JP2684242B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic which has high sensitivity and rapid processing suitability in high-intensity short-time exposure. It relates to a photosensitive material.

(Prior Art) In recent years, a scanner method has been widely used in the field of printing plate making. There are various types of recording devices that use the image forming method by the scanner method, and the light source for recording of these scanner type recording devices includes glow lamps, xenon lamps, tungsten lamps, LEDs, or He-He lasers, argon lasers. , Semiconductor laser, etc.

Various characteristics are required for the photosensitive material used in these scanners, but especially under such conditions, high sensitivity and high contrast can be obtained because of exposure with a short exposure time of 10 ^-3 to 10 ^-7 seconds. Is an essential condition. Especially in the facsimile field, it is important to select suitable for rapid development processing in order to attach importance to promptness, and in the past, in order to speed up scanning and high image quality, increase in number of lines and light beam The squeezing has been desired, and the development of a photosensitive material having high sensitivity and high contrast has been strongly desired.

What is rapid development processing? The time from the insertion of the leading edge of the film into the automatic processor and the time when the leading edge of the film comes out of the drying section after passing through the developing tank, crossover section, fixing tank, crossover section, washing tank and drying section. Is a process that is 20-60 seconds.

If the conveyance speed of the automatic processor is increased to shorten these processes, (1) defective fixing, (2) defective washing with water, (3)
Problems such as poor drying occur. To solve these,
It is effective to reduce the amount of gelatin and the amount of coated silver in the silver halide light-sensitive material as described in Japanese Patent Application No. 2-124727. In this case, there arise problems of (a) lower black density, (b) deterioration of graininess, and (c) deterioration of pressure property.

In order to solve the above (a) and (b), it is necessary to reduce the grain size in the silver halide emulsion.
For this purpose, it is necessary to increase the sensitivity of the silver halide emulsion.
On the other hand, Fe described in Japanese Patent Application No. 1-124726
It is solved by containing salt. However, the problem of deterioration of pressure property was not solved, and it was necessary to solve this problem.

(Object of the Invention) Therefore, firstly, the object of the present invention is to provide a light-sensitive material having high sensitivity during high-illuminance exposure, suitable for rapid processing, and excellent in pressure property, and a second object. It is to provide a photosensitive material having a spectral sensitivity suitable for each scanner light source.

(Structure of the Invention) A first object of the present invention is to provide a silver halide photograph having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on the same surface of a support. In the light-sensitive material, the amount of gelatin on the side having the light-sensitive silver halide emulsion layer and the non-light-sensitive hydrophilic colloid layer on the support is 2.5 g / m ² or less, and the silver halide grains are based on silver. It was achieved by adding a sensitizing dye before chemical sensitization of silver halide grains, containing less than 10 ^-3 mol of iron compound.

The second object was achieved by spectrally sensitizing the silver halide grains of the light-sensitive material with at least one of the sensitizing dyes of the general formulas IV.

(Specific Configuration of the Invention) The specific configuration of the present invention will be described in detail.

The silver halide photographic emulsion according to the present invention may contain any one of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide and silver iodobromide as the silver halide, but the silver chloride content is 30 mol. % Or more, and more preferably 50 mol% or more. The silver iodide content is preferably at most 5 mol%, more preferably at most 2 mol%.

The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but is preferably cubic or tabular. The average grain size of silver halide grains is 0.01 μm ~
1 μm is preferable, but 0.4 μm or less is more preferable, and the variation coefficient represented by {(standard variation of particle diameter) / (average particle diameter)} × 100 is 15% or less, more preferably 10% or less. Those having a narrow diameter distribution are preferable.

The silver halide grains may be composed of a uniform phase in the interior and the surface, or may be composed of different phases.

The photographic emulsion used in the present invention is described by P. Glafkides Chimi.
e et Physique Photograhique (Published by Paul Montel, 1967
Year) GF Duffin Photographic Emulsion Chemistry (T
he Focal Press, 1966), by VL Zelikman et al Ma
king and Coating Photographic Emulsion (The Focal
Press, 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Good.

A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. PA in the liquid phase where silver halide is formed as a form of the double jet method.
A method of keeping g constant, that is, a so-called controlled,
The double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In order to make the particle size uniform, British Patent 1,
No. 535,016, JP-B-48-36890 and JP-B-52-16364, a method in which the addition rate of silver nitrate or alkali halide is changed according to the grain growth rate,
It is preferable to use a method of changing the concentration of an aqueous solution as described in JP-A-Sho 4,242,445 and JP-A-55-158124 to grow the solution quickly within a range not exceeding the critical saturation.

The grain formation of the silver halide emulsion of the present invention is preferably carried out in the presence of a silver halide solvent such as a tetrasubstituted thiourea or an organic thioether compound.

Preferred tetrasubstituted thiourea silver halide solvents used in the present invention are compounds represented by the following general formulas described in JP-A-53-82408 and JP-A-55-77737.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a substituted or unsubstituted alkyl group, an alkenyl group (such as an allyl group) or a substituted or unsubstituted aryl, which may be the same or different from each other. The total number of carbon atoms of R _{1 to} R ₄ is preferably 30 or less. Further, a 5- to 6-membered heterocyclic imidazolidinethione, which is bonded with R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ ,
It is also possible to make piperidine, morpholine, etc. Both linear and branched alkyl groups are used.

As the substituent of the alkyl group, for example, a hydroxy group (-OH), a carboxy group, a sulfonic acid group, an amino group, an alkoxy group having an alkyl residue having 1 to 5 carbon atoms (o-alkyl), a phenyl group or It is a 5- or 6-membered heterocyclic ring (such as furan). The substituent of the aryl group is a hydroxy group, a carboxy group or a sulfonic group.

Here, particularly preferably, among R _{1 to} R ₄ , there are three or more alkyl groups, the number of carbon atoms of each alkyl group is 1 to 5, the aryl group is a phenyl group, and the number of carbon atoms of R _{1 to} R ₄ is The total is 20 or less.

Examples of the compounds that can be used in the present invention include the following.

The organic thioether silver halide solvent preferably used in the present invention is, for example, JP-B-47-11386 (US Pat.
No. 4,628), etc., in which an oxygen atom and a sulfur atom are exposed by ethylene (for example, -O-CH ₂ CH ₂ -S
A compound containing at least one-), an alkyl group at both ends described in JP-A-54-155828 (US Pat. No. 4,276,374), each alkyl group being selected from hydroxy, amino, carboxy, amide or sulfone. A chain thioether compound having at least two substituents). Specifically, the following examples can be given.

HOCH ₂ CH ₂ -S-CH ₂ CH ₂ -S-CH ₂ CH ₂ OH HOCH ₂ CH ₂ CH _2- S-CH ₂ CH _2- S-CH ₂ CH ₂ CH ₂ OH The addition amount of the silver halide solvent varies depending on the kind of the compound used, the intended grain size, the halogen composition, etc., but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

When the grain size becomes larger than intended by using a silver halide solvent, the grain size can be made desired by changing the temperature during grain formation, the addition time of the silver salt solution, the halogen salt solution and the like.

The iron compound used in the present invention is a divalent or trivalent iron ion-containing compound, and is preferably a water-soluble iron salt or iron complex in the concentration range used in the present invention. Specifically, ferrous arsenate ferrous bromide ferrous carbonate ferrous chloride ferrous citrate ferrous fluoride ferrous formate ferrous gluconate ferrous hydroxide iodide ferrate Ferrous lactate ferric oxalate ferrous phosphate ferrous succinate ferrous sulfate ferrous thiocyanate ferrous sulfate ferrous ammonium sulfate basic ferric acetate ferric albumate Ferric acetate ammonium ferric bromide ferric chloride ferric chloride ferric citrate ferric fluoride ferric formate glycerophosphate ferric hydroxide ferric hydroxide acidic phosphate ferric Ferric nitrate ferric nitrate ferric phosphate ferric pyrophosphate sodium ferric pyrophosphate ferric thiocyanate ferric sulfate ferric ammonium sulfate ferric sulfate guanidine ferric ammonium citrate hexane cyanoferrate (II) Potassium pentacyanoammine ferrous potassium Chirenjinitoriro tetraacetate sodium ferric potassium hexacyanoferrate (III) chloride tris (dipyridyl) ferric pentacyano nitrosyl ferric potassium chloride Hekisarea ferric particularly hexacyanoferrate (II), hexacyanoferrate (II
I) Acid salts, ferrous thiocyanate and ferric thiocyanate show remarkable effects.

These iron compounds are used after being dissolved in water or a suitable solvent. Instead of using water-soluble iron, it is also possible to add and dissolve another silver halide grain previously doped with iron at the time of preparing silver halide grains.

The total addition amount of the iron compound according to the present invention is appropriately 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, and preferably 5 × 10 ⁻⁶ to 1 ×, per 1 mol of finally formed silver halide. It is 10 ^-4 mol.

These compounds can be appropriately added during the production of a silver halide emulsion and at each stage before coating the emulsion. In particular, it is possible to add these compounds during grain formation and to incorporate them into silver halide grains. preferable.

The addition position may be evenly distributed in the particles, or may be localized in the early, middle, and late stages of particle formation, but in the latter stage of particle formation, that is, 50% of the final particle size, more preferably It is preferred to add after 80% has been formed.

In the present invention, other metals contained in Group VIII, that is, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like may be used in combination. In particular, the combined use with an iridium salt such as hexachloroiridium, hexaammineiridium, trioxalatoiridium, and hexacyanoiridim is advantageous because an emulsion having high sensitivity and high contrast can be obtained. Further, the combined use with a rhodium salt such as rhodium chloride and ammonium hexachlorodium (II) is advantageous because a high contrast emulsion can be obtained.

The photosensitive silver halide emulsion of the present invention, before chemical sensitization,
It is spectrally sensitized by a sensitizing dye. The sensitizing dye may be added at any time before chemical sensitization, before grain formation of the silver halide emulsion, after grain formation but before water washing step, and after water washing step, but most preferably after water washing step and before chemical sensitization. .

As the sensitizing dye used in the present invention, a cyanine dye,
A merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used.

Useful sensitizing dyes for use in the present invention are, for example, RESEARCH
DISCLOSURR Item 17643 IV-A (December 1978, p. 2
3), Item 1831X (i.e., August 1979, p.437), or cited.

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

For an argon laser light source, see JP-A-60-162247.
JP-A-2-48653, U.S. Pat. No. 2,161,331, and West German Patent 936,071 for simple merocyanines and helium-neon laser light sources, JP-A-50-62425,
For the trinuclear cyan dyes and LDE light sources shown in Nos. 54-18726 and 59-102229, Japanese Patent Publication Nos. 48-42172 and 51-
9609 and 55-39818, thiacarbocyanines described in JP-A-62-284343, and semiconductor laser light sources are described in JP-A-59-191032 and JP-A-60-80841. Tricaorbocyanins and dicarbocyanines containing a 4-quinoline nucleus described in JP-A-59-192242 are advantageously selected.

Among the above sensitizing dyes, it is particularly preferable to use the dyes represented by the following general formulas (I) to (V) from the viewpoint of sensitizing property and residual color.

Z ₁ is a group of non-metal atoms necessary for forming a 5- or 6-membered double ring, and the hetero ring is, for example, a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring. , Benzoxazole ring, naphthothiazole ring, naphthoselenazole ring, naphthoxazole ring, pyridine ring, quinoline ring and the like, and further, these heterocycles may have a substituent, and as these substituents, For example, a halogen atom (for example, chlorine atom, bromine atom), for example, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group), halogenated alkyl group (for example, trifluoromethyl group) ), An alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, n-propyl group). Alkoxy group), a hydroxy group, an aryl group (e.g. phenyl group).

Q ₁ represents a nonmetallic atomic group necessary for forming a 5-membered heterocycle. Examples of the heterocyclic ring include a rhodanine ring, a thiohydantoin ring, a thiooxazolidinedione ring, and a thioselenazolidinedione ring, and these heterocyclic rings may have a substituent. Preferably an alkyl group having 1 to 4 carbon atoms (for example, 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-butyl group), aryl group (eg phenyl group, p-sulfophenyl group) or pyridyl group (eg 2-pyridyl group, 3
-Pyridyl group, methyl-2-pyridyl group).

R ₁ represents an alkyl group or a substituted alkyl group, for example,
1-18 carbon atoms, preferably 1-7, particularly preferably 1-4
An alkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group such as an aralkyl group (for example, benzyl, 2-phenylethyl), a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- ( 2-methoxyethoxy) ethyl) sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- (3
-Sulfopropoxy) ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (for example, 3-sulfatoatopropyl, 4-sulfatobutyl), a heterocyclic-substituted alkyl group ( For example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl, allyl group and the like.

Next, specific examples of the compound represented by the general formula (I) used in the silver halide photographic light-sensitive material of the present invention will be shown. However, needless to say, the compounds used in the present invention are not limited to these.

Representative specific examples of the sensitizing dye represented by formula (I) Z ₂ and Z ₃ each represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. Examples of the above heterocycle include a thiazole ring {for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-di-phenylthiazole, etc.}, benzothiazole ring {for example, benzothiazole,
5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 6-
Iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-carboxybenzothiazole, 5
-Fluorobenzothiazole, 5-dimethylaminobenzothiazole, 5-acetylaminobenzothiazole,
5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, tetrahydrobenzothiazole, etc.}, naphthothiazole ring {for example, naphtho [2 , 1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7
-Ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole, etc.}, selenazole ring {for example, 4-methylselenazole, 4-phenylselenazole}, benzoselenazole ring {for example, benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, 5-methoxybenzoselenazole, 5
-Methylbenzoselenazole, 5-hydroxybenzoselenazole, etc.}, naphthoselenazole ring {for example, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole}, oxazole ring {for example oxazole, 4-
Methyloxazole, 5-methyloxazole, 4,5-
Dimethyloxazole}, benzoxazole ring {for example, benzoxazole, 5-fluorobenzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole, 5-methylbenzoxazole, 5-methyl-6
-Phenylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5,6
-Dimethoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5
-Methoxycarbonylbenzoxazole, 5-acetylbenzoxazole, 5-hydroxybenzoxazole, etc.}, naphthoxazole ring {for example, naphtho [2,
1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, etc.}, 2-quinoline ring, imidazole ring, benzimidazole ring, 3,
3'-dialkyl indolenine ring, 2-pyridine ring, thiazoline ring, etc. are mentioned. Particularly preferably, at least one of Z ₂ and Z ₃ is a thiazole ring, a thiazoline ring,
This is the case of an oxazole ring or a benzoxazole ring.

Examples of the alkyl group represented by R ₂ or R ₃ in the above general formula include alkyl groups having 5 or less carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group}, and substituted alkyl groups. A substituted alkyl group having 5 or less carbon atoms in the alkyl radical (eg, hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group), carboxyalkyl group (eg, carboxymethyl group, 2-carboxy) Ethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2- (2-carboxyethoxy) ethyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group,
3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group,
2- (3-sulfopropoxy) ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2- (3-
Sulfopropoxy) propyl group, 2- [3-sulfopropoxy) ethoxy] ethyl group, 2-hydroxy-3-
(3'-sulfopropoxy) propyl group), aralkyl group (alkyl radical preferably has 1 to 5 carbon atoms, aryl group is preferably phenyl group, for example, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group. , P-tolylpropyl group, p-methoxyphenethyl group, p-chlorophenethyl group, p-carboxybenzyl group, p-suphophenethyl group, p-sulfobenzyl group), aryloxyalkyl group (the number of carbon atoms of the alkyl radical is 1 to 1). 5 is preferable, and the aryl group of the aryloxy group is preferably a phenyl group, for example, a phenoxyethyl group, a phenoxypropyl group, a phenoxybutyl group, p
-Methylphenoxyethyl group, p-methoxyphenoxypropyl group, etc.), vinylmethyl group} and the like, and an aryl group includes a phenyl group and the like. L ₁ , L ₂ and L ₃ are methine groups or substituted methine groups Represents R'is an alkyl group (for example, a methyl group or an ethyl group), a substituted alkyl group (for example, an alkoxyalkyl group (for example, a 2-ethoxyethyl group), a carboxyalkyl group (for example, a 2-carboxyethyl group), an alkoxycarbonylalkyl group ( For example, it represents a 2-methoxycarbonylethyl group, an aralkyl group (eg, benzyl group, phenethyl group), an aryl group (eg, phenyl group, p-methoxyphenyl group, p-chlorophenyl group, o-carboxyphenyl group, etc.) and the like. And L ₁ and R ₂ , L ₃ and
R ₃ may be bonded to each other via a methine chain to form a nitrogen-containing heterocycle. The substituent attached to the nitrogen atom at the 3-position of the thiazolinone ring or imidazolinone ring formed by Q ₂ and Q ₃ is, for example, an alkyl group (preferably having 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group). , Allyl group,
Aralkyl group (alkyl group radical preferably has 1 to 5 carbon atoms, for example, benzyl group, n-carboxyphenylmethyl group), aryl group (total carbon number is preferably 6 to 9, for example, phenyl group, p-carboxyphenyl group) ),
Hydroxyalkyl group (alkyl radical has 1 carbon atom
5 are preferable, for example, 2-hydroxyethyl group), carboxyalkyl group (the number of carbon atoms of the alkyl radical is 1
5 are preferred, for example, a carboxymethyl group), an alkoxycarbonylalkyl group (the alkyl radical of the alkoxy moiety preferably has 1 to 3 carbon atoms, and the alkyl moiety preferably has 1 to 5 carbon atoms, such as a methoxycarbonylethyl group). Can be mentioned.

Examples of the anion represented by X ₁ include halogen ion (iodine ion, bromine ion, chlorine ion, etc.), perchlorate ion, thiocyanate ion, benzenesulfonate ion, p-toluenesulfonate ion, methylsulfate ion, Examples thereof include ethylsulfate ion.

Typical examples of the sensitizing dye represented by the general formula (II) are as follows.

[Wherein Y ₁ and Y ₂ each represent a nonmetallic atom group necessary for forming a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring, and these heterocycles are Lower alkyl group (eg methyl group, ethyl group), alkoxy group (eg methoxy group, ethoxy group), hydroxy group, aryl group (eg phenyl group), alkoxycarbonyl group (eg methoxycarbonyl group), halogen atom (eg chlorine atom) , Bromine atom) or the like. R ₄ and R ₅ are each a lower alkyl group (for example, methyl group, ethyl group, propyl group,
Butyl group), an alkyl group having a sulfo group (for example, β-
Sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (for example, sulfoethoxyethyl group, sulfopropoxyethyl group), alkyl group having a carboxy group (for example, β-carboxyethyl group , Γ-carboxypropyl group, γ-carboxybutyl group, δ-carboxybutyl group).

R ₆ represents a methyl group, an ethyl group or a propyl group. X ₂ represents an anion that is usually used for cyanine dyes (for example, halogen ion, benzene sulfonate ion, p-toluene sulfonate ion, etc.).

n ₄ and n ₅ represent 1 or 2. m represents 0 or 1,
In the case of an inner salt, m = 0.

Specific examples of the compound of (III) R ₇ and R ₈ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably it has 1 to 8 carbon atoms. For example, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl.

Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atom), hydroxyl group, alkoxycarbonyl group (preferably having 8 or less carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), alkoxy group (preferably having 7 or less carbon atoms, for example, methoxy, ethoxy, propoxy, Butoxy, benzyloxy), aryloxy groups (eg phenoxy,
p-tolyloxy), an acyloxy group (preferably having 3 or less carbon atoms, for example, acetyloxy, propionyloxy), an acyl group (preferably having 8 or less carbon atoms, for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (for example, carbamoyl). , N, N-dimethylcarbimoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl group (eg rufamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl), aryl group (eg phenyl, p-hydroxyphenyl, p) Examples include an alkyl group (preferably having 6 or less carbon atoms in the alkyl portion) substituted with -carboxyphenyl, p-sulfophenyl, α-naphthyl) and the like. However, two or more of these substituents may be substituted with an alkyl group.

R ₉ and R ₁₀ are each independently a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl), a lower alkoxy group (preferably having 1 to 4 carbon atoms, for example Methoxy, ethoxy, propoxy, butoxy), phenyl group, benzyl group or phenethyl group. Particularly, a lower alkyl group and a benzyl group are advantageously used.

R ₁₁ and R ₁₂ each represent a hydrogen atom, or R ₁₁
And R ₁₂ combine to form a divalent alkylene group (eg, ethylene or trimethylene). The alkylene group is one, two or more suitable groups such as an alkyl group (preferably having 1 to 4 carbon atoms, eg, methyl, ethyl, propyl, isopropyl, butyl), a halogen atom (eg, chlorine atom, bromine). Atom, or an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy) and the like.

R ₁₃ is a hydrogen atom, a lower alkyl group (preferably having a carbon number of 1 to 4, such as methyl, ethyl, propyl), a lower alkoxy group (preferably having a carbon number of 1 to 4, such as methoxy, ethoxy, propoxy, butoxy), Phenyl, benzyl group, or Represents Here, W ₁ and W ₂ are each independently an alkyl group (including a substituted alkyl group. Preferably, the alkyl moiety has 1 to 18 carbon atoms, more preferably 1 to 4, for example, methyl, ethyl, propyl, butyl, benzyl, Phenylethyl),
Or, it represents an aryl group (including a substituted phenyl group, for example, phenyl, naphthyl, tolyl, p-chlorophenyl), and W ₁ and W ₂ may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. it can. However, R ₉ and R ₁₃ or R ₁₀
And R ₁₃ are linked to form a divalent alkylene group (the above R ₁₁ and R ₁₂
It is also possible to form a divalent alkylene group which is formed by connecting and.

Z ₄ and Z ₅ represent a group of non-metal atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole nucleus [eg, benzothiazole, 4-chlorobenzothiazole,
5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-
Bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-
Phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,
6-dimethylbenzothiazole, 5-hydroxy-6-
Methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-
d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-
d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole,
5-methoxynaphtho [2,3-d] thiazole], selenazole nucleus [eg benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5
-Methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzo Oxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole,
5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-
Hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5
-Ethoxybenzoxazole, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole], quinoline nucleus [eg 2-
Quinoline, 3-methyl-2-quinoline, 5-ethyl-2
-Quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline,
8-fluoro-4-quinoline], 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3
-Diethyl indolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-
Dimethyl-5-chloroindolenine), imidazole nucleus (for example, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1- Methyl-5,6-dichlorobenzimidazole,
1-ethyl-5,6-dichlorobenzimidazole, 1-
Ethyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1- Phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1
-Phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole ) And a pyridine nucleus (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine). Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously.
More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

X ₃ is an acid anion (for example, chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate,
4-chlorobenzenesulfonate, 4-nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate).

m ₃ represents 0 or 1, and in the case of an intramolecular salt, m = 0.

Specific examples of compounds of (IV) R ₄₁ and R ₁₅ may be the same or different,
Each represents an alkyl group (including a substituted alkyl group). Specific examples thereof are the same as those described for R ₇ and R ₈ in the general formula (IV).

R ₁₆ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or a phenethyl group. Specific examples of R ₁₆ are the same as those described for R ₉ and R ₁₀ in the general formula (IV).

V is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl), an alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy, ethoxy, butoxy), a halogen atom (eg, Fluorine atom, chlorine atom) and a substituted alkyl group (preferably having 1 to 4 carbon atoms, for example, trifluoromethyl, carboxymethyl).

Z ₆ represents a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, and specific examples of the 5- or 6-membered nitrogen-containing heterocycle include Z _{4 of} the general formula (IV), It is the same as the ring described in Z ₅ .

X ₄ represents an acid anion, and specific examples of X ₄ are represented by general formula (IV)
The same as the acid anion described in X ₃ of. m ₄ is 0
Alternatively, it represents 1, and m = 0 in the case of an inner salt.
n ₆ and p each independently represent 1 or 2.

Specific examples of compounds of (V) These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. With sensitizing dye,
A dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and which exhibits supersensitization may be contained in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Rese
arch Disclosure) Volume 176 17643 (Issued December 1978) No. 23
It is described in section J on page IV.

The silver halide emulsion in the present invention is usually chemically sensitized. As a method of chemical sensitization, known methods such as a sulfur sensitization method, a reduction sensitization method, and a noble metal sensitization method can be used, and they are used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and iridium may be contained.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiosols, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin.

Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

The silver halide emulsion in the present invention has the following general formula (1
The compounds represented by -a), (1-b) and (1-c) may be included.

(1-a) Z-SO ₂ · S-M Z represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group. Y has 6 to 18 carbon atoms and represents an atomic group necessary for forming an aromatic ring or a hetero ring. M represents a metal atom or an organic cation. n is 2
Represents an integer of 10. Further, the alkyl group, the aryl group, the heterocyclic group, the aromatic ring and the hetero ring represented by Z and Y may be substituted.

Examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, and a carbon number of 1 to 8
Alkoxy groups, halogen atoms such as chlorine, nitro groups, amino groups, and carboxyl groups.

Examples of the hetero ring represented by Z and Y include thiazole, benzthiazole, imidazole, benzimidazole and oxazole rings.

The metal atom represented by M is preferably a metal atom such as a sodium ion or a potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group.

 The following can be mentioned as specific examples.

(5) H ₃ C ・ SO ₂・ SNa The addition amount of the compounds represented by the general formulas (1-a), (1-b) and (1-c) is 0.001 to 1 per mol of silver halide.
g, especially 0.01 to 0.2 g is preferred. The timing of addition may be during the formation of the silver halide emulsion or immediately before coating, but is preferably during the formation of the grain or during the chemical sensitization.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as bench azolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, etc. , Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes) ), Pentaazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. may be added. Can.

Particularly, a polyhydroxybenzene compound is preferable in that pressure resistance is improved without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having any one of the following structures.

X and Y are each -H, -OH, halogen atom -OM (M
Is an alkali metal ion), -alkyl group, phenyl group,
Amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl group, sulfonated amino group,
A sulfonated carbonyl group, a carboxyphenyl group, a carboxyalkyl group, a carboxyamino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkyl ether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group.

More preferably, -H, -OH, -Cl, -Br, -COO
_{H, -CH 2 CH 2 COOH,} -CH 3, -CH 2 CH 3, -CH (CH 3) 2,
_{-C (CH 3) 3, -OCH} 3, -CHO, -SO 3 Na, -SO 3 H, -S
CH ₃ , It is. X and Y may be the same or different.

Particularly preferred representative compound examples are The polyhydroxybenzene compound may be added to the emulsion layer in the light-sensitive material or to a layer other than the emulsion layer. The effective amount of addition is in the range of 10 ^-5 to 1 mol per 1 mol. Yes,
The range of 10 ^-3 mol to 10 ^-1 mol is particularly effective.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for example, polyalkylene oxide or an ether, ester thereof,
Developers such as amine derivatives, thioether compounds, thiamorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and aminophenols may be included.

Among them, 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.) are preferable, and usually 5 g.
/ m ² or less, and more preferably 0.01 to 0.2 g / m ² .

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (Such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholy) carbonyl-3-pyridinio) methanesulfonate, and haloamidinium Salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium and 2-naphthalene sulfonate) can be used alone or in combination. Among them, JP-A-53-41220, JP-A-53-57257, and JP-A-59-16254
6, active vinyl compounds described in JP-A-60-80846 and active halides described in U.S. Pat. No. 3,325,287 are preferred.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating auxiliary liquid, antistatic, anti-slip property improvement, emulsion dispersion, anti-adhesion property and photographic property improvement (for example, development acceleration, contrast enhancement) For various purposes such as sensitization), various surfactants may be included.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Agent: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing acidic groups such as carboxy group, sulfo group, phospho group, sulfuric acid ester group, phosphoric acid ester group such as acid esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid Amphoteric surfactants such as esters, alkyl betaines, amine oxides; alkyl amine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

In order to prevent static electricity, it is preferable to use the fluorine-containing active surface active agent described in JP-A-60-80849.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide and polymethylmethacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The light-sensitive material used in the present invention may contain a water-insoluble or fibrous synthetic polymer dispersion for the purpose of dimensional stability. For example, alkyl (meth) acrylate, alkoxyacrylic (meth) acrylate, glycidyl (meth) acrylate, etc., alone or in combination, or in combination with acrylic acid, methacrylic acid, etc., use a polymer as a monomer component. be able to.

The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can be used.

As a support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper and the like can be used.

There is no particular limitation on the developing agent used in the developer used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used.

The dihydroxybenzene developing agent hydroquinone used in the present invention is preferred.

Examples of the developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-dimethyl-3-pyrazolidone.

As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol is preferable.

The developing agent is preferably used usually in an amount of 0.05 mol / to 0.8 mol /. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is used in an amount of 0.05 mol / -0.5 mol / and the latter is used in an amount of 0.06 mol / or less. preferable. Further, an amino compound described in JP-A-56-106244 and an imidazole compound described in JP-B-48-35493 can be used.

In the developer used in the present invention, the compounds described in JP-A-56-24347 as a silver stain inhibitor, the compounds described in JP-A-62-212,651 as a development unevenness inhibitor, and the dissolution aids The compounds described in JP-A No. 61-267759 can be used.

Further, regarding the development processing method of the light-sensitive material of the present invention,
Japanese Unexamined Patent Publication No. 103536/1990, pages 19 to 20;
The descriptions on pages 13 to 16 of 55349 and pages 16 to 19 of JP 2-10307 can be referred to.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by these.

Example 1 [1] Preparation of emulsion Preparation of emulsion A 1 liquid water 1.0 gelatin 20 g sodium chloride 20 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml Sodium chloride 30.5g Potassium bromide 14.0g Potassium hexachloroiridium (III) (0.001% aqueous solution) 15ml Ammonium hexabromodium (III) (0.001% aqueous solution) 1.5ml In one liquid kept at 38 ℃, pH 4.5 Solution 2 and solution 3 were added simultaneously with stirring for 10 minutes to form 0.16 μm core particles. Then, the following 4 liquid and 5 liquid were added over 10 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation.

4-liquid water 400 ml Silver nitrate 100 g 5-liquid water 400 ml Sodium chloride 30.5 g Potassium bromide 14.0 g After that, washing was carried out by a flocculation method according to a conventional method, and gelatin was added.

The pH was adjusted to 5.1 and pAg7.5, 8 mg of sodium thiosulfate and 12 mg of chloroauric acid were added, and chemical sensitization was performed at 65 ° C to obtain optimum sensitivity, and 4-hydroxy-6-methyl-1, as a stabilizer.
200 mg of 3,3a, 7-tetraazaindene and phenoxyethanol as a preservative were added. Finally 80 mol% of silver chloride
A silver iodochlorobromide cubic grain emulsion having an average grain size of 0.20 μm was obtained. (Variation coefficient 9%) Further, 100 ppm of phenoxyethanol was added as a preservative.

Preparation of Emulsion B After washing with water and adding gelatin in the same manner as in Emulsion A, ortho sensitizing dyes shown in Table 1 were added for ortho sensitization. Furthermore, for supersensitization and stabilization 4,4'-
Bis- (4,6-dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid sodium salt was added in an amount of 300 mg per mol of silver. Otherwise in the same manner as for Emulsion A, the final average grain size was 0.20 μm, containing 80 mol% of silver chloride.
A silver iodochlorobromide cubic emulsion was obtained (coefficient of variation 9%) Preparation of emulsion C Emulsion A except that hexacyanoiron (II) potassium (0.1%) was added to solution 5 in the amounts shown in Table 1. In the same manner, finally, the average particle size containing 80 mol% of silver chloride was 0.20.
A μm silver iodochlorobromide cubic emulsion was obtained (coefficient of variation 8%) Preparation of emulsion D After washing with water in the same manner as in emulsion C, the addition of gelatin was followed by addition of the ortho sensitizing dye shown in Table 1 I made a sense. Further, for supersensitization and stabilization, 300 mg of 4,4'-bis- (4,6-dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid sodium salt was added to 1 mol of silver. Except for these, in the same manner as in Emulsion C, the final average particle size was 0.20 μm containing 80 mol% of silver chloride.
A silver iodochlorobromide cubic emulsion was obtained (coefficient of variation: 9%) 2. Preparation of coating sample Among the emulsions A to D prepared in this manner, Tables 1 and 2 are those which have not been ortho-sensitized yet. Ortho Afterwards, hydroquinone 100m for all emulsions A to D
g / m ² , polyethyl acrylate latex 25% in gelatin binder ratio, 2-bis (vinylsulfonylacetamido) ethane 86 mg / m ² as a hardener, and coated gelatin as shown in Table 1 on polyester support. Gelatin was added in an amount so that coating samples 1 to 20 were coated. At this time, 0.5 g / m ^{2 of} gelatin was used as a protective layer on the upper side of the emulsion layer, and 60 mg / m ^{2 of} polymethylmethacrylate having a particle size of 2.5 μm and 70 mg of colloidal silica having a particle size of 10 mμ were used as a matting agent.
/ m ² , and dodecylbenzenesulfonic acid sodium salt as a coating agent and a fluorine-containing surfactant having the following structural formula were coated simultaneously with the emulsion layer.

The amount of gelatin shown in Table-1 is 0.
It represents the sum of 5 g / m ² and gelatin in the emulsion layer.

The support of the sample used in this example has a back layer and a back protective layer having the following compositions.

[Back layer]

Gelatin 2.0 g / m ² Sodium dodecylbenzene sulfonate 80 mg / m ² Dye 70 mg / m ² Dye 70 mg / m ² Dye 90 mg / m ² 1,3-Divinylsulfonyl 2-propanol 60 mg / m ² [Back protective layer] Gelatin 0.5 g / m ² Polymethylmethacrylate (particle size 4.7μm) 30mg /
m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Fluorosurfactant containing 2 mg / m ² Silicone oil 100 mg / m ² [3] Evaluation of sample i) Evaluation of photographic performance The obtained sample was exposed to quinocene flash light with an emission time of 10 ^-6 sec by interposing an interference filter having a peak at 488 nm and a continuous wedge. Sensitometry was performed using an automatic processor FG-710NH manufactured by Co., Ltd. at the temperature and time shown below.

However, as the developing solution and the fixing solution, the developing solution a and the fixing solution a were used, respectively.

The exposure amount of the logarithm to give the current image 38 ° C. 14 seconds Fixing 37 ° C. 9.7 seconds Washing 26 ° C. 9 seconds squeeze 2.4 seconds Drying 55 ° C. 8.3 seconds Total 43.4 seconds concentrations 3.0 and sensitivity, Table 1 at ^* relative sensitivity It was shown to. In addition, the inclination of the straight line connecting the points of density 0.1 and 3.0 in the characteristic curve is also shown in Table 1 as gradation.

* For each dye, the coating amount of Gel was 2.0 g / m ² , no iron was added, and the sensitivity immediately before coating the dye was set to 100.

ii) Evaluation of suitability for rapid processing Sensitometry was carried out in the same manner as in i) except that the line speed of the FG-710NH automatic developing machine was lowered, the time from development to drying was increased 1.7 times, and the total was 73.8 seconds. ) And the difference in gradation, the rapid processing suitability was evaluated.

iii) Evaluation of pressure property (scratch) After passing the untreated coated sample under the 0.1 mm and 0.01 mm sapphire needles under load, from development to drying under the same conditions as the evaluation of photographic performance. Processed.

The degree of blackening of the portion rubbed with the needle of the sample was visually evaluated and ranked from 5 (good) to 1 (bad).

Developer-i Hydroquinone 25.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3
-Pyrazolidone 0.5 g potassium sulfite 90.0 g ethylenediaminetetraacetic acid disodium 2.0 g potassium bromide 5.0 g 5-methylbenzotriazole 0.2 g 2-methicaptobenzimidazole-5-sulfonic acid 0.
3g Sodium carbonate 20g Add water 1 (Add sodium hydroxide to adjust pH = 10.6) Fixer-ammonium thiosulfate 210g Sodium sulfite (anhydrous) 20g Ethylenediaminetetraacetic acid disodium 0.1g Glacial acetic acid 15g Add water 1 (PH adjusted to 4.8 with ammonia water) Wash water Tap water Sensitivity difference is 73.8 seconds processing sensitivity −43.4 seconds sensitivity Gradient difference represents 〃 gradation − 〃 gradation. That is, the smaller the difference in sensitivity and the difference in gradation, the more suitable it is for rapid processing. As is apparent from Table 1, in order to have high sensitivity, excellent suitability for rapid processing, and good pressure property, a small amount of gelatin coating is good, and an iron compound is contained.
Moreover, it is found that it is necessary to add the sensitizing dye before the chemical sensitization.

Example 2 [1] Preparation of Emulsion Preparation of Emulsion E In the same manner as Emulsion A used in Example 1, after washing with water and addition of gelatin, panchromatic sensitizing dyes shown in Table 2 were added for panchromatic sensitization. .

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt was added in an amount of 300 mg per mol of silver.

Except for this, the same procedure as for Emulsion A was used to finally add silver chloride.
A silver iodochlorobromide cubic emulsion having an average particle size of 0.20 μm containing 80 mol% was obtained (coefficient of variation: 9%) Preparation of emulsion F In the same manner as emulsion C used in Example I, the steps up to gelatin addition after washing with water were carried out. After that, the panchromatic sensitizing dye shown in Table 2 was added to perform panchromatic sensitization.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stillbenzylsulfonic acid disodium salt was added at 300 mg per mol of silver.

Except for this, in the same manner as in Emulsion C, finally a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and having an average grain size of 0.20 μm was obtained (coefficient of variation: 9%) [2] Preparation of coating sample Panchromatic sensitization was performed by adding the panchromatic sensitizing dyes shown in Table 2 to the emulsions A and C prepared in Example I.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt was added in an amount of 300 mg per mol of silver.

Thereafter, the emulsions A, C, E and F were coated in the same manner as in Example 1 to prepare coating samples 1 to 9.

[3] Evaluation of sample i) Evaluation of photographic performance Evaluation was performed in the same manner as in Example-1. However, it was exposed with a xenon flash light of 10 ^-6 sec through an interference filter having a peak at 633 nm.

However, for each dye, the coating amount of Gel was 2.0 g / m ² , iron was not included, and the sensitivity immediately before coating the dye was set to 100.

ii) Evaluation of suitability for rapid processing iii) Evaluation of pressure property (scratch) Both ii) and iii) were evaluated in the same manner as in Example 1.

As is clear from Table 2, not only the ortho dye of the general formula (I) but also the panchromatic dye of the general formula (II) has high sensitivity and excellent rapid processability, and is small in order to improve the pressure property. Contains an iron compound in a gelatin coating amount,
It can be seen that it is necessary to add the sensitizing dye before the chemical sensitization.

Example 3 [1] Preparation of emulsion Preparation of emulsion G In the same manner as the emulsion A used in Example I, gelatin was added after washing with water, and then panchromatic dye of Table 3 was added for panchromatic sensitization.

Except for this, the same procedure as in Emulsion A was performed to finally obtain a silver iodochlorobromide, cubic emulsion containing 80 mol% of silver chloride and having an average particle size of 0.20 μm (coefficient of variation: 9%) Preparation of Emulsion H Example I In the same manner as in Emulsion C used in Example 1, after washing with water and addition of gelatin, panchromatic dyes in Table 3 were added for panchromatic sensitization.

Except for this, the same procedure as for Emulsion C was used to finally add silver chloride.
A silver iodochlorobromide cubic emulsion containing 80 mol% and having an average particle size of 0.20 μm was obtained (coefficient of variation: 9%). [2] Preparation of coating sample Emulsion A and C prepared in Example I Was added to enhance the panchromatic sensitivity.

Thereafter, the emulsions A, C, G and H were coated in the same manner as in Example 1 to prepare coating samples 1 to 9.

[3] Evaluation of sample i) Evaluation of photographic performance Evaluation was performed in the same manner as in Example-1. However, it was exposed with xenon flash light of 10 ^-6 sec through an interference filter having a peak at 670 nm. However, Gel coating is good for each dye
The sensitivity was 2.0 g / m ² , no iron was added, and the sensitivity immediately before coating the dye was set to 100.

ii) Evaluation of suitability for rapid processing iii) Evaluation of pressure property (scratch) Both ii) and iii) were evaluated in the same manner as in Example 1.

As is clear from Table 3, even the panchromatic dye of the general formula (III) has high sensitivity and excellent suitability for rapid processing,
Further, it is necessary to contain the iron compound in a small gelatin coating amount and to add the sensitizing dye before the chemical sensitization in order to improve the pressure resistance.

Example 4 [1] Preparation of Emulsion Preparation of Emulsion I In the same manner as Emulsion A used in Example I, gelatin was added after washing with water, and then an infrared sensitizing dye shown in Table 4 was added to carry out infrared sensitization. I felt.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added to silver 1
300 mg and 450 mg were added to each mole.

Except for this, the same procedure as for Emulsion A was used to finally add silver chloride.
A silver iodochlorobromide cubic emulsion containing 80 mol% and having an average particle size of 0.20 μm was obtained (coefficient of variation: 9%) Preparation of emulsion J In the same manner as emulsion C used in Example I, up to the addition of gelatin after washing with water. After that, the infrared sensitizing dyes shown in Table 4 were added for infrared sensitization.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added to silver 1
300 mg and 450 mg were added to each mole.

Except for this, in the same manner as in Emulsion C, a silver iodochlorobromide cubic emulsion having an average grain size of 0.20 μm and containing 80 mol% of silver chloride was finally obtained (variation coefficient 9%). [2] Coating sample Preparation Infrared sensitization was carried out by adding the infrared sensitizing dyes in Table 4 to the emulsions A and C prepared in Example I.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added to silver 1
300 mg and 450 mg were added to each mole.

Thereafter, emulsions A, C, I and J were coated in the same manner as in Example 1 to prepare coated samples 1 to 9.

[3] Evaluation of sample i) Evaluation of photographic performance Evaluation was performed in the same manner as in Example-1. However, it was exposed with xenon flash light of 10 ^-6 sec through an interference filter having a peak at 780 nm. However, the gel coating amount for each dye
The sensitivity was 2.0 g / m ² , no iron was added, and the sensitivity immediately before addition of the dye was 100.

ii) Evaluation of suitability for rapid processing iii) Evaluation of pressure property (scratch) Both ii) and iii) were evaluated in the same manner as in Example 1.

As is clear from Table 4, the infrared dye of the general formula (IV) is also highly sensitive and has excellent rapid processability, and in order to improve the pressure property, the iron compound is contained in a small gelatin coating amount. And, it is necessary to add the sensitizing dye before the chemical sensitization.

Example 5 [1] Preparation of Emulsion Preparation of Emulsion K In the same manner as Emulsion A used in Example I, gelatin was added after washing with water, and then an infrared sensitizing dye shown in Table 5 was added to carry out infrared sensitization. I felt.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stylbenzylsulfonic acid disodium salt and 2,5-
300 mg and 450 mg of dimethyl-3-allyl-benzothiazole iodo salt were added to 1 mol of silver, respectively.

Except for this, the same procedure as for Emulsion A was used to finally add silver chloride.
A silver iodochlorobromide cubic emulsion containing 80 mol% and having an average particle size of 0.20 μm was obtained (coefficient of variation: 9%) Preparation of emulsion L In the same manner as emulsion C used in Example I, up to the addition of gelatin after washing with water. After that, infrared sensitizing dyes shown in Table 5 were added for infrared sensitization.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added to silver 1
300 mg and 450 mg were added to each mole.

Except for this, in the same manner as in Emulsion C, a silver iodochlorobromide cubic emulsion having an average grain size of 0.20 μm and containing 80 mol% of silver chloride was finally obtained (variation coefficient 9%). [2] Coating sample Preparation Infrared sensitization was carried out by adding the infrared sensitizing dyes shown in Table 5 to the emulsions A and C prepared in Example I.

Furthermore, for supersensitization and stabilization, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added to silver 1
300 mg and 450 mg were added to each mole.

Thereafter, Emulsions A, C, K and L were coated in the same manner as in Example 1 to prepare coating samples 1 to 9.

[3] Evaluation of sample i) Evaluation of photographic performance Evaluation was performed in the same manner as in Example-1. However, it was exposed with xenon flash light of 10 ^-6 sec through an interference filter having a peak at 780 nm. However, for each dye, the gel coating amount was 2.0 g / m ² , no iron was added, and the sensitivity immediately before coating the dye was 100
And

ii) Evaluation of suitability for rapid processing iii) Evaluation of pressure property (scratch) Both ii) and iii) were evaluated in the same manner as in Example 1.

It is highly sensitive to dyes and has excellent suitability for rapid processing.
Further, it is necessary to contain the iron compound in a small gelatin coating amount and to add the sensitizing dye before the chemical sensitization in order to improve the pressure resistance.

Example 6 [1] Preparation of Emulsion Preparation of Emulsion M In the same manner as in Emulsion A except that the iron compound shown in Table 6 was added to Solution 5 of Example 1, finally 80 mol% of silver chloride was added.
A silver iodochlorobromide cubic emulsion having an average grain size of 0.20 μm was obtained (coefficient of variation 8%) Preparation of emulsion N After washing with water and adding gelatin in the same manner as in emulsion M, the ortho sensitizing dyes shown in Table 6 were added. In addition, ortho-sensitized. In the same manner as Emulsion M except the above, finally a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and having an average grain size of 0.20 μm was obtained (variation coefficient 9%). [2] Preparation of coating sample Among the emulsions M and N thus prepared, the ortho sensitizing dyes shown in Table 1 were added to M for ortho sensitization.

Thereafter, the emulsions M and N were coated in the same manner as in Example 1 to prepare coated samples.

[3] Evaluation of sample Evaluation was performed in the same manner as in Example 1.

As is apparent from Table 6, various iron compounds can be used in the present invention.

Example 7 [1] Preparation of Emulsions Preparation of Emulsions P, Q, R and S Emulsions A, B, C, except that the amounts of sodium chloride and potassium bromide in the third and fifth solutions of Example 1 were changed to 20.2 g and 35.1 g, respectively. In the same manner as in D, finally, a silver iodochlorobromide cubic grain emulsion containing 50 mol% of silver chloride and having an average grain size of 0.19 μm was finally obtained.

Preparation of Emulsions T, U, V, and W Emulsions A, B, C, and D, respectively, except that the amounts of sodium chloride and potassium bromide in solutions 3 and 5 of Example 1 were changed to 9.9 g and 56 g, respectively. Finally, silver iodochlorobromide cubic grains containing 20 mol% of silver chloride and having an average grain size of 0.19 μm were obtained.

[2] Preparation of Coated Samples Among the emulsions P to W, P, R, T and V which were not spectrally sensitized were spectrally sensitized in the same manner as in Example 1.

Thereafter, the emulsions P to W were coated in the same manner as in Example 1 to prepare coated samples.

[3] Evaluation of sample Evaluation was performed in the same manner as in Example 1.

From Table 7, the effect of the present invention is recognized even if the halogen composition changes.

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on the same surface of the support, and a light-sensitive material on the support. The amount of gelatin on the side having the light-sensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer is 2.5 g / m ² or less, and the silver halide grains are 10 ^-3 relative to silver.
A silver halide photographic light-sensitive material containing an iron compound in an amount of less than or equal to mol and containing a sensitizing dye before the chemical sensitization of silver halide grains. 2. The silver halide emulsion layer contains at least one of the sensitizing dyes represented by the following general formulas (I) to (V), wherein the silver halide emulsion layer contains at least one sensitizing dye. Silver halide light-sensitive material. General formula (I) Z ₁ represents a non-metal atom group necessary for forming a 5- or 6-membered heterocycle, and Q ₁ represents a non-metal atom group necessary for forming a 5-membered nitrogen-containing heterocycle. R ₁ represents an alkyl group or a substituted alkyl. n ₁ represents 1 or 2. Z ₂ and Z ₃ each represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₂ and R ₃ each represent an alkyl group, a substituted alkyl group or an aryl group. Q ₂ and Q _{3 taken} together are 4-thiazolidinone, 5
-Thiazolidinone or represents a group of non-metal atoms necessary to complete a 4-imidazolidinone nucleus. L ₁ , L ₂ and L ₃ each represent a methine group or a substituted methine group. n ₂ and n ₃ each represent 1 or 2. X ₁ represents an anion. m ₁ represents 0 or 1, and when forming an intramolecular salt, m = 0
It is. Y ₁ and Y ₂ each represent a group of non-metal atoms necessary for forming a heterocycle such as a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring, The ring is a lower alkyl group,
It may be substituted with an alkoxy group, a hydroxy group, an aryl group, an alkoxycarbonyl group, or a halogen atom. R ₄ ,
R ₅ each represents an alkyl group having a lower alkyl group, a sulfo group, or a carboxy group. R ₆ represents a lower alkyl group. X ₂ represents an anion.
n ₄ and n ₅ represent 1 or 2. m ₂ represents 0 or 1, and in the case of an intramolecular salt, m = 0. R ₇ and R ₈ each represent an alkyl group or a substituted alkyl group. R ₉ and R ₁₀ each independently represent a hydrogen atom lower alkyl group, lower alkoxy group, phenyl group, benzyl group or phenethyl group. R ₁₁ and R ₁₂ each represent a hydrogen atom,
Alternatively, R ₁₁ and R ₁₂ are linked to each other to form a divalent alkylene group. R ₁₃ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or Represents However, W ₁ and W ₂ each independently represent an alkyl group or an aryl group, and W ₁ and W ₂ may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Further, R ₉ and R ₁₃ or R ₁₀ and R ₁₃ may be linked to each other to form a divalent alkylene group. Z ₄ and Z ₅ each independently represent a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₃ represents an acid anion. m ₃ represents 0 or 1, and m ₃ = 0 when forming an intramolecular salt. R ₁₄ and R ₁₅ each represent an alkyl group or a substituted alkyl group.
R ₁₆ is a hydrogen atom, a lower alkyl group, a lower alkoxy group,
It represents a phenyl group, a benzyl group or a phenethyl group.
V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z ₆ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₄ represents an acid anion. n ₆ represents 1 or 2. m ₄ represents 0 or 1, and in the case of an inner salt, m ₄ = 0. p represents 1 or 2.