JPH0239A - Silver halide photographic sensitive material having high contrast - Google Patents

Abstract

PURPOSE:To obtain the title material which has safety in a yellow safety lamp and high sensitivity against the laser ray source and high contrast by incorporating a specified compd. in an emulsion layer contg. a silver halide having a specified mean particle size and a specified degree of monodispersion. CONSTITUTION:The silver halide particle contd. in the silver halide emulsion layer has the mean particle size of 0.05-0.5mum, and the degree of monodispersion of a range of 5-20. At least one kind of the compds. shown by formulas I, II and III, and the compd. shown by formula IV are incorporated in the emulsion layer. In formula I, R1 and R2 are each aryl group, R is an org. binging group. In formula II, R21 is an aliphatic group, R22, P1 and P2 are each hydrogen atom. In formula III, Ar is an anti-dispersible group or aryl group, R31 is a substd. alkyl group. In formula IV, R1 and R2 are each aryl group, R is an org. binding group. The photosensitive material which has the safety in the yellow safety lamp, and the high sensitivity against the laser ray source and the excellent high contrast is obtd. by mounting the emulsion layer on a supporting body.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material with extremely high contrast.The photographic light-sensitive material of the present invention can be handled under, for example, a yellow safety light. It can be used as a silver halide photographic light-sensitive material for plate making, such as a line drawing light-sensitive material for laser scanners or a reverse light-sensitive material.

[Background of the invention]

In recent years, the use of bright rooms in the plate-making process has progressed, and silver halide photographic materials that can be handled under white fluorescent lamps or yellow safety lamps have come into wide use9.

The performance required of a photosensitive material used in such a bright room is that it has high contrast and sufficient maximum density, and can be handled for a long time in a bright room (under white fluorescent light or yellow safety light). It also has high sensitivity to printer and scanner light sources.

On the other hand, it has become common to use scanners in photolithography processes. Scanners are used for color separation of color originals and layout of printed originals. Laser light is generally used as the light source for scanners, and lasers that emit light in the blue region are often used, but even in processes that use such scanners, photosensitive materials can be handled under bright yellow safety lights. You are required to do so.

In addition, in the plate-making process, a so-called hatching process is necessary to convert the gradation of the original image, which has continuous gradations, into the area of halftone dots. It is common practice to directly obtain halftone images. Therefore, as a photosensitive material used in such a scanner, a silver halide photographic material is required that has high photosensitivity to ^r laser light and extremely high contrast suitable for forming halftone dots. A photosensitive material suitable for carrying out 11-point formation is, for example, a fine silver halide grain with an average grain size of about 0.5 μm or less, a narrow particle size distribution, and a uniform grain shape. A silver halide photosensitive material consisting of a silver chlorobromide or silver chloroiodide emulsion having a high content of, for example, 50 mol% or more, is processed using an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions. So-called lithographic photosensitive materials are used for development, but such developers have poor stability and are susceptible to auto-oxidation, so plate makers have to work hard to consistently obtain high-quality halftone negative or halftone positive images. In this case, it is necessary to manage the developer in order to keep the activity of the developer constant, which decreases with time or use, and the operation becomes complicated.

As one of the methods to solve these problems,
JP-A-67419 discloses a silver halide photographic material containing a tetrazolium compound. Although this photographic light-sensitive material has extremely high contrast and can form excellent halftone images, it is also greatly affected by the sensitizing dyes and other additives that are used in combination. It has been difficult to produce a photosensitive material with high sensitivity and little fogging caused by yellow safety lights.

[Problem that the invention seeks to solve]

The object of the present invention is to provide a silver halide photographic material that is safe to handle under yellow safety lights, has high sensitivity to laser light sources, and provides excellent halftone dots with high contrast. It is on offer.

Other objects of the invention will become apparent from the description in Book 7a.

[Means for solving problems]

The above object is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the silver halide contained in at least one of the silver halide emulsion layers has an average grain size of 0.05. ~0.5μ, monodispersity of 5 to 25, and at least one compound selected from the following general formulas [1], [2], and [3] in at least one of the silver halide emulsion layers. types of compounds,
and at least one type of compound selected from the compounds represented by the following general formula [4]. .

General formula [1] In the formula, R8 and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is θ~6, and l is O
or represents l.

Here, examples of the aryl group represented by R1 and R1 include phenyl group, naphthyl group, etc., and examples of the heterocyclic group include pyridyl group, benzothiazolyl group, quinolyl group, thienyl group, etc. Preferably it is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R1 and R2. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, inzoloboxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamino groups. (e.g. acetylamino, bivalylamino,
Benzoylamino, tetradecanoylamino, α-(2
, 4-di-t-amylphenoxy)butyrylamino, etc.), sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylaminonylaminourea groups (e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g., phenylthiourea, ethyl thiourea, etc.), hydroxy group, amine group, alkylamino group (e.g., methylamino, dimethylamino, etc.), carboxy group, alkoxycarbonyl group (e.g., ethoxycarbonyl), carbamoyl group, sulfo group, etc. Represented by R Examples of divalent organic groups include alkylene groups (e.g., methylene, ethylene,
trimethylene, tetramethylene, etc.), arylene group (
Example, t. Examples include phenylene, naphthylene, aralkylene groups, etc., but alkylene groups include oxy groups, thio groups, seleno groups, carbonyl groups, -N- groups (R3
represents a hydrogen atom, an alkyl group, an aryl group), a sulfonyl group, etc. Various substituents can be introduced into the group represented by R.

Examples of the substituent include -CONHNHR. (R
4 is the above-mentioned R. and R2), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group,
Examples include a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

Among the compounds represented by the general formula [1], preferably R1
and R1 is a substituted or unsubstituted phenyl group, and n-
A compound in which m=1 and R represents an alkylene group.

Specific compounds of typical compounds represented by the above general formula [1] ■ tC-++ ■ ■ ■ = 25 ■ ■ ■ ■ tC, H tc@H++ tC@H+.

■ -53 ■ ■ -52 Next, the aliphatic group represented by R21 for general formula [21] preferably has 6 carbon atoms.
Among the above, it is particularly a straight chain, branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, or a sulfoxy group.

The aromatic group represented by R2 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a virolazole ring, a quinoline ring, an inquinoline ring, a benzimidazole ring, a deazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as RZ+ is an aryl group.

The aryl group or unsaturated heterocyclic group of R31 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably an alkyl group having 1 to 20 carbon atoms). monocyclic or bicyclic), alkoxy groups (preferably those with 1 to 20 carbon atoms), substituted amino groups (
(preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably substituted with an alkyl group having 2 to 30 carbon atoms)
), sulfonamide group (preferably one carbon number)
~30), ureido group (preferably 1 carbon number)
~30).

Among the groups represented by R1ff in general formula [2], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by R12 in general formula [2], the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkoxy group, R2, which includes a cyano group, etc. Among the groups represented by, preferred are an optionally substituted alkoxy group or an amino group.

It may be a cyclic structure containing an alkyl group, an alkoxy group, or a 10--S--N- group bond that may be Atlt-substituted. However, R1 is never a hydrazino group.

RlI or Ro in the general formula [2] may have a ballast group, which is commonly used in immobile photographic additives such as couplers, incorporated therein.

The ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a fninoxy group,
It can be selected from alkylphenoxy groups, etc.

R81 or R1 in general formula [2] may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, a triazole group, etc. as described in U.S. Pat.
;The base can be mentioned. Among the compounds represented by the general formula [2], the compounds represented by the following general formula [2-al] are particularly preferred.

General formula [2-al In the above general formula [2-al, Ro and R14 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, -cyanoethyl group,
2-chloroethyl group), an optionally substituted phenyl group,
Naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, a-hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group) group, pyrrolidyl group, 4-methyl-2
-pyrrolidyl group), R1 is a hydrogen atom or an optionally substituted benzyl group,
Alkoxy and alkyl groups (e.g. benzyl, p-
methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), Ro and Rtt represent a divalent aromatic group (e.g. 7-enylene group or naphthylene group), and Y
represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -S O! CH* Cf'f * N 11
S Oz N II, -0CH! So, NH, -0
--C)l-N-), R□ represents -NR'R" or -OR, R', R
” and Ro are hydrogen atoms, optionally substituted alkyl groups (
(e.g., methyl group, ethyl group, dodecyl group), phenyl group (e.g., phenyl group, p-methylphenyl group, p-methoxyphenyl group) or 7thyl group (e.g., α-naphthyl group, β-naphthyl group), m and n represent 0 or 1. When R8 represents OR, Y preferably represents a sulfur atom.

Typical - represented by the above general formulas [2] and [2-al]
Specific example of crest needle [2]■ CF.

■ ※→HNHCCOCH,Cllff1SO□CH,CH
20H*-NHNHCCOCH2CI2SCH,CH,
To OH, H,n = 43 * ■ 1l -NHNHCCNHC,! 11□ Next, among the above specific compounds, compound 2-45゜2-4
7 will be used as an example to show its synthesis method.

Synthesis of compound 2-45 Synthesis scheme (A) (B) (E) Compounds 4-nitrophenylhydrazine 1539 and 500
Mix tnQ diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 5 of the obtained crystals (A)
09 was heated and dissolved in 1000+aQ methanol, pd
/C (palladium on carbon) catalyst under a pressure of 50 Psi of H and reduced in an atmosphere to obtain compound (B).

22g of this compound (B) was added to 200m<1 of acetonitrile.
Compound (C) 2 was dissolved in a solution of 16y and pyridine at room temperature.
A solution of No. 49 in acetonitrile was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D).

Compound (D) 309 was hydrogenated in the same manner as above to obtain Compound (E) 20p.

Compound (E) 109 was dissolved in 100 mff of acetonitrile, 3.0 g of ethyl isothiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) 7 was purified by crystallization.
．． Obtained 0g. Compound (F) 5.09 methanol 5
Methylamine (40% aqueous solution 8mQ
) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out, recrystallized and purified to obtain Compound 2-45.

Synthesis of Compound 2-47 Synthesis Scheme (B) (C) (D) (E) Compound 2-47 Dissolve compound a (B) 229 in 200 ml of pyridine and add p-nitrobenzenesulfonyl chloride to a stirring vessel. Added 22g. The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). Compound 2-47 was obtained by reacting this compound CC) in the same manner as compound 2-45 according to the synthesis scheme.

Next, general formula [31] will be explained.

-Crest needle [31.

Ar NIINII CRs+ In the general formula [3], Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group,
The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

Rsl represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, inglovir, pentyl, cyclohexyl, and the like.

Substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy, p-chlorophenoxy, etc.), peterocyclic oxy (e.g., pyridyloxy, etc.), mercapto, alkylthio (methylthio), etc. , ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl ( (e.g., benzenesulfonyl, etc.), heterocyclic sulfonyl (e.g., pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (e.g., acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyl (e.g., ethoxycarbonyl, me-xycarbonyl, etc.), aryloxy Carbonyl (e.g. phenoxycarbonyl, etc.), carboxy, hrbamoyl, alkylcarbamoyl (e.g. N-methylcarbamoyl, N,N-
dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-7enylcarbamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino,
naphthylamino, etc.), acylamino (e.g., acetylamino, benzoylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy, benzoyloxy), ), alkylaminocarbonyloxy (e.g., methylaminocarbonyloxycarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), arylsulfamoyl (e.g., phenylsulfamoyl, etc.)
There are various stores such as.

The hydrogen clove of hydrazine is substituted with a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), a heptadyl group (e.g., acetyl, trifluoroacetyl, etc.), or an oxalyl group (e.g., ethoxalyl, etc.). Good too.

Representative compounds represented by the above-mentioned needle [31] include:
There are the following.

=14 ta υ -22 =24 *-N11N11CCI! QC)1IC11,QC)+
2CII! OH got it.

General formula [
The amount of the compounds 1], [2], and [3] is preferably from X10-' to X10-' mol per 1 mol of silver halide contained in the silver halide photographic material of the present invention. Synthesis examples of compounds I, preferably X 10-' to Compound 3-5 will now be described.

Synthesis of Compound 3-5 Synthesis Scheme Compound 3 was synthesized according to the synthesis method of Compound 2-45 according to the general formula [4] [However, in the general formula [4], R41 is an alkyl group, specifically, for example, a carbon number of 1 to 8. Alkyl groups, such as methyl group, ethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2
-carboxyethyl group, 3-carboxypropyl group, 4
-carboxybutyl group, sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group,
Vinyl methyl group, benzyl group, phenethyl group, n-propyl group, isopropyl group, n-butyl group, etc. are preferred, and 2 is a nonmetallic atomic group necessary to form a 5-membered or 6-membered heterocycle. Examples of the heterocycle include a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring, a benzoxazole ring, a naphthothiazole ring, a naphthoselenazole ring, a naphthoxazole ring, a pyridine ring, a quinoline ring, etc. Further, these heterocycles may have a substituent, and these substituents include, for example, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms. groups (e.g., methyl group, ethyl group, n-propyl group, etc.), halogenated alkyl groups (e.g., trifluoromethyl group, etc.), alkoxy groups, preferably alkoxy groups having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, (n-propyloxy group, etc.), hydroxy group, aryl group (for example, phenyl group, etc.). Ql represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and examples of these heterocycles include rhodanine ring, thiohydantoin ring, thioxazolidinedione ring, thioselenazolidinedione ring, etc. is possible,
These heterocycles may have a substituent, and these substituents are an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, 2-
Hydroxyethyl group, 2-hydroxyethyloxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-
Carboxypropyl group, 4-carboxybutyl group, 2-
sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, benzyl group, phenethyl group, n-propyl group, n-butyl group, etc.), aryl group (
For example, phenyl group, p-sulfophenyl group, etc.), pyridyl group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4-methyl-2-pyridyl group, etc.). In addition, Peng represents 1 or 2, ] the above general formula [4]
Examples of the compounds represented by are the following 4-1 to 4-25.

(Exemplary Compound) C1l 2 Cll = CH2 CI+3 2Hs 2HS The compound represented by the above general formula [4] used in the present invention is:
For example, it can be easily synthesized based on the methods described in US Pat. No. 2,161,331 and West German Patent No. 936.071. The above general formula [4
In order to use the compound represented by C in a silver halide emulsion, it can be added and dissolved in a coating solution, or dissolved in water or an organic solvent such as methanol, ethanol, acetone, etc. alone or in a mixture thereof, and then prepared at any time. It can be added to the coating solution. Usually, it can be added at any time from after the completion of ripening to just before coating. Preferably, it can be added to the silver halide emulsion layer. However, if necessary, it may 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. be able to.

The amount of the compound represented by the general formula [4] 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 silver halide 1 5a+g to 5 per mole
The silver halide to be used in the silver halide photographic material of the present invention will be described below. Silver halides of any composition can be used, such as silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide, or silver chloroiodobromide. The average diameter of the silver halide grains is preferably in the range of 0.05 to 0.5 .mu.-, particularly preferably 0.10 to 0.40 .mu.-.

Although the grain size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted so that the monodispersity value defined below is in the range of 1 to 30, more preferably in the range of 5 to 2o.

Here, the monodispersity is defined as the value obtained by dividing the standard deviation of particle diameter by the average particle diameter times 100. For convenience, the grain size of silver halide grains is expressed by principal in the case of cubic grains, and other grains are expressed as octahedral, tetradecahedral, etc.)
is calculated by the square root of the projected area.

When carrying out the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, such as silver chloride in the core and silver bromide in the shell. For example, silver chlorobromide particles having a core portion of silver bromide and a shell portion of silver chloride can be used. At this time, iodine can be contained in any layer within 5 mol%.

Furthermore, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example, activated gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacinate, etc.),
Selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, silver 1 tin chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate,
2-Aurosulfobenzothiazole methyl chloride,
Various noble metal sensitizers represented by ammonium chloroparadate, potassium chlorooleate, sodium chloroparadite, etc. 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 silver halide grains used in the present invention can be preferably applied to grains with surface sensitivity higher than internal sensitivity, so-called 110 silver halide grains that give negative images. can be increased.

Further, the silver halide emulsion used in the present invention includes mercapto compounds (1-phenyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole) benzotriazoles (5-brombenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nidropenzimidazole), etc. can be used to stabilize or suppress fog. Incidentally, a sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardening agent, etc. can also be added to the silver halide emulsion used in the present invention.

When the compounds of general formulas [1], [2], and [3] according to the present invention are added to a hydrophilic colloid layer, gelatin is suitable as a binder for the hydrophilic colloid layer, but hydrophilic compounds other than gelatin Colloids can also be used. These hydrophilic binders were applied on both sides of the support at 10g/each.
It is preferable to apply the coating in m2 or less.

Examples of supports that can be used in carrying out the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports may contain alkanolamines such as jetanolamine or triethanolamine, diethylene glycol, or triethylene as an organic solvent in the developing solution used in the present invention depending on the intended use of the silver halide photographic light-sensitive material. May contain glycols such as glycol, diethylamino-1゜2-propanediol,
Alkylamino alcohols such as butylamitubrobanol can be particularly preferably used.

〔Example〕

Examples of the present invention will be described below. It should be noted that, as a matter of course, the present invention is not limited only to the following examples.

Example-1 In the silver halide emulsion layer of a photographic light-sensitive material, formulas [1] and [
2], [3], and [4] (the types of which are shown in Table 1 below) are added in the following manner,
Samples were prepared.

<Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (Japanese Patent Application Laid-open No. 59-199
41 Example-1 method) with a thickness of 100μ
On one undercoat layer of the polyethylene terephthalate film of III, a silver halide emulsion layer of the following formulation (1) was coated so that the amount of gelatin was 1.5 g/m" and the amount of silver was 3.3 g/m2. Then, on top of that, a protective layer of the following formulation (2) was applied so that the amount of gelatin was 1.0 g/m'', and on the other undercoat layer on the opposite side, the following formulation (3) was applied. Sample No. .

1 to 13 were obtained.

Prescription (1) [Silver halide emulsion layer composition] Gelatin
1.5g/2 silver iodobromide (8gBr
99 mol%, 8g 11 mol%, monodispersity = 12.5.
Contains 0.7 mol/^g mol of Ir>
3.3g/ugly 2 antifoggant: 4-hydroxy-6=methyl-1,3,3a.

7-Titrazaindene 0.30 g/m” Compound of the present invention or comparative compound: According to Table 1 Surfactant: Saponin 0.1 g/m2 Latex polymer (styrene-acrylic acid-butyl acrylate ternary copolymer) 1.0 g /Peng 2 prescription (2) [Emulsion protective layer composition] Gelatin 1.0g/Export 2 Matting agent: Polymethyl methacrylate with average particle size of 3.0 to 5.0μ 0.05g/m” Surfactant: n
- Sodium dodecylbenzenesulfonate 0.01H/m2 Hardener: Formalin 0.03g/m2 Glyoxal 0.01g/Orchid 2 prescription (3) [Backing layer composition] 1 17m2 1 gets2 Surfactant: Saponin 0.1g/ Hardener 2: Glyoxal O, 1g/s+” prescription (4)
[Backing protective layer composition] Gelatin 1 g/Mat 2 Matting agent: 0.5 g/m2 of polymethyl methacrylate with an average particle size of 3.0 to 5.0 μm Surfactant: p-dodecylbenzenesulfonic acid sodium 0.01 g/ m2 Hardening agent: Formalin 0.03 g/m" Glyoxal 0.01 g/m2 The obtained sample was subjected to a halftone quality test according to the following method.

(Testing method for halftone dot quality) A halftone screen (150 lines/inch) with a halftone dot area of 50% is attached to a part of the step wedge, the sample is brought into close contact with this screen, and exposed to light using a xenon light source for lXl0-' seconds. ,
This sample was developed under the following conditions in an automatic processing machine for rapid processing using the following developer and fixer, and the halftone dot quality of the sample was observed with a 100x magnifying glass. is ranked as "5", and is ranked as "4", "3", and "2" below.
, 5 ranks up to "1". Note that ranks "1" and "2" are levels that are not desirable in practical terms.

Fog in halftone dots is also evaluated in the same way, and the highest rank is "5" when there are no black spots in the halftone dots, and ranks r4J, r4J,
R3J, ``2'', and ``IJ'' were evaluated by lowering their ranks sequentially. Ranks ``1'' and ``2'' have large black bins and are at a practically unfavorable level.

(Developer formulation) (Composition A) Pure water (ion-exchanged water) 150ml 1-engineered ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50g Potassium sulfite (55% w/v aqueous solution) 100d Potassium carbonate 50° Hydroquinone
15g 5-methylbenzotriazole
200 mg 1-phenyl-5-mercaptotetrazole 30 g Potassium hydroxide Amount to bring the DH after use to 11.5 Potassium bromide (composition) g ll11 Pure water (ion exchange water) Diethylene glycol diethylamino-1,2-propanediol 15g Ethylenediaminetetraacetic acid disodium salt 0g 5B Acetic acid (90% aqueous solution) 0.3 rings 1 5-nitroindazole 110ng 1-phenyl-3-pyrazolidone 500+++g When using a developer, dissolve in 500ml of water in the order of composition A and composition above. , 11 was used.

(Fixer formulation) (Composition A) Ammonium thiovilate (72.5%-/V aqueous solution) 7g 6゜5g g g 13.6+*Z Sodium sulfite Sodium acetate trihydrate Boric acid Sodium citrate diwater Acetic acid salt (90% w/w aqueous solution) (Composition) Pure water (ion exchange water) 17 mf sulfuric acid (
50% w/w aqueous solution) 4.7 g aluminum sulfate (^a20. conversion, aqueous solution with a content of 8.1% w/-) 2
6.5g When using a fixer, the above composition A was dissolved in water 500+*1 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 40°C for 15 seconds Fixation 35°C for 10 seconds Washing with water
30℃ for 10 seconds.
As a comparative compound added to the silver halide emulsion layer in 1), 300 mg/8 g mol of the following compound (a) was added as a comparison of the compound represented by the general formula [4], ] and [3], the following compounds (b) to (d) were used.

Table 1 (Test results) Table 1 shows the compounds added to the silver halide emulsion layer for samples Nos. 5 to 20 of the present invention and samples Nos. 1 to 4 and 21 prepared using the above comparative compounds. The amount added is shown. In addition, the compounds of general formulas [1] to [4] in Table 1 are shown by the numbers of the above-mentioned exemplified compounds.

Table 2 shows the results of the halftone quality test and sensitivity, ranked for each of the above samples.

As is clear from Table 2, in terms of halftone quality, samples Nos. 005 to 20 according to the present invention all rank [4].
'' or higher, the rank ``5'' indicates more results, and comparative sample Nos. 1 to 4.21 all have the rank ``3'' or lower. Considering that ranks "1" and "2" are at a level that cannot be used in practical use, sample No.
Although samples Nos. 4.21 and 4.21 cannot be said to have good halftone dot quality, samples Nos. 095 to 20 according to the present invention were all found to have extremely high and good halftone dot quality.

In addition, regarding the occurrence of black bottles, which is an indicator of fogging,
Sample Nos. 5 to 20 according to the present invention are all ranked r
5. Comparative samples 1 to 4 were all ranked "2" and showed very good results with no fog.
It was found that the result was less than 100%, which is unsuitable for practical use.

〔Effect of the invention〕

To provide a silver halide photographic material that is safe to handle under a yellow safety light, has high sensitivity to a laser light source, and provides excellent halftone dots with high contrast. was completed.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer provided on a support, the silver halide contained in at least one layer has an average grain size of 0. 05 to 0.5 μm, and a monodispersity of 5 to 25, and at least one compound selected from the following general formulas [1], [2], and [3] is contained in at least one of the silver halide emulsion layers. types of compounds and the following general formula [
4] A silver halide photographic material containing at least one compound selected from the compounds shown in [4]. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6, m is 0
or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R_3_1 represents a substituted alkyl group.) General formula [4] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, general formula [4] R_4_1 is an alkyl group, Z is 5
or a group of nonmetallic atoms necessary to form a 6-membered heterocycle; Q is a group of nonmetallic atoms necessary to form a 5-membered heterocycle; m represents 1 or 2; ]