JPS6395437A - Method for forming image having improved trace due to taping - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material having good quality of negative character, and less trace due to taping by exposing a silver halide photographic sensitive material contg. a tetrazolium compd. and a specific compd., with a light source having the max. value of specific energy at a specific wavelength. CONSTITUTION:The silver halide photographic sensitive material comprises the tetrazolium compd., the silver halide particle contg. at least 50mol% silver chloride, and the compd. having the max. absorption at the longer wavelength than the max. photosensitive wavelength of the silver halide particle by at least 50nm. Said silver halide photographic sensitive material is exposed with the light source having the max. value of the specific energy at the wavelength of 390-430nm. The compd. having the max. absorption at the longer wavelength than the max. photosensitive wavelength of the silver halide particle by at least 50nm wavelength is preferably used in range of 5mg-3g/m<2>. The optical density of said material at the max. absorption wavelength is preferably >=0.10. Thus, the image of the silver halide photographic sensitive material having the good performance with exposure of a selected light source, especially, the good photographic performance such as the good quality of negative character in repeating performance and reduced trace due to taping, can be formed.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an image forming method for a silver halide photographic light-sensitive material. The present invention relates to an image forming method of a silver halide photographic light-sensitive material that can be handled in a suitable environment and that provides good return characteristics such as improved pasting 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 rational work environment, there has been a demand for technology that allows film making and so-called film reversal processes, which were traditionally done in a dark room, to be performed in a bright room. Improvements have been made to equipment such as printers.

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

However, it is known that conventional photosensitive materials that can be handled in a bright room are inferior in the following performance compared to photosensitive materials that can be handled in a dark room. In other words, line drawing performance (cutting character performance) when exposing a halftone image and a line image as a returned original in an overlapping manner.
Another disadvantage is that when a line drawing original or halftone original is pasted and fixed on the base with transparent plate-making tape, traces of this tape remain (pasting tape mark), which impairs the quality of the finished image. , this improvement was desired.

[Purpose of the invention]

An object of the present invention is to provide an image forming method for a silver halide photographic light-sensitive material that exhibits good performance when exposed to light using a selected light source, in particular has good cut-out character quality in terms of photographic performance and return characteristics, and also does not leave tape pasting marks. There is a particular thing.

[Structure and operation of the invention]

The object of the present invention is to provide silver halide grains containing a tetrazolium compound and at least 50 mol% of silver chloride, and at least 5 Qn from the maximum photosensitive wavelength of the silver halide grains.
This is achieved by an image forming method in which a silver halide photographic material containing a compound having a large II absorption at m long wavelengths is exposed with a light source having a maximum specific energy at 390 to 43 Q nm.

Further, 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. The method is to form an image by exposing to a light source with a maximum value of .

The present invention will be explained in detail below.

The silver halide photographic material used in the present invention contains a tetrazolium compound. As the tetrazolium compound, compounds represented by the following general formulas CI) to (I[I) are typically preferably used.

General formula (n) General formula (I[I) [In the formula, R1, RI Rt, Rs+ R11, R9, R
1° and R1+ are each an alkyl group (e.g. methyl group, ethyl group, propyl group, dodecyl group, etc.), an allyl group,
Phenyl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, amino β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group,
(aminonaphthyl group, etc.), and heterocyclic groups (e.g., thiazolyl group, benzothiazolyl group, oxacylyl group, pyrimidinyl group, pyridyl group, etc.), all of which form metal chelates or complexes.
It can be a base. R2, R6 and R7 are each an allyl group,
Phenyl group, naphthyl group, heterocyclic group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, mercaptomethyl group, mercaptoethyl group, etc.), hydroxyl group, alkylphenyl group, alkoxyphenyl group, carboxyl group or their salt, carboxyalkyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), amino group (
(e.g., amino group, ethylamino group, anilino group, etc.), mercapto group, nitro group, and hydrogen atom, D represents a divalent aromatic group, and E represents an alkylene group, arylene group, aralalkylene group. represents a group selected from
Xe represents an anion, and n represents 1 or 2. However, when the compound forms an inner salt, n is 1. ] Next, specific examples of the cation moiety of the tetrazolium compound used in the present invention will be shown, but the cation moiety of the compound that can be used in the present invention is not necessarily limited to these.

(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-)rifhenyl-2H-tetrazolium (4) 2,3.5-)-(p-carboxyethylphenyl)-2H-tetrazolium(5)2-(benzothiazol-2-yl)-3-phenyl-5-(o
-chlorphenyl) = 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-(4-1-lyl)-2H~tetrazolium(13) 2-(benzothiazol-2-yl)-
5=(4-chlorophenyl)-3-(4-nitrophenyl)-2H-tetrazolium (14) 5-ethoxycarbonyl-2,3-di(3-nitrophenyl)
~2H~ Tetrazolium (15) 5-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium (16) 2. 5-diphenyl-3-(p-)lyl)-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-)lychlorphenyl)-
2H-tetrazolium (20) 3- (p-hydroxyphenyl)-
5-(p-nitrophenyl)-2-phenyl-2H
-tetrazolium(21)5- (3,4-dimethoxyphenyl)-3
-(2-ethoxyphenyl)-2-(4-%toxyphenyl)-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-(fluor-2yl)-2,3-diphenyl-2H-tetrazolium (26) 5-(cheso-2yl)-2,3-diphenyl-2H -Tetrazolium (27) 2. 3-diphenyl-5-(pyrido-
4yl)-2H-tetrazolium (28) 2. 3-diphenyl-5-(quinol-
2yl)-2H-tetrazolium (29) 2. 3-diphenyl-5-(benzoxazol-2yl)-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-dimethylthiazol-2yl)-3,5-diphenyl-2H ~ tetrazolium (34) 3. 5-diphenyl-2-(triazin-2yl)-2H-tetrazolium (35) 2-(benzothiazol-2yl)-3-
(4-methoxyphenyl)-5-phenyl-2H-
Tetrazolium (36) 2. 3-dimethoxyphenyl-5-phenyl-2H-tetrazolium (37) 2,3.5-tris(methoxyphenyl)-2
■(-Tetrazolium (38) 2. 3-dimethylphenyl-5-phenyl-2H-tetrazolium (39) 2. 3-Hydrohonshochiruzuichi phenyl-2
H-tetrazolium (40) 2. 3-Hydroxymethyl-5-phenyl-211-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 When the tetrazolium compound contained in the photosensitive material used in the present invention is used as a non-diffusible compound, a non-diffusible compound obtained by appropriately selecting a cation moiety and an anion moiety 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,
Acid groups of organic acids such as carboxylic acids, lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as lauryl sulfate anions, etc. FJ ester anion, dialkyl sulfosuccinate anion such as di-2-ethylhexyl sulfosuccinate anion, polyether alcohol sulfate ester anion such as cetyl polyethenoxy sulfate anion, higher fatty acid anion such as stearate anion, polyacrylic Examples include polymers such as acid anions with acid groups attached.

By appropriately selecting the anion moiety and the cation moiety, the non-diffusible tetrazolium compound according to the present invention can be synthesized. The compounds according to the present invention synthesized in this way include, for example, 2゜3.5-)lipheny-2H-tetrazolium-dioctylsuccinate sulfonate, and these are as described in detail in the examples below. In some cases, the soluble salt is dispersed in gelatin and then mixed and dispersed in the gelatin matrix, and in other cases, crystals of the oxidizing agent are synthesized pure and then dissolved in a suitable solvent (e.g. dimethyl sulfoxide). It may then be dispersed in a gelatin matrix. If it is difficult to achieve uniform dispersion, emulsification and dispersion using an appropriate homogenizer such as ultrasonic waves or a Manton-Gorlin homogenizer may give good results. It is also possible to microdisperse it in a high boiling point solvent such as dioctyl phthalate, protect it, and disperse it in a hydrophilic colloid layer.

As mentioned above, by using a plurality of preferred compounds in combination, advantages such as particularly wide development tolerance can be obtained in the present invention, and they may be used in any combination depending on 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 can be prepared by dissolving the tetrazolium compound used in the present invention in a suitable organic solvent and applying it directly to the outermost part of the silver halide photographic material or to the outermost part during production by an overcoating method or the like. They may be incorporated into the silver halide photographic material of the present invention.

The tetrazolium compound used in the present invention is preferably 0.0001 mol or more and up to 10 mol, more preferably 0.0001 mol or more per 1 mol of silver halide contained in the silver halide photographic light-sensitive material used in the invention. 1
It is preferable to use it in a molar range.

The silver halide photographic light-sensitive material to which the image forming method of the present invention is applied must contain at least 50 nm of the maximum photosensitive wavelength of silver halide grains so that it can be handled in a bright room.
Contains a compound that has maximum absorption at long waves.

The optimal maximum absorption wavelength of the above compound varies to some extent depending on the various conditions of the silver halide emulsion used, but
It can be easily found by measuring the optical spectrum. Although such a compound may be contained in the silver halide emulsion layer, it is more effective to contain it in a layer located farther from the emulsion layer than the support, such as a protective layer. Furthermore, it may be contained in an intermediate layer between the silver halide emulsion layer and the protective layer. The effects of the present invention can be further enhanced by using a substance capable of fixing the above compound, such as basic mordant or acid-treated gelatin with a high isoelectric point, in the layer containing the above compound.

At least 50n from the maximum photosensitive wavelength of silver halide grains
The above-mentioned compound having maximum absorption at m-long wavelength is about 5~3g/
It is preferable to use it within the rt range, and it is desirable that the optical density at the maximum absorption wavelength is 0.10 or more. In addition, the maximum absorption wavelength is at least 50 nm long wavelength, but in order to exhibit a sufficient effect, it is preferably 300 nm or less long wavelength, and more preferably 200 nm or less long wavelength.
It is preferable that it is 00 nm or less. Further 50-110
More preferable results can be obtained by containing a combination of two or more types, such as a compound with a long wavelength of 0 nm and a compound with a long wavelength of 100 to 200 nm. These compounds have, for example, the following general formula (IV)-(a), (b), (
c) and specific exemplary compounds, but are of course not limited to these.

General formula (■)-(a) (cuz)m+ is an atomic group, where 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 its sodium
Represents a potassium salt, R4□ and R43 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-mentioned 10X group, and is substituted with a Qlam potassium salt. L represents a phenyl group, a sulfoalkyl group, a sulfoalkoxyalkyl group, a sulfoalkylthioalkyl group, and L represents an optionally substituted methine group. R44 represents an alkyl group, a carboxy group, an alkyloxycarbonyl group, or an acyl-substituted, sulfo-substituted, or unsubstituted amino group. m+ represents an integer 0.1 or 2, and m2 represents an integer aQ or 1, respectively.

General formula CrV) -(b) in the formula R4S+ R461R41+ R49 and R3
゜ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group, a sulfone group, or a sodium or potassium salt thereof, and R47 represents an alkyl group or a carboxyl group.

General formula (■)-(c) In the formula, R5I and R5Z are an alkyl group, a directly substituted alkyl group,
represents an aryl group, an alkoxycarbonyl group, or a carboxyl group, and R5ff and R54 represent an alkyl group substituted with a sulfonic acid group or a carboxyl group, or an aryl group substituted with a sulfonic acid group, a carboxyl group, or a sulfonic acid group; It represents a potassium salt, and L represents a substituted or unsubstituted methine chain. M represents sodium, potassium or hydrogen atom; m represents 0 or 1;

Typical specific examples of compounds according to the general formula [1''/)-(a), (b), and (c) are shown below.

(IV-1) 5υ3Na (rV-2) (TV-3) (IV-4) (IV-5) (TV-6) N Cl1zCHzCHzSOJa (IV-7) H (IV-8) (rV-9) CHzCHzCIIzSOJa SO,Na SO,Na (IV-12) (IV-13) SO,Na (rV-14) (IV-15) OJa (IV-16) (■-17) (IV-18) (IV-19) (IV-21) (IV-22) (IV-23) (IV-24) l (TV-26) (IV-27) 03Na (rl/-28) CH3-C-C= C1l -C-C- C1hII
I 11! 1 (IV-29) SO, Na 's03~a The image forming method of the present invention uses a light source having a maximum specific energy value between 390 and 430 nm as a light source for exposing the silver halide photographic light-sensitive material used in the present invention. . Preferably 400-4
Exposure is performed using a light source having a maximum value at 20 nm, but any light emitting format may be used as long as the light source meets this condition.

For example, the presence or absence of filaments and the presence or absence of electrodes are not limited. Further, the luminescent gas contained in the luminescent electrode tube may also be a halogen gas, a rare gas, or a mixture. Further, a light-emitting metal may be contained at the same time as the gas.

Preferred light sources most suitable for this purpose include an ultra-high pressure mercury lamp, a metal halide lamp, and an electrodeless discharge tube with a V-bulb type emission spectrum, which will be described later.

This type of luminous discharge tube is manufactured by FUSIO
N) and other light source manufacturers, specifically, U.S. Pat. Nos. 4,254,363 and 40
10400, 3993379, 3950670, 3873884, 3790852, 3787705
, 378630B, 3645629, 45366
75, 4422017, 4415838, 439
0813, 4383203, 4359668, 3
911318, 3872349, 3983039,
4042850, 4208587, 431396
9, No. 4,269,581, and the like.

In addition, in the present invention, a light source having a maximum specific energy in the range of 390 to 430 nm is an absorption filter that cuts short waves of 390 nm or less above the ultra-high pressure mercury lamp or metal halide lamp light source in order to obtain the above-mentioned spherical emission spectrum. (Even if you cut long waves of 430nm or more, it will not be shrunk (
This also includes those equipped with a device (which may also be used), thereby achieving the effects of the present invention. This filter can be used near the light source or on the glass plate (second
There are methods such as replacing the glass plate (as shown in the figure) with 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, etc. of any composition, and contains at least 50 mol % of silver chloride. The average particle size of silver halide grains is 0.025 to 0.5
Those in the μm range are preferably used, but from 0.05 to
More preferably 0.30 μm.

The monodispersity of the silver halide grains according to the present invention is expressed by the following formula (
1), and its value is preferably adjusted to 5-60, more preferably 8-30.

The grain size of the silver halide grains according to the present invention is conveniently expressed by the edge length of the cubic grain, and the monodispersity is expressed by the value obtained by dividing the standard deviation of the grain size by the average grain size times 100.

Furthermore, as the silver halide that can be used in the present invention, a small amount (
In both cases, a type having a multilayer laminated structure of two layers can be used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or conversely, silver bromide in the core and silver chloride in the shell. At this time, iodine can be contained in any layer within 5 mol%.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparing 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, etc. are used.

The amount of rhodium salt added can be freely changed depending on the required sensitivity and gradation, but from 10-9 mol to 1 mol to 1 mol of rhodium salt.
A range of O-4 moles is particularly useful.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts are often used in amounts ranging from 10''9 to 10@-4 moles per mole of silver, often for the purpose of improving high-intensity properties.

The silver halide used in the present invention can be enhanced with various chemical sensitizers. As an exacerbating agent,
For example, activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triple (ethylenetetramine, stannous chloride, etc.), such as potassium chloroaurite, potassium aurithiocyanate, potassium chloride elate, 2-ourosulfobenzothiazole methyl chloride, ammonium chlorovaladate, potassium chloroplatinate, sodium chlorovaladite, etc. Various representative noble metal sensitizers can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The effects of the present invention can be further enhanced by incorporating a desensitizing dye and/or an ultraviolet absorber into the silver halide photographic material according to the present invention.

As the reducing dye, the following general formula (V), -(a) to (e) is used.
Those represented by can be preferably used.

As the ultraviolet absorber, the following general formula (V)-(f) is used.

Those represented by (g) can be preferably used.

These compounds are described in U.S. Patent No. 3,567.456;
3,615,639. 3,579,345. Same 3,
615,608. 3.598,596. 3,598
,955. 3,592,653. 3,582.34
No. 3, Special Publication No. 40-26751. 40-27332.
43-13167, 45-8833. 47-87
It can be synthesized by referring to the specifications of No. 46 and the like.

General formula (V)-(a) X+.

General formula (V)-(b) [In the formula, R61 and R6□ represent hydrogen, a halogen atom, a cyano group, or a nitro group. Also, R61 and ・R6
□ may form an aromatic ring. R6ff and R64
each represents an alkyl group, a lower alkenyl group, a phenyl group, or a lower hydroxyalkyl group, and when R61 and R6□ are other than a hydrogen atom, they may be an aryol group, and m4 is a positive integer of 1 to 4. , R6S represents a lower alkyl group or a sulfonated lower alkyl group, and Xl represents an acid anion] General formula CV)-(c) [In the formula, R6 & and R6 are each a hydrogen atom or a nitro group, R611 and R69 are Lower alkyl group, allyl group or phenyl group, Zl is nitrohendithiazole nucleus, nitrobenzoxazole nucleus, 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,
Atom group necessary for forming a nitrothiazole nucleus, a nitronaphthothiazole nucleus, a nitrooxazole nucleus, a nitronaphthoxazole nucleus, a nitroselenazole nucleus, a nitronaphthoselenazole nucleus or a nitropyridine nucleus, X2
represents an anion, m and n each represent 1 or 2.

However, when the compound forms an inner salt, n represents 1] General formula (V)-(d) [In the formula, R1゜+ Roll Rtz and R71 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Aryloxy group or nitro group, R? 4 represents a hydrogen atom, an alkyl group or a nitro group. Z2 is unsubstituted or each lower alkyl group, phenyl group, chenyl group,
Halogen atom, alkoxy group, hydroxy group, cyano group, alkylsulfonyl group, alkoxycarbonyl group,
Thiazole nucleus substituted with phenylsulfonyl group, trifluoromethyl group, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, thiazoline nucleus, Represents an atomic group necessary to form a pyridine nucleus, a quinoline nucleus, an isoquinoline nucleus, a 3,3-dialkyl-3H-indole nucleus, an imidazole nucleus, a benzimidazole nucleus, or a naphthoimidazole nucleus, and Ll and L2 are each unsubstituted or lower Represents a methine chain substituted with an alkyl group or an aryl group, and R? 5 and RY& each represent an unsubstituted or substituted alkyl group, alkenyl group, aryl group, sulfoalkyl group or aralkyl group, X2 represents an anion, and m6 and n each represent 1 or 2. However, when the compound forms an inner salt, n represents 1] General formula (V)-(e) [R7 in the formula? and R? 9 is an alkyl group, Rol
l represents an aryl group. Ll and 2 each represent a methine chain that is unsubstituted or substituted with a lower alkyl group or an aryl group; Z3 is a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus,
Benzoselenazole nucleus, naphthoselenazole nucleus, thiazoline nucleus, pyridine nucleus, quinoline nucleus, 3,3-dialkylindolenine nucleus, imidazole nucleus, imidazo[4,5-
b] Atom group necessary to form a quinoxaline nucleus, χ
2 is an anion, m7 is a positive integer of 1 to 3, m8 is 1 or 2] General formula (V)-(f) [In the formula, R8 represents an alkyl, hydroxyalkyl, cyanoalkyl, or sulfoalkyl group. Z4 represents an oxazole, thiazole, benzoxazole, benzothiazole, imidazole, or benzimidazole ring, and A represents an atomic group necessary to form a pyrrole ring or pyrrolidine ring.

] General formula (V)-(g) [In the formula, R11I+ Ro, R113+ R84 represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group or a sulfoalkyl group. RBS and Rsb represent a sulfonic acid group and an alkylsulfonic acid group. ] Next, specific exemplary compounds of desensitizing dyes and ultraviolet absorbers preferably used in the present invention are shown, but the present invention is not limited thereto. (In addition, some of the examples V-1 to ■-36 shown below do not correspond to the above general formula. Also, pt
s represents a para-toluenesulfonic acid group, ) (V-1) (V-2) (V-3) (V-4) (V-5) 6H5 (V-6) zlls +13 (V-7 ) cHzcn□OH ■ (V-8) CHzCHCHz ゛(V-9) C,H5 (V-10) (V-11) (V-12) (V-13) (V-14) (V-15) (V-16) (V-17) (V-18) (V-19) (V-20) (V-21) (V-22) (V-23) (V-26) (V-27) Js (V-28) C11° (V-29) ■ SO,Na (V-31) (V-32) bU3Na bsu3Na Further, the silver halide emulsion used in the present invention is, for example, disclosed in U.S. Patent No. 2.444. .607, same No. 2,716,06
No. 2, No. 3,512.982, West German Application Publication No. 1
, No. 189゜380, No. 2,058,626, No. 2,118,411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342.596, Japanese Patent Publication No. 47-4417, West-Germany Application Publication No. 2,149,789, Special Publication No. 1973
-2825, Japanese Patent Publication No. 49-13566, etc., preferably compounds described in specifications or publications such as 5.6-)rimethylene-7-hydroxy-S-)riazolo(1,5-a)pyrimidine , 5,6-titramethylene-7-hydroxy-S-triazolo(1,5-a)
Pyrimidine, 5-methyl-7-hydroxy-5-)riazolo(1,5-a)pyrimidine, 7-hydroxy-8-
triazolo(1,5-a)pyrimidine, 5-methyl-6
-promorph-hydroxy-S-)riazolo(1゜5-
a) Pyrimidines, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1-phenyl-5
-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazole@(6-nidrobenzimidazole), etc. for stabilization.

The hydrophilic colloid particularly advantageously used in the present invention is gelatin, but hydrophilic colloids other than gelatin include:
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. Second
．． Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in each specification of U.S. Pat. No. 525,753, or U.S. Pat. Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and meccrylic ester as described in Colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, interlayers, etc.

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

Examples of developing agents used in developing the silver halide photographic material according to the present invention include the following. HO-(
Typical examples of -OH type developing agents include hydroquinone, as well as catechol, pyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, and 2.3 dibromohydroquinone. , 2.5-diethylhydroquinone, catechol, 4-
Examples include chlorocatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, ascorbic acid sorta, and the like.

In addition, typical HO-(CH=CH),,-NJIz type developers include ortho and rose aminophenols, 4-aminophenol, 2-amino-6-
Examples include phenylphenol, 2-amino-4-chloro-6-phenylphenol, N-methyl-p-aminophenol, and the like.

Furthermore, H2N-(CH=CH) 1l-NH□ type developer, for example, 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N- (4-amino-3-methylphenyl)-morpholine, p-phenylenediamine, and the like.

Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. Examples include 3-viratritones, 1-phenyl-4-amino-5-pyrazolone, and 5-aminouracil.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocessFourth Edition) 2nd
91-334 and Journal of the American Chemical Society.
e American Chemical 5ocie
ty) Vol. 73, p. 3.100 (1951) can be effectively used in 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 sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material according to the invention, the effects of the invention will not be impaired. Hydroxylamine and hydrazide compounds can also be used as preservatives, and in this case, the amount used is preferably 5 to 500 g per 11 of the developer, more preferably 20 g.
~200g.

Further, 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, and 5-bentanediol. etc., but diethylene glycol is preferably used. The preferred amount of these glycols used is 5 to 500 g per 11 of the developer.
The amount is more preferably 20 to 200 g. These organic solvents can be used alone or in combination.

By developing the silver halide photographic material according to the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.

The pH value of the developer having the above composition is preferably 9 to 12.
However, the pH value is 10 to 1 from the viewpoint of storage stability and photographic properties.
A range of 1 is more preferred.

The silver halide photographic window optical material according to the present invention can be processed under various conditions. Regarding the processing temperature, for example, the development temperature is preferably 50°C or less, particularly around 30°C, and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes for good effects. often brings. Processing steps other than development, such as washing, stopping,
It is optional to adopt steps such as stabilization, fixation, and if necessary, preduralization and neutralization, and these may be omitted as appropriate.
You can also do that. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕 EXAMPLES The present invention will be specifically explained below with reference to Examples.

Note that, as a matter of course, the present invention is not limited to the embodiments described below.

Example ~ 1 The average grain size and silver halide composition shown in Table I below, containing 10-5 mol of rhodium per mol of rhodium, were prepared by controlled double jet method in an acidic atmosphere of pH 3.0,
Monodisperse particles were created. The growth of particles was carried out in a system containing 30 mg of benzyladenine per 11 of a 1% gelatin aqueous solution. After mixing silver and halide, 6-methyl-4
-Hydroxy-1,3゜3a,7-chitrazaindene was added at a rate of 600 μm per mole of halogenated compound, then washed with water,
Desalted.

Then, 60 μm of 6-methyl-
After adding 4-hydroxy-1,3,3a,7-chitrazaindene, sulfur sensitization was performed. As a stabilizer after sulfur exacerbation, 6-methyl-4-hydroxy-1,3,3a,7
- Added Citrazaindene.

(Silver halide emulsion layer) Additives were added to each of the above emulsions in the amounts shown below, and polyethylene (100 μm thick) was coated with latex subbing according to Example 1 of JP-A-59-19941. Coated on a telescopic support.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer 1.0g/m Saponin 200■/Ipolyethylene glycol 15■/Sodium idodecylbenzenesulfonate 100■/d Hydroquinone 200■/d Styrene-maleic acid copolymer 200■/r! ? Gallic acid butyl ester 500■/d Tetrazolium compound 5-methylbenzotriazole shown in Table-■ 30■/A-reducing dye or ultraviolet absorbing dye 2-Mercaptobenzimidazole-5-sulfonic acid shown in Table-■ 30mg/n? Inert ossein gelatin 1.5 g/m Amount 2.8 g/ld (emulsion layer protective film) The following coating amount was prepared and applied as an emulsion layer protective film.

Fluorinated dioctyl sulfosuccinate 300mg/
m polyethylene glycol (molecule 2000) 30■/d
Matting agent: Synthetic silica (average particle size 3.5μm) 100m
g/% Styrene-maleic acid copolymer 100 mg/m Acid-treated gelatin (isoelectric point 7.0) 1.2 g/
Compounds with absorption maximum at rd5Qnm long wavelength Table - Hardener shown in ■ 2.4-Dichloro-6-oxy-5-) lyazine acid 50■/m' Mordant (Banking N) Add additives in the following amounts. It was coated on the opposite side of the support from the emulsion layer.

Latex polymer: Butyl acrylate-styrene copolymer 0.5 g/m Citric acid 't Omg
/ m saponin 200■
/po-5-nitroindazole 100■/rd
Hydroquinone 100++++r
/+d Phenidon 30■/M
Backing dye Ossein gelatin 2.0g/m Styrene-maleic acid copolymer 0.2g/r+? (Backing layer protective film) Additives were prepared and applied in the amounts shown below.

Dioctyl sulfosuccinate ester 300■/d Lithium nitrate 30■/11 (Matting agent: Polymethyl metatalate (average particle size 4.0 μm) 100■/1 Ossein gelatin (isoelectric point 4.9) 1.1 g/ m Sodium fluorinated dodecylbenzenesulfonate 50■/M2.4-
Dichloro-6-oxy-8-triazine acid 150% (The sample obtained as above was exposed to the light source shown in Table I and developed using the developer and fixer shown below. .

(Exposure method) The spectrum shown in FIG. 1(a) (400 to 420 n
An electrodeless discharge light source manufactured by Fusion, Inc. in the United States called "7-bulb" (having a maximum specific energy at
A conventional light source called a "D sphere" (which has a maximum specific energy at 0 nm) was installed under the glass plate, and a light source was placed on the glass surface, as shown in Figure 2, so that it was possible to evaluate the pasting marks and cutout character quality. Place the original and photosensitive material (starting from the glass side, 6
．． Cut mask film, 5. pasting base, 4. 3. A film on which a line drawing positive image is formed; pasting base,
2. A film on which a halftone image is formed, 1. Photosensitive material for return) was exposed.

Developer formulation> (Composition A) Pure water (ion-exchanged water) 150 g Ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50 g Potassium sulfite (55% W/V aqueous solution) 100 Potassium carbonate 50 g Hydroquinone 15 g 5-Methyl Benzotriazole 200 ■ 1-phenyl-5-mercaptotetrazole 30 ■ Potassium hydroxide Amount to bring the PL+ of the working solution to 10.4 Potassium bromide 4.5 g (composition) Pure water (ion exchange water) 3 ml Diethylene glycol 50 g Ethylene diamine Tetrastic acid disodium salt 5 mg Acetic acid (90% aqueous solution) 0.3 m7 5-nitroindazole 110 ■ 1-phenyl-3-pyrazolidone 500 ■ When using a developer, add the above composition A and composition in 500 rnl of water. They were dissolved in order and finished to 11 for use.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 40
m7 Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g Sodium citrate dihydrate 2B Vinegar M (90% W/W water soluble 'It>
13.6 if (composition) Pure water (ion-exchanged water) 17 m7 sulfuric acid (50% - aqueous solution) 4.7 g aluminum sulfate (A 1203 equivalent content 8.1% IA aqueous solution) 2
When using a 6.5 g fixer, the above composition A was dissolved in 500 mt of water in the order of composition A and composition 11 was used.

The pH of this fixer was about 4.3.

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

(Photographic performance evaluation method) (1) As shown in Figure 2 of pasting marks, a mesh film was placed on the pasting base, the periphery of the mesh film was further fixed with transparent scotch tape for plate making, and exposed and developed. After this tape trace (
A five-point rating was given, with ``5'' indicating that there were no pasting marks) and ``1'' indicating the worst level of conspicuous marks.

(2) Cut-out character quality Cut-out character quality is determined by properly exposing the halftone dot area of the halftone film in FIG. 2 so that the halftone dot area of the return window optical material becomes 50%. The image quality in which the line width of 50 μm on the line drawing film in FIG.

From Table 1, it is found that a silver halide photographic window optical material containing monodisperse fine grain silver halide with a high silver chloride content, a compound having an absorption maximum at a wavelength 59 nm longer than the maximum photosensitive wavelength of the grains, and a tetrazolium compound. , 38 to normal light source
When exposed with an absorption filter that cuts short waves of 5 nm or less (sample measurement 4), comparative samples (positive 1 to 3)
), it can be seen that the pasting mark performance is better than that of the previous method. Furthermore, a sample prepared by adding a desensitizing dye and/or an ultraviolet absorber to the above-mentioned silver halide photographic window optical material was heated at 400 to 420 nm.
It can be seen that when exposed with "7 bulbs" having a maximum specific energy value at m (samples 11h5 to 9), a silver image with extremely good cutout character quality and no pasting marks can be obtained.

In addition, Dainippon Screen Co., Ltd. Akishiro printer P-627F
A Kodak Power Printing Filter CP-2B was attached to the upper part of the light source of M, and the results of exposing Sample 4 in Table 1 were the same as those of Sample No. 4.

〔Effect of the invention〕

As described above, according to the image forming method of the present invention, it is possible to produce silver halide photographs that exhibit good performance when exposed to light using a selected light source, in particular have good cut-out character quality in terms of photographic performance, and also have no traces of tape pasting. Images can be formed on photosensitive materials.

[Brief explanation of the drawing]

FIG. 1(a) shows the spectrum of an electrodeless discharge light source called "V bulb" used in the present invention, and FIG. 1(b) shows "
This is the spectrum of a conventional light source called "D-sphere." Second
The figure is a diagram showing the relationship between the document and the photosensitive material during the cut-out character return operation. 1... Photosensitive material for return, 2... Film on which a halftone image was formed, 3, 5... Pasting base, 4... Film on which a line drawing positive image was formed, 6... Cut mask film. Patent applicant Konishiroku Photo Industry Co., Ltd. Representative patent attorney Toru Takatsuki (a) V Luko Wang (b) D sphere Figure 1

Claims (1)

[Claims] 1. Silver halide grains containing a tetrazolium compound and at least 50 mol % of silver chloride, and a halide containing a compound having maximum absorption at a wavelength at least 50 nm longer than the maximum photosensitive wavelength of the silver halide grains. 1. An image forming method comprising exposing a silver photographic material to light with a light source having a maximum specific energy in the range of 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 light with a light source having a maximum specific energy at 390 to 430 nm. Claim 1:
Image forming method described in section.