3-methylphenyl) -morpholine, p-phenylenediamine, and the like.

Heterocyclic developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 3-pyridolidones, 1-phenyl-4-amino-5-pyrazolone, 5-aminouracil and the like can be mentioned.

In addition, TH Theory of the Photographic Process 4th Edition by TH James (The Theory of the
Photographic Process Fourth Bdition, pages 291-334 and the Journal of the American Chemical Societ.
y) Developers such as those described in Vol. 73, page 3,100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination. Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material according to the present invention, the effect of the present invention is not impaired. Hydroxylamine and hydrazide compounds can be used as preservatives.
The amount is preferably 5 to 500 g, and more preferably 20 to 200 g.

The developer may contain glycols as an organic solvent, and examples of such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol,
Although there are 1,5-pentanediol and the like, diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, and more preferably 20 to 200 g, per developer. These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing using a developer containing the above-mentioned development inhibitor to obtain a light-sensitive material having extremely excellent storage stability.

The pH value of the developer having the above composition is preferably 9 to 12, but the pH value is more preferably 10 to 11 from the viewpoint of preservability and photographic characteristics.

The silver halide photographic light-sensitive material according to the present invention can be processed under various conditions. Regarding the processing temperature, for example, the developing temperature is preferably 50 ° C. or lower, particularly preferably around 30 ° C., and the developing time is generally completed within 3 minutes,
Particularly preferably, within 2 minutes often brings a favorable effect. Further, it is optional to employ processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening and neutralization steps, which can be omitted as appropriate. Furthermore, these processes may be so-called hand development processes such as plate development and frame development, or mechanical development such as roller development and hanger development.

〔Example〕

 The present invention will be specifically described below with reference to examples.

It should be understood that the present invention is not limited to the examples described below.

Example-1 Grains having an average grain size, a silver halide composition, and a monodispersity degree shown in Table I below containing 10 ^-5 mol of rhodium per 1 mol of silver by a controlled double jet method under an acidic atmosphere of pH 3.0 It was created. Particles grow with 1 benzyladenine
% Gelatin aqueous solution 30 mg per 1% gelatin aqueous solution.
After mixing silver and halide, 6-methyl-4-hydroxy-1,3,
600 mg of 3a, 7-tetrazaindene per mol of silver halide
Was added, followed by washing with water and desalting.

Then, 60 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added per mol of silver halide, followed by sulfur sensitization. 6-Methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer after sulfur sensitization.

(Silver Halide Emulsion Layer) Additives were prepared and added to the above emulsions in the amounts shown below, and subjected to latex undercoating (100 μm thickness) polyethylene according to Example 1 of JP-A-59-19941. It was coated on a terephthalate support.

Latex Polymer: Styrene-Butyl Acrylate-
Acrylic acid ternary copolymer 1.0g / m ₂ saponin 200mg / m ₂ polyethylene glycol 15mg / m ₂ sodium dodecylbenzene sulfonate 100mg / m ₂ hydroquinone 200mg / m ₂ styrene-maleic acid copolymer 200mg / m ₂ gallic acid Butyl ester 500 mg / m ₂ tetrazolium compound 5-methylbenzotriazole 30 mg / m ₂ desensitizing dye or UV absorbing dye shown in Table-I 2-mercaptobenzimidazole-5-sulfonic acid 30 mg / m ₂ inert ose In-gelatin 1.5 g / m ₂ Silver amount 2.8 g / m ₂ (emulsion layer protective film) An emulsion layer protective film was prepared and coated in the following amounts.

Fluorinated dioctyl sulfosuccinate 300 mg / m ₂ Polyethylene glycol (Molecular 2000) 30 mg / m ₂ Matting agent: Synthetic silica (average particle size 3.5 μm) 100 mg / m ₂ Styrene-maleic acid copolymer 100 mg / m ₂ Acid-treated gelatin (Isoelectric point 7.0) 1.2g / m ₂ 50nm to 300nm Compounds with absorption maximum on the long-wave side Shown in Table-1 (“50nm long-wave compound” column) Hardener 2,4-dichloro-6-oxy- S-triazine acid 50mg / m ₂ mordant (Backing layer) Additives were coated on the support on the side opposite to the emulsion layer so as to have the following amounts.

Latex polymer: butyl acrylate-styrene copolymer 0.5g / m ₂ citric acid 40mg / m ₂ saponin 200mg / m ₂ 5-nitroindazole 100mg / m ₂ hydroquinone 100mg / m ₂ phenidone 30mg / m ₂ backing dye Ocein gelatin 2.0 g / m ₂ Styrene-maleic acid copolymer 0.2 g / m ₂ (backing layer protective film) Additives were prepared and coated in the amounts shown below.

Dioctyl sulfosuccinate 300 mg / m ₂ Lithium nitrate 30 mg / m ₂ Matting agent: Polymethylmethacrylate (average particle size 4.0 μm) 100 mg / m ₂ Ocein gelatin (isoelectric point 4.9) 1.1 g / m ₂ Fluorinated dodecylbenzene Sodium sulfonate 50mg / m ₂ 2,4-dichloro-6-oxy-S-triazinic acid 150mg / m _{2 The} sample obtained as above was exposed with the light source shown in Table-I to the developer shown below. Then, development processing was performed using a fixing solution.

(Exposure Method) An electrodeless discharge light source manufactured by Fusion Corporation of the United States called "V sphere" called a "V sphere" (having a maximum of specific energy at 400 to 420 nm) shown in Fig. 1 (a), or Fig. 1 (b). ) The conventional light source called "D sphere" (having a maximum of specific energy in 350 to 380 nm) shown in Fig. 2) is attached under the glass plate, and the sticking mark, as shown in Fig. 2, on the glass surface, Place the original and photosensitive material so that the quality of the extracted characters can be evaluated (6.
5. Laminating base, 4. Film with line image positive image formed, 3. Laminating base, 2. Film with rope image, 1. Photographic material for return) Exposure.

<Developer formulation> (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Potassium bromide 4.5g (Composition B) Pure water (ion exchange water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) ) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-5-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 before use.

<Fixing solution formulation> (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% W / V aqueous solution) 13.6ml (Composition B) Pure water (ion exchanged water) 17ml Sulfuric acid (50% W / W aqueous solution) 4.7g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / W aqueous solution) 26.5g Use of fixer At times, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was finished to 1 before use.

The pH of this fixer was about 4.3.

<Development processing conditions> (Process) (Temperature) (Time) Development 28 ° C 30 seconds Fixing 28 ° C 20 seconds Washing with water at room temperature 20 seconds Evaluation was performed as follows, and the results are shown in Table-I.

(Photographic performance evaluation method) (1) Trace of sticking In FIG. 2, a mesh film was placed on the sticking base, and the periphery of the mesh film was fixed with a transparent scotch tape for plate making, and exposed and developed. After that, when the tape mark (paste mark) was not present, "5" mark was conspicuous and the worst level was "1", and the evaluation was performed on a 5-point scale.

(2) Extracted character quality The extracted character quality is measured when the exposure is properly performed so that the portion having a halftone dot area of the halftone film of FIG. 2 has a halftone dot area of 50% on the return photosensitive material. The image quality with which a line width of 50 μm on the line drawing film in FIG. 2 is reproduced is referred to as "5" for the very good extracted character image quality, and "1" for the worst character level, and was evaluated on a 5-point scale.

From Table-I, a silver halide photographic light-sensitive material containing a compound containing a monodispersed fine grain silver halide having a high silver chloride content and having a maximum absorption wavelength at a wavelength of 50 nm longer than the maximum photosensitive wavelength of the grain and a tetrazolium compound, It can be seen that when exposed with a normal light source equipped with an absorption filter that cuts short waves of 385 nm or less (Sample No. 4), the sticking trace performance is improved as compared with the comparative samples (Nos. 1 to 3). Further, a sample prepared by adding a desensitizing dye and / or an ultraviolet absorber to the above silver halide photographic light-sensitive material is exposed with "V sphere" having a maximum value of specific energy at 400 to 420 nm (Sample No. 5 to
9), it can be understood that a silver image having a markedly excellent extracted character quality and having no sticking mark can be obtained.

The Kodak Color Printing Filter CP-2 is located above the light source of the bright room printer P-627FM manufactured by Dainippon Screen.
The result of exposing Sample No.4 of Table-I with B mounted is Sample No.4.
It was similar to the result of.

[Advantages of the Invention] As described above, according to the image forming method of the present invention, good performance is obtained by exposure with a selected light source, particularly good bleeding character quality in return characteristics as photographic performance, and further appearance of tape sticking marks. No silver halide photographic material can be imaged.

[Brief description of drawings]

FIG. 1 (a) is a spectrum of an electrodeless discharge light source called “V sphere” used in the present invention, and FIG. 1 (b) is
It is a spectrum of a conventional light source called "D sphere". FIG. 2 is a diagram showing the relationship between the original and the photosensitive material during the operation of returning the extracted characters. 1 ... Photographic material for returning, 2 ... Film on which halftone image is formed, 3,5 ... Lamination base, 4 ... Film on which positive line image is formed, 6 ... Cut mask film.

Claims (2)

[Claims] 1. A silver halide grain containing tetrazolium and at least 50 mol% of silver chloride, and a compound having a maximum absorption on the long-wave side in the range of 50 nm to 300 nm from the maximum photosensitive wavelength of the silver halide grain. An image forming method comprising exposing the silver halide photographic light-sensitive material to a light source having a maximum value of specific energy at 390 to 430 nm. 2. The silver halide photographic light-sensitive material contains a desensitizing dye and / or an ultraviolet absorber, and the silver halide photographic light-sensitive material is exposed to a light source having a maximum specific energy at 390 to 430 nm. Claim 1 characterized in that
The image forming method according to item.