JPH0659372A - Prefogged type direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the prefogged type direct positive silver halide photographic sensitive material good in reversal performance when it is exposed to light high in illuminance for a short time, CONSTITUTION:This prefogged type direct positive silver halide photographic sensitive material has an emulsion layer containing a compound represented by formula I in which each of A and A' is an atomic group necessary to form an optionally substituted aromatic ring; L is a trivalent bonding group obtained by combining an optionally substituted methine group car 3, 5, or 7 optionally substituted methine groups through a conjugated double bond system; each of R<1>, R<2>, R<11>, and R<12> is H, optionally substituted alkyl, such phenyl, such acyl, such alkoxy, or such a 5- or 6-membered heterocyclic group: each of R<3> and R<13> is optionally substituted alkyl; X<n-> are anions; n is 1, 2, or 3; and m is 0 or 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a red-sensitive and infrared-sensitive precoated direct reversal silver halide photographic material.
More specifically, the present invention relates to a precoating type direct reversal silver halide photographic material used in a system which is exposed to a high illuminance by laser light or the like.

[0002]

2. Description of the Related Art The silver halide used in the silver halide photographic light-sensitive material for direct positive of the present invention has been previously fogged, and it can be exposed to light by utilizing the solarization or Herschel effect. It is a direct-positive silver halide photographic light-sensitive material which gives a positive image by destroying. The light-sensitive materials for direct positive are, as disclosed in JP-B-50-3938 and JP-B-50-3937, a light-sensitive material for camera photography using a desensitizing dye, and JP-A-6-63.
There are light-sensitive materials for a bright room that can be handled under a bright room, as shown in Nos. 2-234156 and 61-251843. These light-sensitive material systems are premised on being used in low-illuminance exposure for approximately 1 to 100 seconds, and when these light-sensitive materials are exposed to high illuminance such as a laser, reversibility is poor. However, there was a problem that Dmin was high and the photosensitivity to red or infrared laser light was insufficient.

US Pat. Nos. 4,007,170 and 374.
No. 3640, No. 3615639, No. 357934
No. 6, No. 3723422, No. 35586671.
No. 350570, No. 3941602, No. 3846137, German Patent No. 1153246, No. 2121783, US Pat. No. 3,141,602, No. 3816141, No. 3764338, No. 388.
No. 7380, No. 3970461, Japanese Patent Publication No. 55-47
No. 373, No. 52-6617, JP-A No. 63-1834.
Various desensitizing dyes are described in No. 3 and the like. These have been developed for low light exposure, and none have been found to exhibit good reversibility at high light exposure in combination with the emulsions described herein.

When the desensitizing dye is made to be red-sensitive and infrared-sensitive, the bleaching power of the Ag nuclei of the dye holes is reduced and the reversal property is deteriorated. Also, in high-illuminance exposure, holes move slowly, so Ag
The bleaching efficiency of the nucleus is reduced and the reversibility is deteriorated. Therefore, there has been a demand for the development of a direct reversal light-sensitive material that exhibits good reversibility under exposure with high illuminance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a direct reversal silver halide light-sensitive material which has been previously fogged, with a high illuminance light such as a laser light and a good reversibility in a short exposure time. A second object is to provide a precoated direct reversal silver halide photographic material having red-sensitivity or infrared-sensitivity.

[0006]

The above object is to provide a silver halide photographic light-sensitive material having at least one prefogged direct reversal silver halide emulsion layer on a support, said emulsion layer comprising: This is achieved by a red-sensitive and / or infrared-sensitive pre-covered direct reversal light-sensitive material characterized by containing a compound of the following general formula (I).

[0007]

[Chemical 2]

[In the formula, A and A ′ each represent an atomic group for completing an aromatic ring which may have a substituent, and L represents a methine group which may have a substituent. Or a trivalent linking group formed by linking 3, 5 or 7 methine groups which may have a substituent by a conjugated double bond, and R ¹ , R ² , R ¹¹ and R ¹² are Each represents a hydrogen atom or an alkyl group which may have a substituent, a phenyl group, an acyl group, an alkoxy group or a 5- or 6-membered heterocyclic group, and R ³ and R ¹³ are each a substituent (anion). May have a substituent)
Represents an alkyl group optionally having X ^{n −} represents an anion, n represents 1, 2 or 3, m represents 1 or 0, and R ³ or R ¹³ has an anion. When having a group as a substituent, m is 0. ]

In the compound represented by the above general formula (I) used in the present invention, preferably R ¹ and R ¹¹ and R ²
And R ¹² , R ³ and R ¹³ , R ⁴ and R ¹⁴ , and A and A ′ are the same. The atom group for completing the aromatic ring represented by A and A ′ is preferably an optionally substituted benzene ring or naphthalene ring. The substituent is preferably a halogen atom such as F or Cl, a cyano group, a nitro group, a carboxyl group, an acyl group, an alkylsulfonyl group having 1 to 8 carbon atoms, an arylsulfonyl group having 1 to 8 carbon atoms, Alkoxycarbonyl group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms, aryl group, alkoxy group having 1 to 8 carbon atoms, and 1 carbon atom
To 8 aryloxy groups, alkylthio groups having 1 to 8 carbon atoms, arylthio groups, sulfamoyl groups, N-substituted sulfamoyl groups, carbamoyl groups, N-substituted carbamoyl groups and 5- or 6-membered heterocyclic groups. it can. Among these, a substituent having a positive Hammett's σ constant or its converted value is more preferable. Most preferably, halogen atoms such as F and Cl, and the number of carbon atoms is 1 to 4
And halogenated alkyl groups (eg, trifluoromethyl group), cyano groups and alkoxycarbonyl groups having 1 to 4 carbon atoms (eg, ethoxycarbonyl group). Preferred as the linking group represented by L is a conjugated methine group which may have a substituent consisting of 3 or 5 methine groups, and the substituent is preferably a halogen atom or a C1-8 carbon atom. And alkyl groups, alkoxy groups having 1 to 6 carbon atoms and aralkyl groups. Among these substituents, more preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms,
A benzyl group and a phenyl group. Most preferably,
A halogen atom such as a methyl group, a benzyl group and Cl.

R¹, R², R¹¹And R¹²Group represented by
Is preferably a carbon atom which may be substituted.
Alkyl group of number 1-18 (eg, methyl, ethyl, buty
, Isobutyl, 2-ethylhexyl, dodecyl, tri
Fluoromethyl, 2-ethoxyethyl, 2-hydroxy
Ethyl, 3-sulfopropyl, 3-sulfobutyl, 2-
Sulfoethyl), optionally substituted carbon atoms
6-18 phenyl or naphthyl groups (eg phenyl
Group, 4-methylphenyl group, 3,5-dichlorophenyl
, 4-methoxyphenyl, β-naphthyl, 2,5-di
-T-amylphenyl and the like). More preferably
Is an unsubstituted alkyl group having 1 to 8 carbon atoms or non-substituted
A phenyl group or a naphthyl group, most preferably
Is a methyl group, an ethyl group, an n-propyl group and a phenyl group.
A group can be mentioned. R³And R¹³Represented by
The group preferably has 1 to 18 carbon atoms (preferably 1 carbon atom).
~ 5) alkyl groups each having 1 to 4 carbon atoms.
Lucoxy group, alkylthio group having 1 to 4 carbon atoms, carbon
Alkoxycarbonyl group having 1 to 4 atoms, 1 carbon atom
~ 4 sulfonyl group, halogen atom or hydroxy
It may be substituted with a group. More preferably,
Cyl group, ethyl group, isopropyl group, sec-butyl
Group, cyclohexyl group, 2-ethylhexyl group, benzyl
Group, 2-phenylthio group, dodecyl group, 2-ethoxy
Ethyl group, 3-ethoxypropyl group, hydroxyethyl
Group, 3-acetoxypropyl group, ethoxycarbonyl
Cyl group, 3-sulfopropyl group, 2,3-tetrafluor
Propyl group, allyl group, 2-methylthioethyl group, 3
-Methoxypropyl group, phenyl group, 4-methylphenyl
Group, 3,5-dichlorophenyl group, 4-methoxyphen
Nyl group, β-naphthyl group and 2,5-di-t-amyl
It is phenyl. Most preferably, methyl group, ethyl
Group, sec-butyl group, 2-ethoxyethyl group, 3-d
Toxypropyl group, 3-methoxypropyl group, hydroxy
Ciethyl group, 3-acetoxypropyl group, ethoxycarl
Bonylmethyl group, 3-sulfopropyl group and 2,3-
It is a tetrafluoropropyl group. Also represented by X
As a preferable anion, a halide ion is preferable.
(Eg Cl^-, Br^-, I^-), Sulfonate
On (eg CH₃SO ₃ ^-, CF₃SO₃ ^-, CH
₃OSO₃ ^-, Naphthalene-1,5-disulfonate
ON), ClO_Four ^-, BF_Four ^-

[0011]

[Chemical 3]

[0012] There can be mentioned. Of these, particularly preferable anions are ClO ₄ ⁻ , BF ₄ ⁻ , I ^−, and

[0013]

[Chemical 4]

[0014] Examples of specific compounds represented by the general formula (I) include the following I-1 to I-20.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

The dye represented by the general formula (I) of the present invention is
By FS Babichev and AF Babicheva, abstracted in Chemical Abstracts, Vol. 69, Item 60031V.
Khim. Geterotsikl. Soedin. Magazine, 1967, 917-
On page 922, a portion (A and A'in the general formula (I) are unsubstituted benzene rings, R ¹ , R ² , R ³ , R ¹¹ , R ¹² and R ^12
13 in all methyl groups, X ^n-is ClO ₄ ^- A, L other with the dye and L is trimethine group having a structure consisting of an unsubstituted methine group two dyes having the same structure as the former) Is listed. However, there is no description about application of these dyes to photographic light-sensitive materials. Other dyes can also be synthesized with reference to these.

Next, the synthesis method will be specifically described with reference to synthesis examples of the dye represented by the general formula (I) of the present invention. Synthesis Example 1 (Synthesis of Dye I-4) 25 ml of acetone was added to 4.58 g of 5,6-dichloro-1-ethyl-2-methylbenzimidazole to dissolve it, and then 3 ml of α-bromopropiophenone was added to give 100 Heated to reflux for minutes. After distilling off acetone, 1 at 100 ℃
Heated for hours. Acetone (100 ml) was added to the reaction mixture and the mixture was stirred, and the resulting colorless crystals were collected by filtration, washed with acetone and dried. Yield 5.4g. The crystals were mixed with sodium carbonate 1.
It was added to an aqueous solution prepared from 3 g and 60 ml of water and heated on a steam bath for 80 minutes. After cooling, the resulting crystals were collected by filtration and washed with water to obtain 4.8 g of colorless crystals. The crystals were recrystallized from 600 ml of methanol to give 2 g of colorless needle crystals 6,7-
Dichloro-4-ethyl-1-methyl-2-phenylpyrrolo [1,2-a] benzimidazole was obtained. To 1 g of this crystal, 20 ml of acetonitrile and 0.3 g of paratoluenesulfonic acid monohydrate were added and dissolved, and 1,3,3
1 ml of trimethoxypropene was added and the mixture was heated under reflux for 5 minutes. After standing to cool, the resulting crystals were collected by filtration and washed with acetonitrile 25
Washing with ml gave 0.75 g of compound crystals. Melting point 247-249 ° C λ Max. (Methanol): 626 nm

Synthesis Example 2 (Synthesis of Dye I-18) To 2.57 g of 5,6-dichloro-1-isopropyl-2-methylbenzimidazole, 1.52 ml of α-bromopropiophenone and 1 ml of anisole were added and vaporized. 2 on the bath
After heating for an hour, 50 ml of acetone was added. The crystals formed were collected by filtration, 40 ml of 2% aqueous sodium carbonate solution was added, and the mixture was heated on a steam bath for 80 minutes. After cooling, the resulting crystals were collected by filtration, washed with water and 6,7-dichloro-4-isopropyl-1.
-Methyl-2-phenylpyrrolo [1,2-a] benzimidazole was obtained. To 0.6 g of this crystal, 11 ml of acetonitrile and 0.17 g of paratoluenesulfonic acid monohydrate
And 0.6 ml of 1,3,3-trimethoxypropene were added and the mixture was heated under reflux for 15 minutes. After cooling, the resulting crystals were collected by filtration,
Washing with acetonitrile gave 0.2 g of compound. Melting point 167 [deg.] C. λ Max. (methanol): 626nm

The amount of the compound of the general formula (I) used in the present invention is 50 mg to 20 g, preferably 1 per mol of silver.
It is preferably used in the range of 00 mg to 10 g. As an addition method, it may be added at any time during the production of the raw milk, or may be added after the raw milk is dissolved and before the coating, and these addition methods may be used in combination.

The grain size of the silver halide used in the present invention is particularly preferably 0.40 to 0.10 μm.
When the particle size is large, graininess deteriorates and reversal is poor,
Dmin becomes high. On the other hand, if the particle size is small, Dma
It is difficult to obtain x, the reversal is poor, and Dmin becomes high. This tendency becomes particularly strong when a red-sensitive or infrared-sensitive desensitizing dye is used, and therefore, in a light-sensitive material having such a light-sensitive area, a particularly optimum particle size exists.
Also, in high-intensity short-time exposure of 10 ^-2 seconds or more,
Particle size is important and Dmax and Dmi for low light exposure
There is almost no dependence on the particle size in n, and the development efficiency is high and high Dmax can be obtained and Dmin is low in any size, but in high-intensity exposure, there is an optimum particle size region. Of.

On the other hand, in the covering step after the particles are formed and washed with water, the amount of the gold compound such as the chloroauric acid compound used varies depending on the particle size and the halogen composition.
It is preferably used in the range of 0.05 to 0.0005 mmol per mol. If the amount of gold compound is large, Dmin becomes high, and if it is small, Dmax becomes difficult to come out. General formula (I)
In a pre-processed light-sensitive material which is exposed to a high illuminance using the desensitizing dye, the development is particularly remarkable, and an optimum amount of the gold compound exists. The halogen composition of the silver halide used in the present invention has a silver chlorobromide content of 5 mol% or more Br.
Silver bromide, silver chloroiodobromide, and silver iodobromide are preferable, and silver chloride has a poor reversal property.

The silver halide emulsion used in the present invention may be produced by any of the acidic method, the neutral method and the ammonia method, and as the silver halide, silver bromide, silver chloride, silver chlorobromide, Examples thereof include silver iodobromide and silver chloroiodobromide. The silver halide grains used in the present invention have an average grain diameter of 0.4 to
0.1 micron is good. The particle size frequency distribution may be wide or narrow, but is preferably narrow. In particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of grains falls within a grain size range of ± 40%, preferably ± 20% of the average grain size is preferable. The silver halide grains may have a single crystal habit or a mixture of various crystal habits, but a single crystal habit is preferable.

Substitution positive type silver halide used in the present invention
Is an inorganic desensitizer (ie silver halide grains)
Noble metal atoms contained in the child) and the surface of the silver halide
Contains adsorbing organic desensitizers alone or in combination
be able to. Halogenated inorganic desensitizer used in the present invention
Even if it is a water-soluble precious metal compound to be contained in silver particles,
Iridium, rhodium, ruthenium, etc. Periodic Group 8 gold
Chlorides of the genus 10 per mol of silver halide^-7-10^-2
Mol, preferably 10^-Five-10 ^-3Mole, silver halide grain
It may be added as an aqueous solution when preparing the baby.

Direct positive type silver halide used in the present invention
The fog is generated after the silver halide precipitate is formed.
Conventionally known technology after removing water-soluble salts
It should be done by. Fog is a fogging agent (reduction
Agent) is more electrically positive than fogging agent, gold compound and silver
May be used in combination. Scarecrow
Typical of fogging agents useful for making emulsions
For example formalin, hydrazine, polyamine (triethyl
Lentetramine, tetraethylenepentamine, etc.), thio
Urea dioxide, tetra (hydroxymethyl) phospho
Aluminum chloride, amine borane borohydride compound,
Contains stannous chloride, tin (II) chloride, etc.
Representative of useful more electrically positive metal compounds
Include gold, rhodium, platinum, palladium, iridium, etc.
Soluble salts of, for example, potassium chloroaurate, chloroauric acid, chloride
Palladium ammonium, iridium sodium chloride, etc.
Is included. Fogging agents are generally silver halide.
1.0 × 10 per le^-6~ 1.0 x 10 ^-1For molar range
Can be Typical gold compounds are chloroauric acid and chlorochloride.
Examples include sodium aurate, gold sulfide, and gold selenide.
Generally 1.0 x 10 per mol of silver halide^-8~ 1.0x
10^-FourIt is preferably contained in a molar range.

The degree of fogging of the pre-fogged direct positive type silver halide emulsion used in the present invention can be varied within a wide range. The degree of fogging depends on the type and concentration of the fogging agent used, the concentration, and the time of application of fog, as well as the silver halide composition and grain size of the silver halide emulsion used as well known to those skilled in the art. PH of emulsion, p
It is related to Ag, temperature time and the like. The silver halide photographic light-sensitive material for direct positive of the present invention may contain various other photographic additives generally used. As the stabilizer, for example, triazoles, azaindenes, quaternary benzothiazolium compounds, mercapto compounds, or water-soluble inorganic salts such as cadmium, cobalt, nickel, manganese, gold, thallium, and zinc may be contained. Further, as a hardener, for example, aldehydes such as formalin, glyoxal, mucochromic acid, S-triazines, epoxies, aziridine, vinyl sulfonic acid, etc., or as a coating aid, for example, saponin, sodium polyalkylene sulfonate, lauryl polyethylene glycol. Alternatively, oleyl monoether, amylated alkyl taurine, fluorine-containing compound, etc., and a sensitizer such as polyalkylene oxide and its derivative may be contained. Further, it is possible to contain a color coupler. In addition, a whitening agent, a UV absorber, an antiseptic, a matting agent, an antistatic agent, etc. can be added as required.

The dye used in the present invention has a main absorption in the visible wavelength range of the intrinsic photosensitive wavelength range of the silver halide emulsion used for preventing fog under irradiation prevention or safelight. is there. Λ _max
Dyes having a value of 350 nm to 600 nm are preferred. There is no particular limitation on the chemical structure of the dye, and oxonol dye, hemioxonol dye, merocyanine dye, cyanine dye, azo dye, etc. can be used, but a water-soluble dye is useful in terms of eliminating residual color after processing. Is. Specifically, for example, a pyrazolone dye described in JP-B-58-12576, a pyrazolone oxonol dye described in U.S. Pat. No. 2,274,782, and a U.S. Pat. No. 2,956,87.
Diarylazo dyes described in No. 9, US Pat. No. 3,42
3,207, 3,484,487, styryl dyes and butadienyl dyes, US Pat. No. 2,527,
No. 583, merocyanine dyes, US Pat.
86,897, No. 3,652,284, No. 3,
718,472, merocyanine dyes and oxonol dyes, US Pat. No. 3,976,661, enaminohemioxonol dyes, and British Patent 584,6.
09, No. 1,177,429, JP-A-48-85.
No. 130, No. 49-99620, No. 49-11442.
No. 0, US Pat. Nos. 2,533,472 and 3,14.
No. 8,187, No. 3,177,078, No. 3,2
47, 127, 3,540, 887, 3,
The dyes described in 575,704 and 3,653,905 are used. Examples of the developing agent used in the development processing of the silver halide photographic light-sensitive material according to the present invention include
Organic or inorganic developers and development aids described in "The Theory of the Photographic Process," 3rd edition, pp. 278-381 (1966), by K.M.T.H. James. A single agent or a combination of a plurality of agents may be used. Preferably, ferrous oxalate,
Hydroquinones such as hydroxylamine, N-hydroxymorpholine, hydroquinone, hydroquinone monosulfonate, chlorohydroquinone, t-butyl hydroquinone, catechol, resorcin, pyrogallol, amidole, phenidone, 4-hydroxymethyl-4-methyl-1. -Pyrazolidones such as phenyl-3-pyrazolidone, paraaminophenols such as paraaminophenol, glycine, methol, paraphenylenediamine, paraphenylenediamines such as 4-amino-N-ethyl-N-ethoxyaniline, ascorbine An acid or the like. More preferably, methole alone,
Combinations of phenidone and methol, combinations of methol and hydroquinone, phenidone, methol and t-butylhydroquinone, phenidone and ascorbic acid, phenidone and paraaminophenol, etc. You can get good results.

The developing agent as described above, which is contained in the developing solution of the silver halide photographic light-sensitive material used in the present invention, may be used generally in an amount of 1 × 10 ^-5 to 1 mol / l developing solution. Particularly, hydroquinone is preferably used in an amount of 20 g / liter or more, more preferably 25 g / liter. The developing solution for the silver halide photographic light-sensitive material used in the present invention includes the above-mentioned developing agents and preservatives such as sulfite and hydroxylamine, as well as caustic alkali, alkali carbonate and borohydride used in general black and white developing solutions. PH adjustment and buffer function such as acid alkali, amines, etc., inorganic development inhibitors such as promkari, benzimidazole, benztriazole and British Patent No. 1,37.
It is optional to add an organic development inhibitor such as nitroindazole shown in the specification of US Pat. No. 6,600.

The direct-positive silver halide photographic light-sensitive material of the present invention is applied to various uses. For example, various photographic light-sensitive materials for printing such as duplicating, re-protection and offset master, special photographic light-sensitive materials such as X-ray, flash photography, electron beam photography or general copying, micro copying, direct positive type It is used for various direct positive photographic light-sensitive materials for color, quick stapled, diffusion transfer, color diffusion transfer, one-bath developing and fixing, and the like.
These direct-positive silver halide photographic light-sensitive materials are harder than conventional ones and have extremely high stability for long-term storage and high temperature and high humidity. Hereinafter, the present invention will be described more specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.

Developer (A) 1,2-dihydroxybenzene-3,5-disulfonic acid sodium soda 0.5 g diethylenetriamine-pentaacetic acid 2.0 g sodium carbonate 5.0 g boric acid 10.0 g potassium sulfite 85.0 g sodium bromide 6.0 g Diethylene glycol 40.0 g 5-Methylbenzotriazole 0.2 g Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g 2,3,5,6,7,8- Hexahydro-2-thioxo-4- (1H) -quinazolinone 0.09 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 0.3 g Potassium hydroxide is added, water is added to 1 liter and pH is adjusted to 10.7. To match. 1 liter

Fixer Formulation (B) Sodium thiosulfate 1.1 mol / liter Ammonium thiosulfate 0.2 mol / liter Sodium sulfite 0.1 mol / liter Sodium metabisulfate 0.08 mol / liter Disodium ethylenediaminetetraacetate・ Dihydrate 0.1 g / liter Adjust pH to 6.0 with sodium hydroxide and add water to make 1 liter.

[0037]

【Example】

 Example 1 Citric acid was added to a gelatin aqueous solution kept at 50 ° C.
Ether (HOCH₂CH₂SCH ₂-CH₂SCH₂CH₂OH) in the presence of
AgNO by the troll double jet method₃And halogen melt
The solution was added for 60 minutes, and the cube size was 0.24μ.
A dispersed silver bromide emulsion was prepared. This emulsion is mixed with floccure
Desalting by the cation method, and then adding gelatin to add 6
Formamidinesulfin, after keeping at 5 ℃ pH6.0
Add 0.001 mmol / Ag mol of acid and tetrachloroauric acid
After aging, the pH was maintained at 6.5 and the temperature was lowered. This emulsion
a. In this emulsion, as a desensitizing dye, a compound represented by the general formula (I)
20 mg / m of compound I-2²Add polyethylene
Silver 3.0 g / m on the rephthalate film²Painted to become
Clothed 1.2 g / gelatin as a protective layer on this
m², Atypical SiO with an average particle size of 3μ₂Matting agent 20
mg / m², Methanol silica 0.1g / m²And with coating aids
Then, the fluorine-based surfactant (C₈F₁₇S
O₂N (C₃H₇) CH₂COOK) and dodecylbenzene sulfonate
In addition, KBr solution to adjust the pAg of the membrane
At the same time as the protective layer containing
Applied. This sensitive material is designated as A. This sensitive material is exposed to Xe
Using a meter, use an interference filter of 780 nm and a density difference (△
D)_0.1Through the step wedge of 10⁰1
0^-310,^-Four10,^-6Sensitometric exposure in seconds,
After that, using the developer A and the fixer B, Fuji Photo Fiber
38 ° C. with an automatic processor FG660F manufactured by RUM Co., Ltd.
Processing was carried out under the developing condition of 0 ″, and Dmax and Dmin were measured.

[0038]

[Table 1]

Even in high illuminance exposure (10 ^-3 seconds or more),
It can be seen that it exhibits a low Dmin.

Example 2 In the emulsion a of Example 1, cubic monodispersed silver bromide emulsions having different sizes as shown in Table 2 were prepared by changing the temperature at the time of grain formation or the amount of thioether. This emulsion was desalted by the flocculation method, and then gelatin was added, the mixture was kept at 65 ° C. and pH 6.0, and then formamidinesulfinic acid and tetrachloroauric acid were added and ripened, and the pH was adjusted to 6.5. The temperature was kept down. These emulsions are designated as b, c, d, e, f and g, respectively.
And Using these emulsions, in the same manner as in Example 1,
After preparing the light-sensitive materials B, C, D, E, F and G, Dmax and Dmin were measured in the same manner. The results are shown in Table 2. It can be seen that in the particle size range of 0.1 to 0.40, a low Dmin of 0.08 or less is exhibited even at high illuminance exposure of 10 ^-3 seconds or more.

[0041]

[Table 2]

Example 3 Instead of the desensitizing dye I-2 of the light-sensitive material A prepared in Example 1,
I-3, I-4, I-9, I-18, and I-30 were added as shown in Table 3, and the photosensitive materials A-1, A-2, A-3, and A- were added.
4, A-5 was produced. These photosensitive materials were processed in the same manner as in Example 1 to measure Dmax and Dmin. The results are shown in Table 3. It can be seen that a low Dmin of 0.08 or less is exhibited even at high illuminance of 10 ⁻³ seconds or more.

[0043]

[Table 3]

Example 4 As shown in Table 4, by changing the halogen composition of the halogen solution of the emulsion a prepared in Example 1 and changing the amount of thioether and the addition time, a cubic salt having a particle size of 0.24 μ was prepared. Ten kinds of silver bromide emulsions were prepared. Desalting these emulsions by the flocculation method, and then adding gelatin,
After maintaining the pH at 63 ° C. at 5.8, formamidinesulfinic acid and tetrachloroauric acid were added and aging was performed, and the pH was maintained at 6.5 and the temperature was lowered. These emulsions were treated with h, i, j, k, l, m,
Let n, o, p, q. Example 1 using these emulsions
Sensitive materials H, I, J, K, L, M,
N, O, P, Q are produced, exposed and developed in the same manner, and Dma
x and Dmin were measured. The results obtained are shown in Table 4. B
It can be seen that a silver chlorobromide emulsion having an r of 5 mol% or more shows a low Dmin of 0.08 or less even when exposed to high illuminance for 10 ^-3 seconds or more.

[0045]

[Table 4]

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one prefogged direct positive silver halide emulsion layer on a support, wherein the emulsion layer comprises a compound of the following general formula (I): A precoated direct inversion silver halide photographic light-sensitive material comprising: [Chemical 1] [In the formula, A and A ′ each represent an atomic group for completing an aromatic ring which may have a substituent, and
Represents a methine group which may have a substituent, or a trivalent linking group formed by linking 3, 5 or 7 methine groups which may have a substituent by a conjugated double bond. , R ¹ , R ² , R ¹¹ and R ¹² each represent a hydrogen atom or an optionally substituted alkyl group, a phenyl group, an acyl group, an alkoxy group or a 5- or 6-membered heterocyclic group, R ³ and R ¹³ each represent an alkyl group which may have a substituent (which may be a substituent having an anion), and X ^{n −} represents an anion,
n represents 1, 2 or 3, m represents 1 or 0, and when R ³ or R ¹³ has a group having an anion as a substituent, m is 0. ] 2. The precoated direct reversal silver halide photographic light-sensitive material according to claim 1, wherein the average grain size of the silver halide grains is 0.10 to 0.40 μm.