JPS6313030A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having high sensitivity and low fogging to He-Ne laser light and excellent halftone quality by incorporating a specific compd. together with a silver chlorobromide or silver chloroiodobromide having a prescribed grain size and compsn. into a silver halide emulsion layer. CONSTITUTION:At least one kind each of the compd. selected from the formula I or II and the compd. selected from the compd. expressed by the formula III are incorporated together with the silver chlorobromide or silver chloroiodobromide having 0.05-0.5mum average grain size and <=20 monodispersion and contg. at least 50mol% silver chloride into the silver halide emulsion layer. In the formula, Y1, Y2 are S, Se atom, R1, R2 are a lower alkyl group, alkyl group having a sulfo group, R is a prescribed group such as a lower alkyl group, A, B naphthol group, Z1, Z2 are an atomic group necessary for forming 5-6-membered nitrogenous heterocycles, R3 and R4 are an unsatd. aliphat. group, Q, Q1 are an atomic group necessary for forming a prescribed ring such as 4-thiazolidinone, L1-L3 are a methin group, X is a mineral acid or org. acid anion, n is 0 or 1.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide photographic material.

More specifically, the present invention relates to a silver halide photographic material having high sensitivity, especially to helium-neon lasers, excellent halftone dot quality, and improved capri.

[Conventional technology]

In recent years, various scanner systems have been developed and used to automate camera work in printing. There are black and white, color, drum type, and flat type types, but we will explain this using color printing as an example.

To perform color printing, it is first necessary to separate the original into four color separation negatives of yellow, magenta, cyan, and black, and then perform color correction and gradation correction by masking. Performing this with a camera requires a high level of skill and complex photo manipulation, so a color scanner was developed in an attempt to automate everything under electronic control.

A color document wrapped around a document drum is scanned with a white light spot,
Transmission (or reflection), the light is separated into three components by a semi-transparent mirror and a filter, each converted into an electrical signal and input into a calculation circuit. The total W section calculates all tone compression adjustment, color correction, undercolor removal, etc., and outputs the required densities for each of the yellow, magenta, cyan, and black plates as electrical signals. This is converted into light intensity by a light modulating discharge tube, and the film on the image receiving drum is scanned and exposed to obtain a corrected negative (or positive). The film used for this) is a so-called scanner film, and this type of scanner uses a continuous-tone, high-sensitivity silver halide photographic material with good linearity.

In addition, in recent years, direct scanners have been developed that use a powerful laser beam as a light source, and scan and expose a taxi screen and lithographic film wrapped around an image-receiving drum to obtain a decomposed net (or decomposed positive). Methods such as dot generators that create dots have been developed, but recently the dot generator method has become mainstream. This type of scanner uses particularly high-contrast silver halide photographic materials.

Until now, argon lasers have been mainly used as the light source for dot generator type scanners. However, although the argon laser has a high output, it has the disadvantages of being expensive and having a short lifespan. Therefore, recently, helium-neon lasers have attracted attention as a light source to replace argon lasers and have been put into practical use. Helium-neon lasers are cheaper and have a longer lifespan than argon lasers. However, the output is inferior. Therefore, scanner films suitable for helium-neon lasers are required to have high sensitivity, low fog, high contrast, and excellent halftone quality, but there is currently no film that fully satisfies these requirements. It is.

[Problem that the invention seeks to solve]

As mentioned above, with the spread of scanner systems in recent years, helium-neon lasers, which are dot generator type and are inexpensive and have a long life, are increasingly being used as light sources.

However, since helium neon lasers have inferior output compared to argon lasers, high sensitivity is required for scanner films.

That is, a first object of the present invention is to provide a silver halide photographic material that has high sensitivity to a helium-neon laser light source and has little fog.

Furthermore, a second object of the present invention is to produce a helium-neon laser.
The object of the present invention is to provide a silver halide photographic material having high sensitivity to a light source, low fog, and excellent halftone dot quality.

[Means for solving problems]

It is an object of the present invention to solve the above-mentioned problems and provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which a halogenated material contained in at least one of the silver halide emulsion layers is provided. Silver has an average particle size of 0.
Silver chlorobromide or silver chloroiodobromide having a monodispersity of 05 to 0.5 μm1 of 20 or less and containing at least 50 mol% of silver chloride, and the light-sensitive material has the following general formula (1) or [I
A silver halide photographic material containing at least one compound selected from the compounds represented by I) and at least one compound selected from the compounds represented by the following general formula CI[[]. This was achieved by using .

The silver halide photographic material of the present invention has an average grain size of 0.0.
An emulsion layer consisting of a silver halide emulsion having a monodispersity of 20 or less and containing silver halide grains of 5 to 0.5 μm size is formed on a support, and the silver halide in the emulsion layer is silver chloride. It contains at least 50 mol% of. Such a silver halide emulsion layer is particularly suitable as a light-sensitive material for laser beams, and exhibits unprecedented resolution.

The sensitizing dye shown in the general formula (11) used in the present invention will be explained as follows: General formula CI In the formula, Yl-Y2 represent a sulfur atom and a selenium atom, respectively. (Except that Y, Y2 are selenium atoms at the same time) R1-R2 are lower alkyl groups (e.g. methyl, ethyl, propyl, butyl, etc.), furkyl groups having a sulfo group (e.g. β-sulfoethyl) group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (for example, sulfoethoxyethyl group, sulfopropoxyethyl group).

R represents a lower furkyl group (eg, ethyl group, propyl group).

A and B represent a group of nonmetallic atoms necessary to complete a tothiazole ring, benzothiazole ring, naphthoselenazole ring, or benzoselenazole ring. Each of these rings has a lower alkyl group (e.g. ethyl group, methyl group, etc.)
, alkoxy groups (e.g. methoxy group, nidoxy group, etc.),
It represents a hydroxyl group (eg, phenyl group), an alphkyl dicarbonyl group (eg, methoxycarbonyl group), a halogen atom (eg, chlorine atom, bromine atom, etc.), and a hydrogen atom.

Further, the lower 11 fulkyl group may be substituted.

Examples of the 7-tothiazole ring, benzothiazole ring, naphthoselenazole ring, and benzoselenazole ring completed by the nonmetallic atom group substituting these substituents are α-7-tothiazole, β-7-tothiazole, β, β-su7toti7zole, benzothiazol, 5-methylbenzothiazole, 5-chlorobenzothiazole, 5-nodoxybenzothiazole, 5-bromobenzothiazole, 5*
6-ymethylbenzothiazole, 5-cyano-benzothiazole, 5-phenylbenzothiazole, 5-hydroxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5-nitoxy -6-methylbenzothiazole,
5-ethoxy-6-methylbenzothiazole, 5-carboxy-benzothiazole, a-7toselenazole,
β-su7toselenazole, β, β-su7toselenazole, benzoselenazole, 5-methylbenzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-phenyl-benzoselenazole, 5
, 6-nomethylbenzoselenazole, and 5-hydroxybenzoselenazole.

X represents an anion commonly used in cyanine dyes (eg, halogen ion, benzenesulfonate ion, 9-)luenesulfonate ion, etc.).

The term represents 1 or O, and when it is an inner salt, it represents -=0.

Next, specific examples of the sensitizing dye represented by the general formula CI) are shown in Table 1, but the sensitizing dye represented by the general formula (I) is not limited to these.

The sensitizing dyes used in the silver halide photographic material of the present invention are described in U.S. Patent No. 2.5.03,776, British Patent No. 742,112, and French Patent No. 2,065,662. If you refer to the Japanese Patent Publication No. 40-2346,
It can be easily synthesized by related engineers. -Next, general formula CII) will be explained.

General formula (n) where 2S2. each form a 5-shell and/or 6-shell nitrogen-containing heterocycle commonly used in cyanine dyes (the carbon atoms of this heterocycle may have a substituent that does not adversely affect sensitization). represents the atomic group necessary for
The above-mentioned heterocycles include, for example, a thiazoline ring, a thiazole ring, a benzothiazole ring, a dithiazole ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, and a 2-quinoline ring. , 4-quinoline ring, 2-pyrinone ring, 4-pyridine ring, 3t 3-dialkylindolenine ring, penzimiguzole ring, etc., and the carbon atoms of this heterocycle include a halogen atom, an alkyl group, and an alkoxy group. , a hydroxy group, a monoaryl group, or the like may be substituted.

R and R each represent a saturated or unsaturated aliphatic group, such as a lower alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. having 8 or less carbon atoms), a substituted alkyl group ( Preferably, the number of carbon atoms in the alkyl radical is 5 or less) such as a hydroxy group, an acetoxy group, an alkoxy group, a carboxy group, a flufucidicarbonyl group,
It represents a group having a substituent such as a sulfo group, a vinyl group, or a mono-7-aryl group. Specific examples of substituted alkyl groups include β-
Hydroxyethyl group, γ-hydroxypropyl group, β-
7 setoxyethyl group, γ-7 setoxyprobyl group, β-
Methoxyethyl group, γ-methoxypropyl group, carboxymethyl group, β-carboxyethyl group, γ-carboxypropyl group, δ-carboxybutyl group, ω-carboxypentyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, β- methoxycarbonylethyl group,
γ-nodoxycarbonylpropyl group, δ-methoxycarbonylbutyl group, β-sulfoethyl group, γ-sulfoglovir group, γ-sulfobutyl group, δ-sulfobutyl group, vinylmethyl group, benol group, 7enethyl group, p-carboxy Examples include benol group and p-sulfo7enethyl group.

Q and Q (combination) represent an atomic group necessary to form 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone.

Examples of the substituent attached to the nitrogen atom at position 3 of thiazolidinone or imidazolinone include an alkyl group, (
Methyl group, ethyl group, propyl group, etc.) allyl
l) groups, aralkyl groups (bennol group, p-carboxyphenylmethyl group, etc.), aryl groups (phenyl group, p-carboxyphenyl group, etc.), hydroxyalkyl groups (β-hydroxyethyl group, etc.), carboxyalkyl groups (carboxymethyl groups), alphkidicarbonyl alkyl groups (
methoxycarbonylethyl group, etc.).

L mouth L2. L is a methine group or a substituted methine group (= C-
). R2 represents an optionally substituted lower alkyl group or aryl group. Examples of unsubstituted lower alkyl groups for R2 include methyl groups and ethyl groups; examples of substituted alkyl groups include those substituted with alkoxy groups, carboxyl groups, alkoxycarbonyl groups, and monoaryl groups; more specifically, β- Ethoxyethyl group, β-carboquinethyl group, β-methoxycarbonylethyl group,
The benzyl group, 7enethyl group, etc. and the naryl group include unsubstituted ones, substituted ones with alkoxy groups, halogen atoms, carboxy groups, etc., and more specifically, phenyl groups, p
Examples include -methoxyphenyl group, p-chlorophenyl group, and 0-carboxyphenyl group.

Alternatively, R, L, and R3 may each be bonded via a methylene chain to form a nitrogen-containing heterocycle (for example, 5-shell, 6-shell, etc.).

11=n represents O or 1, respectively.

When 0, the dye forms a betaine structure.

X represents a mineral or organic acid anion such as chloride, bromide, yogate, verchlorate, benzenesulfone), p-)luenesulfonate, methylsulfate, ethylsulfate, and the like.

Next, the sensitizing dye represented by the general formula (Il) used in the present invention will be illustrated.However, the sensitizing dye is not limited to this.

■-1 ゛・〜、-ノ' Do I-3 Do ■-5 Do I-8 Do ■-10 ■-11 ■-12 ■- ■-13 ■-14 ■-15 One ■-16 Shi215 ■ -17! - ■-18 ■- ■-19 ■-20 ■-21 ■-22 ■-23 Do ■-24 ■- ■-25 ■-26 ■-29 n-30 ■-31 ■-32 r- ■-33 ■- ■-34 ■-35 ■-36 ■- ■-37 ■-38 To use the compound represented by the above general formula (1) (It, ) in a silver halide emulsion, add it to the coating solution. It may be added by dissolving it, or by dissolving it in water or an organic solvent such as methanol, ethanol, acetone, etc. alone or in a mixture thereof. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance.

The amount of the compound used in the present invention when added to a silver halide emulsion varies depending on the type of silver halide emulsion and the type of compound, but is usually in the range of 5 mg to 1000+++ g per mole of silver halide.

The compound according to the present invention may be added to the silver halide emulsion at any time, but it is usually desirable to add it at any time during ripening or at any time after completion of ripening and immediately before coating.

Further, the compounds represented by the general formulas (1) and (II) used in the present invention may be used alone or in combination of two or more types.

Next, to explain the general formula CI[[), the general formula (I
[[) %Formula% At least two sites are hydroxyl groups, and the remaining sites are hydrogen atoms and halogen atoms (e.g. chlorine atom, bromine atom, etc.)
, a sulfonic acid group, or an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, or a carbonyl group which may have a substituent, for example, as a substituent for the alkyl group, a hydroxyl group, an alkoxyl group, etc. Substituents for aryl groups such as sulfone groups and sulfone groups include furkyl groups, hydroxyl groups, and nitro groups; substituents for aralkyl groups include alkyl groups and hydroxyl groups; and substituents for heterocyclic groups include alkyl groups and hydroxyl groups. , alkoxyl group, ami7 group, etc., the substituent of carbonyl group is an alkyl group, hydroxyl group, alkoxyl group, etc., or represents -〇-R, □ or -8-R, □, R6-Ry-R □R,,
R. Two adjacent sites of tRll may form a five-shell or six-shell carbocycle or a heterocycle.

RI2 is an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group which may have a substituent, and when it has a substituent, for example, the substituent of the alkyl group includes a hydroxyl group, an alkoxyl group, a sulfone group, etc. Substituents for aryl groups include alkyl groups, hydroxyl groups, nitro groups, etc.; substituents for aralkyl groups include alkyl groups, hydroxyl groups, etc.
Substituents of the heterocyclic group include an alkyl group, a hydroxyl group,
These include an alkoxyl group, an amine 7 group, and the like. ) Next, the above general formula (III) contained in the photosensitive material of the present invention
Specific examples of compounds represented by are shown in Table 2, however,
Naturally, the compounds used in the present invention are not limited to these.

The compound represented by the general formula (Ii[) of the present invention is disclosed in, for example, U.S. Patent Nos. 2,008,032 and 2,008
, No. 337, No. 2,732,300, No. 3,37
9,529, JP-A-49-129536, JP-A-50-93971, and E. C. Armstrong et a.
l) Journal American Chemical Society (J, 8m, Chew, Soc,) 82.19
28-1935 (1960), D.E. Core Lens (D.

E, Koalens) Journal American Chemical Society (J, ^m, Chea+, So
e, ) 56.2478-2481 (1934), Pharmaceutical Journal 56.814-828 (1936) Although the amount of the compound of general formula (III) used in the present invention is arbitrary, the silver halide photograph of the present invention It is preferably used in an amount up to tog per mole of silver halide contained in the light-sensitive material.

The compound represented by the general formula (III) can be dissolved in a suitable solvent such as water, methanol, ethanol, etc. and added to the constituent elements of the silver halide photographic light-sensitive material according to the present invention. The compound represented by the general formula (I[[) is preferably added to the silver halide emulsion layer. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance. Further, these compounds represented by the general formula (I[[) can be added to the constituent elements of the silver halide photographic material at any time during the production process of the photographic material. When added to a silver halide emulsion layer, it is preferably added before chemical ripening or coating.
The compounds of general formula (III) used in the present invention may be used alone or in combination of two or more.

The silver halide used in the silver halide photosensitive material of the present invention is silver chlorobromide or silver chloroiodobromide, and at least 50 mol%
contains silver chloride. If the silver chloride content is less than 50 mol%, the high contrast will be impaired.The average grain size of the silver halide used is in the range of 0.05 to 0.5μ-, with a zero grain size of 0.05μ- If it is smaller than 0.5 μm, the necessary sensitivity cannot be obtained, and if it is larger than 0.5 μm, the necessary practical density cannot be obtained, which is not preferable.

In practicing the invention, the photographic emulsion may be, for example,
Graph Kid (P, (:Iafkides) M
"Chimie et PF + ysi" published by Paul Montell
que Photography; Paul
In 1967, G. F. Duffin published "Photographic Emuls 1 Chemistry" published by The 7 Orcal Press.
ion Ches+1try; The Focal
Published by Press'> 1988, Boo! /I, -
Zelikmaneta (V, L, Zelikmaneta
l) Making and Coating Photographic Emalreno 3'The 7 Ocal 7'
Published by Hakingand Coating Pho
tographic Emulsion,' TheF
7!411! using the method described in (Published by Ocal Press) in 1964, etc. ! can do. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided synthesis method, simultaneous mixing method, or a combination thereof. Preferably used in the present invention is a combination of acidic and simultaneous mixing methods.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a so-called monodisperse silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The monodispersity of silver halide grains used in the present invention can be defined by the following formula.

In the present invention, the grain size of silver halide grains is conveniently expressed by the edge of cubic crystal grains, or in the case of non-cubic grains, by the diameter of the projected area converted into a circle, and the average value thereof is expressed as the average grain size. , monodispersity is the standard deviation of the particle size as the average particle size m″Ch?Fl
The value is multiplied by 100.

Here, if we express the degree of monodispersity in the formula, becomes.

In the present invention, it is important to adjust the silver halide grains so that this value is 20 or less. If the monodispersity exceeds 20, high contrast will be impaired and sharpness will deteriorate, which is not desirable. In particular, such monodisperse emulsions are more preferable as photosensitive materials for helium and neon lasers, and appropriate halftone dot quality can be obtained.

Here, contrast is defined as the difference between bright and dark areas in a photographic image.
It represents the degree of degree difference. Also sharpness (S)
The term "barpness" refers to the degree to which the boundaries of an image are clear and even minute details are shown.

To produce the silver halide grains used in the present invention, for example, in the step of mixing a water-soluble silver salt solution and a water-soluble halide solution in the presence of a protective colloid to form silver halide grains, the During the period during which at least 30 mol% of the total halogen content is produced, the pAg of the emulsion in which this production takes place is between 5°0 and 9.5, preferably pAg6.
Control within the range of ~8.

The silver halide photographic emulsion used in the present invention can be improved in high-intensity, short-exposure characteristics by using in combination a compound containing a metal of Group 8 of the periodic table.

Metals belonging to Group 8 of the periodic table include iron, cobalt,
It refers to nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, and particularly preferred compounds containing these metals include ferric chloride, red blood salt, cobalt chloride), cobalt nitrate, ruthio salt, Nickel chloride, nickel sulfate, ruthenium chloride, ruthenium hydroxide, rhodium chloride, ammonium hexachlororhodate, sodium hexachlororhodate,
Potassium hexabromorodate, palladium chloride, palladium nitrate, potassium hexachloropalladate, osmium chloride, iridium chloride (IrCNa and IrC1,)
, potassium hexachloroiridate, ammonium hexachloroiridate, potassium hexachloroplatinate, and the like. These compounds may be added in an amount of generally 10-1 to 10-6 mol per mol of silver halide, preferably as an aqueous solution, during or after grain formation, physical ripening, or chemical ripening of the silver halide emulsion. In particular, when desensitization or reversal is likely to occur due to the type of metal in the compound used, the method of preparing the emulsion, or the development method, it is recommended to use 10-8 to 10-7 per mole of silver halide before the end of physical ripening. preferable.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, a Nudel water washing method that involves gelatinization may be used, and inorganic salts, anionic surfactants, anionic polymers (e.g. A precipitation method (70 curation) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used.

The silver halide emulsion used in the present invention is chemically sensitized in the usual manner. For chemical sensitization, e.g. Die
Grundlagen der Photogr
aphischen prozesse wit S
ilberhalogeniden,'^kademi
sche Verlags Ge5ellschaft
) 1968, pages 675-734 can be used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates,
Sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol
A wide variety of synthetic hydrophilic polymeric materials can be used, such as monopolymers or copolymers of polyvinylpyrazole, polyvinylpyrazole, and the like.

In addition to lime-processed gelatin, acid-processed gelatin and Pretin of Society of Science of 7 Otography Op Japan (Bu
ll, Soc, Sci, Phot, Japan)
, No. 16, page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanate U, bromoacetic acid, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The product obtained by reacting is used.

When carrying out the present invention, the photographic emulsion may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroingsoles,
Triazoles, benzotriazoles, benzimidazoles (especially dinitro- or halogen-substituted compounds); heteromercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1 -722-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthion; azaindenes such as tetraazaindenes ( In particular, many compounds known as anti-capri agents or stabilizers can be added, such as 4-hydroxy substituted (1,3I 3a!7) tetraazaindenes); benzenethiosulfonic acid; benzenesulfinic acid; etc. can.

Further, a polymer latex can be contained in the silver halide photographic emulsion used in the present invention. As the polymer latex, an aqueous dispersion of homo or fuvolimer such as methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, glycinol acrylate, styrene, vinyl chloride, vinylidene chloride, etc. is used.

The silver halide photographic emulsion used in the present invention includes commonly used chemical sensitizers, stabilizers, toning agents, hardeners other than those of the present invention, anti-capri agents, surfactants, thickeners, plasticizers, and slippery agents. Agents, development inhibitors, ultraviolet absorbers, irradiation inhibitors, dyes, heavy metals, matting agents, etc. can be further incorporated by conventional methods.

The silver halide photographic emulsion used in the present invention is usually applied to a suitable support, such as a plastic film, a cellulose derivative film such as cellulose triacetate, a synthetic resin film such as polyethylene terephthalate, baryta paper, resin coated paper, synthetic paper, etc. It can be applied by the following method.

After exposure, the silver halide photographic material according to the present invention can be developed by various commonly used methods.

The black and white developer contains hydroxybenzenes, 1-phenyl-
3-pyrazolidones, aminophenols! It is an alkaline solution containing a developing agent such as amine/benzene, etc., and may also contain other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

However, as a matter of course, the present invention is not limited to this.

Example 1 A 35 mol % silver chlorobromide gelatin emulsion containing bromide was prepared by a simultaneous mixing method at 45° C. over 35 minutes. The emulsion thus prepared was desalted and redispersed, with an average grain size of 0.2 μm.
In this emulsion, a monodisperse emulsion of m is obtained.
．． Contains 0 mol. This emulsion was chemically sensitized with 5B of sodium thiosulfate and 8 mg of chloroauric acid in 1 mole of HgX at a stoichiometric ratio of 55"C for 70 minutes. This chemically sensitized emulsion was divided into 10 equal parts. As shown in the table, Compound l-15 represented by the general formula CI) and Compound I [[-1,II[41■8 represented by the general formula] were added to prepare Samples Nos. 1 to 10, respectively. Sample Nol~N in Table 3
ol0 contains antifoggant and 1-phenyl-5-
7 mj of 0°4% solution of Mercaptotheraseel! , 6-methyl-4-hydroxy-1,3,3a as a stabilizer
v 1% solution of 7-chitrazaindene at 150II1
1. In addition, 10ml of 20% saponin aqueous solution as a spreading agent.
．． 7 ml of 3% formalin aqueous solution as a hardening agent, and sodium-2,6-dichloro-1,
0.8 g of 3,5-) riazine-4-olate was added, and further 35 g of a high molecular weight latex polymer of ethyl acrylate was added. Each of these emulsions was coated on a film support with a silver content of 3.5. /112, and further as a W1 membrane, add 5% to an aqueous solution of 500 g of inert gelatin.
Gelatin was added with 8011 formalin and 15 g of amorphous silica with an average particle size of 2 μm. The above emulsion layer and this protective layer were simultaneously coated at an Ig/function ratio of 2.

Table 3 The 10 types of films thus obtained were each exposed to a helium-neon laser and Sakura automatic development fiGR-
In No. 27, development was carried out at 38° C. for 20 seconds using a developer having the following developer formulation 1 and a fixer having the fixer formulation to effect fixation.

Further, the unexposed sample was developed and fixed using the above-mentioned automatic processor at 40° C. for 60 seconds using the following developer and fixer. This is called the degree of overdevelopment fog.

The sensitivity was expressed as the reciprocal of the exposure amount of Capri density + 3.0.

Furthermore, for this sample, the helium neon laser
% Halftone dots were not formed before exposure, and the temperature was increased to 38°C in the same manner as above.
, development for 20 seconds, fixing, and evaluation of halftone dot quality.

The quality of the halftone dots is determined by visually checking the condition of fringes (blurring) that occur around the halftone dots! Evaluation was made on a five-point scale, with 5 indicating the smallest fringe. That is, "5" means excellent, and "1" means extremely poor. Generally, if the evaluation of 50% halftone dots is "3" or less, Xiaomi cannot accept it.

<Developer prescription>-1 Pure water (ion exchange water) approximately 1300 mj
! Potassium sulfite 60g Ethylenediamine diacetate dilium salt 2g Potassium hydroxide 10.5g 5-methylbenzotriazole 300+*H diethylene glycol 25゜1-phenyl-4,4-tumethyl-3-virazolidi/one
300mg1-7enil'5
-Mercaptotetrazole 60-g potassium bromide
3.5g hydroquinone
20g potassium carbonate
15 g of pure water (ion-exchanged water) was added to make the total volume to 1.000 ml. When using the developer, the entire amount of the above-mentioned developer was dissolved in 3N of pure water (ion-exchanged water).

The pH of the developer B before diluting with water was about 11.4, and the pH of the developer after diluting with water was about 10.8.

<Fixer formulation> (M composition) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0 theory! Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90%W/
W aqueous solution) 13.6mf (composition) Pure water (ion exchange water) 17 +
a 1 sulfur # (50% W/W aqueous solution)
4.7g aluminum sulfate (^120.w, rt
(8.1% W/W aqueous solution) 26
．． When using 5g fixer, the above composition A in 500ml of water,
AM and B were dissolved in this order and finished to 11 for use.

The pu of this fixer was about 4.3.

The results of these measurements are shown in Table 4. That is, samples No. 2 to No. 10 containing both the compounds belonging to the general formula (1) and CI [[] according to the present invention have a sensitivity of 246 to 250, a fog of 0.01 to 0.02 in normal processing, and a fog of 0.01 to 0.02 in overdevelopment. The processing is 0.05-0.11 and the halftone quality is 4.5-4.
It was good at 75.

On the other hand, the sample Mol containing only the compound belonging to the general formula [1] has a sensitivity of 250 and a fog of 0 in normal processing.
．． 07, and 0.27 in over-development processing, which is clearly high 6
The halftone quality is also inferior at 2.0. That is, the method of the present invention clearly obtained excellent results.

Table 4 Example 2 The compounds of the present invention in Example 1 were added as shown in Table @S, and the other conditions were the same as in Example 1 to prepare samples No.
20 were produced. The developer is formulation 2, and the normal processing is 28°.
C for 30 seconds and over-development treatment at 38° C. for 60 seconds. All other evaluations were made in the same manner as in Example 1.

The results of these measurements are shown in Table 6. That is, samples No. 11 to No. 20 containing both compounds belonging to general formulas (II) and (III) according to the present invention had a sensitivity of 299 to 302, a fog of 0.01 to 0.02 in normal processing, and 0.0 in overdevelopment.
8 to 0.15, and the halftone dot quality is 4.5 to 4.75. On the other hand, sample No. 11, which is a comparison sample and contains only compounds belonging to the general formula [I[), usually has a fog of 0.
．． 06, overdevelopment is 0.26, and halftone quality is 2.
5 and inferior.

That is, the method of the present invention yielded clearly excellent results.

゛゛ケノ' 5th table Developer formulation>-2 (Composition A) Pure water (ion-exchanged water) 1501Ill Ethylenediaminetetraacetic acid disodium salt 2g Ethylene glycol Sog Potassium sulfite (55%-/V aqueous solution) 100n1 Carbonic acid Potassium 50g Hydroquinone 15g 5-methylbenzotriazole 200mg 1-phenyl-5-mercaptotetrazole 30IIg Potassium hydroxide Amount to bring the pH of the working solution to 10.4 Potassium bromide 2g (composition) Pure water (ion-exchanged water) 3I111 Diethylene glycol 50g Ethylene diamine Tetraacetic acid dinasylium salt 258 acetic acid (90
% aqueous solution) 0.3s15-nitroingsol 110mg1-phenyl-3-pyrazolidone 500gWhen using a developer, the above composition A was dissolved in the order of composition A and composition 11 in water 500II11, and the composition was finished to 11 and used.

Table 6 The present invention makes it possible to provide a film that is highly sensitive to helium-neon laser light sources, has little capri, and has excellent halftone dot quality, thereby providing a light source for scanner systems. This makes it possible to use a helium-neon laser light source, which is cheaper and has a longer lifespan than a fulbone laser.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide contained in at least one of the silver halide emulsion layers has an average grain size of 0. 05 to 0.5 μm, a monodispersity of 20 or less, and silver chlorobromide or silver chloroiodobromide containing at least 50 mol% of silver chloride, and the light-sensitive material has the following general formula [
A silver halide characterized by containing at least one compound selected from the compounds represented by [I] or [II] and at least one compound selected from the compounds represented by the following general formula [III] Photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y_1 and Y_2 represent a sulfur atom and a selenium atom, respectively. (Except that Y_1 and Y_2 are both selenium atoms.) R_1 and R_2 represent a lower alkyl group and an alkyl group having a sulfo group, respectively. R represents a lower alkyl group, and A and B represent a group of nonmetallic atoms necessary to complete the naphthothiazole ring, benzothiazole ring, naphthoselenazole ring, or benzoselenazole ring. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included. represents a group of atoms. R_3 and R_4 each represent a saturated or unsaturated aliphatic group. Q and Q_1 (combination) represent an atomic group necessary to form a 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone ring. L_1, L_2, L_3 are methine groups, and L_1 and R_
3. L_3 and R_4 may each be bonded through a methylene chain to form a nitrogen-containing heterocycle. m and n represent 0 or 1. X represents a mineral acid or organic acid anion. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R_6, R_7, R_8, R_9, R_1_0, R_
At least two sites in 1_1 are hydroxyl groups, and the remaining sites are hydrogen atoms, halogen atoms, sulfonic acid groups, alkyl groups, aryl groups, aralkyl groups, carbonyl groups, heterocyclic groups, or -OR_1_2 or -S-
Represented by R_1_2, or R_6, R_7, R_8
, R_9, R_1_0, and R_1_1, two adjacent sites may form a 5- or 6-membered carbocycle or heterocycle. R_1_2 is an alkyl group,
Represents an aryl group, an aralkyl group, or a heterocyclic group. ]