JP2651614B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material, and more particularly, to an increase in spectral sensitivity in a green light wavelength region and an improvement in storage stability. It relates to an excellent silver halide photographic material.

[Background of the Invention]

Conventionally, silver halide photographic materials having improved spectral sensitivity in the green light region include oxacarbocyanines in combination of two types, for example, JP-B-44-32753, JP-A-52-239.
No. 31 or a combination of oxacarbocyanine and benzimidazolocarbocyanine.
No. 646 or a combination of oxacarbocyanine and oxathiacarbocyanine, for example, JP-A-60-42750
And No. 63-167348 are known.

However, most of these prior arts have a desensitization property when a silver halide photographic light-sensitive material is coated in multiple layers.

Such disadvantageous phenomena, which are relatively invisible in a single-layer configuration, are not clear, but may be due to the desorption of adsorbed dyes or the rearrangement of the dyes due to the multilayer configuration.

For this reason, measures have been taken to increase the dye adsorbability by changing the halide composition of the silver halide emulsion or the crystal wall of the silver halide crystal, or by adding halogen, but changing the emulsion side in this way The heat treatment conditions and other conditions are different from each other, resulting in a bad influence on the photographic performance or storage stability balanced with other layers, and these methods have limitations.

Therefore, a new spectral sensitization method which does not have the above-mentioned disadvantages and has high green light sensitivity has been strongly desired.

[Object of the invention]

The present invention is to spectrally sensitize a silver halide photographic material. A first object of the present invention is to provide a silver halide photographic material having enhanced spectral sensitization of green light, and a second object of the present invention. Another object of the present invention is to provide a silver halide photographic material having low desensitization due to direct detachment of a dye from silver halide.

A third object is to provide a green-sensitive silver halide photographic material having excellent storage stability.

[Configuration of the invention]

The present inventor has conducted intensive studies in order to develop a silver halide photographic light-sensitive material satisfying such demands.
When a specific combination of two different symmetrical dyes and an asymmetrical dye having a common structure with the dye is used, there is no desensitization due to desorption of the dye and excellent storage stability. We found that we could obtain photosensitive material.

The supersensitizing effect is not yet clear, but a strong intermolecular force can be exerted between the symmetric dye and the asymmetric dye, thereby preventing the desorption of the dye and improving the spectral sensitization efficiency. Is considered to have been obtained.

The present invention has been made based on such findings.

That is, an object of the present invention is to provide a symmetrical carbohydrate represented by the following general formulas [I] and [II] wherein at least one of the silver halide emulsion layers coated on the support has the same left and right heterocyclic structure. The following general formula [III] having at least one of each of the cyanine dyes and one of the same heterocyclic structures as the dyes
At least one of the asymmetric carbocyanine dyes represented by
This is achieved by a silver halide photographic light-sensitive material characterized in that supersensitive sensitization is performed by combining the two.

General formula [I] General formula (II) General formula (III) In the formula, Z ¹ represents a nonmetal atom group necessary for forming a naphtho [2,3-d] oxazole ring. Z ² is naft [1,2
-D] oxazole ring or naphtho [2,1-d] oxazole ring represents a nonmetallic atom necessary for forming the ring. Z ³
Z ¹ and represents Z ¹ having a substituent group as defined synonymous or Steri mol parameter _{L / B 1 ≦ 2.2, Z} 4 is defined by Z ² synonymous or Steri mol parameter L / B ₁ ≦ 2.2 Z ² having the following substituents.

R ¹ and R ² represent an alkyl group or a substituted alkyl group which may be the same or different. L ¹ , L ² and L ³ represent a methine group or a substituted methine group.

 X Represents an anion and n represents 1 or 2.

The substituent defined by the sterimol parameter which may be substituted for Z ³ and Z ⁴ in the general formula III is such that the value of S represented by S = L / B ₁ is 2.2 or less. and a substituent having a value of B _1. Here L and B ₁ are Ferloop, Hogenstraten, Tipcar (A.Verloop.W.Hoogen
straaten.J.Tipker, “Drug Design (Drug)
Design), Volume 7, (EJArins)
Ed represents the L and B ₁ of STERIMOL parameters described in and New York, pp 180-185 in (1976)). (Unit: Δ) The value of S calculated from each substituent is shown in the table below.

In the formula, the optionally substituted alkyl group represented by R ¹ and R ² includes, for example, 1 to 18 carbon atoms, preferably 1
To 7, particularly preferably 1 to 4, alkyl groups, unsubstituted alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl and the like), substituted alkyl groups, for example, aralkyl groups ( For example, benzyl, 2-phenylethyl and the like, hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl and the like), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, carboxyethyl, 3-carboxy) Propyl group, 4-carboxybutyl group, carboxymethyl group, etc., alkoxyalkyl group (eg, 2-methoxyethyl group, 2- (2-methoxyethoxy) ethyl group, etc.), sulfoalkyl group (eg, 2-sulfoethyl group) A 3-sulfopropyl group, - sulfobutyl group, 4
Sulfobutyl group, 2- [3-sulfopropoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group, etc., sulfatoalkyl group (for example, 3-sulfatopropyl group, 4- A sulfatobutyl group, a heterocyclic-substituted alkyl group (eg, 2-pyrrolidin-2-one-1-yl) ethyl group, a tetrahydrofurfuryl group, a 2-morpholinoethyl group, etc.),
2-acetoxyethyl group, carbomethoxyethyl group, 2
-Methanesulfonylaminoethyl group, allyl group, etc.),
An aryl group (eg, phenyl group, 2-naphthyl group, etc.), a substituted aryl group (eg, 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group,
A 3-methylphenyl group, a heterocyclic group (for example, 2-
Pyridyl group, 2-thiazolyl group, etc.).

In the formula, among the methine groups and substituted methine groups represented by L ¹ , L ² and L ³ , examples of the substituent include an alkyl group (for example, methyl and ethyl), an aryl group (for example, phenyl), aralkyl Group (eg, benzyl group) or halogen (eg, chloro, bromo, etc.), alkoxy group (eg, methoxy, ethoxy, etc.), or 4 to 6 when bonded to methine chain substituents or R ¹ or R ^2. A member ring may be formed.

 X Represents an anion, and n represents 1 or 2.

Next, the dyes of the general formulas [I], [II] and [III] according to the present invention will be described in detail.

The general formula [I] includes a symmetric oxacarbocyanine of the general formula [II] shown below.

General formula [II] V ¹ and V ² in the formula may be the same or different, and each may be a hydrogen atom, a halogen atom (eg, a chlor atom, a bromo atom, a fluorine atom, etc.) and an alkyl group having 6 or less carbon atoms (eg, a methyl group, an ethyl group, A propyl group, a butyl group, a cyclohexyl group, etc.) an aryl group (eg, a phenyl group), an alkoxy group having 4 or less carbon atoms (eg, a methoxy group,
Ethoxy group, butoxy group, etc.) aryloxy group (eg, phenoxy group, etc.) acyl group having 7 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, etc.) alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl group, ethoxy group) A carbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group, etc.) a hydroxy group, a cyano group, a trifluoromethyl group and the like are preferable.

R ³ represents an alkyl group having 2 or less carbon atoms (eg, a methyl group or an ethyl group).

 R¹, R^TwoAnd (X ) N_-2Is synonymous with that described above.

Next, the dye represented by the general formula [II] is symmetrical as in the general formula [I], but has a naphtho [1,2-
d] a symmetric oxacarbocyanine having an oxazole ring or a naphtho [2,1-d] oxazole ring;
The dye represented by the general formula [III] represents a symmetric oxacarbocyanine while the former two are symmetric oxacarbocyanines.

 In addition, the substituent R of these general formulas [II] and [III]¹, R^Two,
Chin chain L¹~ L^ThreeAnd the counter anion (X ) N-₁
Has the same meaning as in the general formula [I].

Next, typical examples of the compounds represented by the above general formulas [I] to [III] and used in the present invention are shown below, but the scope of the present invention is not limited only to these compounds.

Example of compound of general formula [III] The general formulas [I], [II] and [II] used in the present invention.
The sensitizing dye represented by the formula (I) is described in "Heterocycrli" by FM Hamer.
c compounds Cyaninedyes and related compounds "(Heterocyclic Compounds-Cyanine Soybeans and Related Compounds) IV.V.VI, Chapters 86-199
Page Johnwiley & sone (newyok.london), 1964, or DMSturmer, “Heterocycrlic compoundsspecial
topics in Heterocycrlic chmistry Chapter VIII IV 482-5
15 pages John Wiley & soney (newyok london) 1977,
Can be easily synthesized based on the method described in, for example.

 Each of the above general formulas is one state of the resonance structure.
Just showed Heterocyclic nitrogen atom with symmetric charge
It means the same substance even when expressed in an extreme state
It is.

The general formulas [I] and [II] used in the present invention.
In order to add the sensitizing dyes represented by (III) and (III) to the silver halide emulsion, conventionally known methods can be applied. For example, Japanese Patent Application Laid-Open Nos. 50-80826 and 50-80827 disclose the protonation dissolving method, Japanese Patent Publication No. 49-44895, and the method of dispersing and adding with a surfactant described in Japanese Patent Application Laid-Open No. 50-11419. 3,676,
No. 147, 3,469,987, 4,247,627, JP-A-51-599
No. 42, No. 53-16624, No. 53-102732, No. 53-102733
And the method of adding as a solid solution described in East German Patent 143,324, and the like. In addition, for example, Research Disclosure No. 71802, Japanese Patent Publication No. 50-40659
And water-soluble solvents described in JP-A-59-14805, such as water, methanol, ethanol, propyl alcohol, acetone, fluorinated alcohol, dimethylformamide, etc., alone or in a mixture thereof, and added to the emulsion. There is also a way to do it. The timing of addition may be at any stage during the emulsion production process, but is preferably during chemical ripening or after chemical ripening.

Prior to the addition of the sensitizer in the chemical ripening step, or immediately after the addition of the sensitizer, the addition of the sensitizing dye according to the present invention has no gradation change and no sensitivity change accompanying the chemical ripening. It has the effect of shortening the induction period and is particularly preferably used.

The sensitizing dye used in the present invention may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount also varies over a wide range depending on the emulsion conditions, but is preferably 1 × 10 ^{-6 to} 5 × 10 ^-3 mol, preferably 3 × 10 ^{-6 to} 2.5 × 10 ^-3 mol per mol of silver halide. Range.

The addition ratio of the general formulas [I], [II] and [III] can be varied over a wide range depending on the emulsion conditions, but preferably [I] / [II] is 0.05 to 20 and [II] / [ II
I] is from 0.05 to 20, and more preferably [I] / [II
I] is 0.1 to 10 and [II] / [III] is 0.1 to 10.

The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention may be any of silver bromide, silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide. In particular, silver iodobromide is preferred from the viewpoint that high sensitivity can be obtained.

In the case of silver iodobromide, the average silver iodide content in the silver halide grains is 0.5 to 10 mol%, preferably 1 to 8 mol%, and the inside of the grains has a high concentration of at least 20 mol% or more. There is a localized portion where silver iodide is localized.

In this case, it is preferable that the inside of the particle is as inner as possible from the outer surface of the particle, particularly 0.01
It is preferable that a localized portion exists at a portion separated by μm or more. Further, the localized portion may be present in a layer inside the particle, or may have a so-called core-shell structure, and the entire core may be a localized portion. In this case, it is preferable that a part or all of the grain core except for a shell part having a thickness of 0.01 μm or more from the outer surface is a localized part having a silver iodide concentration of 20 mol% or more.

The concentration of the silver iodide in the localized portion is preferably in the range of 30 to 40 mol%.

The outside of such a localized portion is usually covered with silver iodide-free silver halide. That is, in a preferred embodiment, 0.01 μm or more from the outer surface, particularly 0.01
A shell portion having a thickness of .about.1.5 .mu.m is formed of silver iodide-free silver halide (usually silver bromide).

In the present invention, the inside of the particle (preferably from the outer wall of the particle)
As a method for forming a localized portion of silver iodide having a high concentration of at least 20 mol% or more (inside of a grain separated by 0.01 μm or more), a method without using a seed crystal may be used.

When seed crystals are not used, there is no silver halide which becomes a growth nucleus before the start of ripening in the reaction liquid phase containing the protective gelatin (hereinafter referred to as mother liquor). A growth nucleus is formed by supplying a halide ion containing a high concentration of iodine ion. Then, the particles are further grown from the growth nuclei by continuing the addition and supply. Finally, a shell layer having a thickness of 0.01 μm or more is formed with silver halide containing no silver iodide.

When a seed crystal is used, at least 20 mol% or more of silver iodide may be formed only in the seed crystal and then covered with a shell layer. Alternatively, the amount of silver iodide in the seed crystal is set to 0 or within the range of 10 mol% or less, and at least 20 mol% of silver iodide is formed inside the grains in the step of growing the seed crystal, and then the shell layer is used. It may be coated.

In the silver halide photographic light-sensitive material according to the present invention, at least 50 silver halide grains present in the emulsion layer are contained.
% Is preferably grains having a silver iodide-containing portion as described above.

A preferred embodiment of the silver halide photographic light-sensitive material of the present invention is to use silver halide grains having a localized structure or form having a silver iodide-localized portion as described above.

The term silver halide grains having a regular structure or morphology herein means grains that do not include anisotropic growth such as twin planes and grow all isotropically, for example, cubic, tetrahedral, octahedral, Or it has a shape such as a sphere. Methods for producing such regular silver halide grains are known, for example, J. Phot.Sci.,
5 , 332 (1961), Ber. Bunsenges. Phys. Chem. 67 , 949 (196)
3), Intern, Congress Phot. Sei. Tokyo (1967).

Such regular silver halide grains can be obtained by adjusting reaction conditions when growing silver halide grains using a double jet method.

In such a simultaneous mixing method, silver halide grains are
It is prepared by adding substantially equal amounts of a silver nitrate solution and a silver halide solution to a protective colloid aqueous solution with vigorous stirring. The supply of silver ions and halide ions is necessary and sufficient for the growth of only existing grains without causing the existing crystal grains to be eroded with the growth of the crystal grains, and conversely not allowing the generation and growth of new grains. It is preferable that the growth rate be increased continuously or stepwise within the limit growth rate for supplying silver halide, or within the allowable range. As a method of this increase, Japanese Patent Publication No. 48-36890 and 52-16364
And JP-A-55-142329.

The critical growth rate varies depending on temperature pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, distance between grains, crystal habit, or type and temperature of protective colloid, It can be easily determined experimentally by a method such as microscopic observation and turbidity measurement of emulsion particles suspended in a liquid phase.

In a preferred embodiment, it is desirable that at least 50% by weight of the silver halide grains contained in the suspended silver emulsion layer be regular grains as described above. Another preferred embodiment is to use a monodisperse emulsion having a silver iodide-localized portion as described above.

The monodisperse emulsion referred to here is, for example, The Photographic
Journal, 79 , 330-338 (1939), when measuring the average particle diameter by the method reported by Trivelli, Smith et al.
At least 95% of the grains by weight or number consist of silver halide emulsions within ± 40%, preferably ± 30%, of the average grain size. Such monodisperse emulsion grains are made using a double jet method, as in the case of regular silver halide grains. The conditions at the time of the simultaneous mixing are the same as in the method for producing regular silver halide grains.

Methods for producing such monodispersed emulsions are known, for example, J. Pho
t.Sic., 12,242-251 (1963) JP-A-48-36890, 52
16364, 55-142329 and 58-49938.

In order to obtain the above-mentioned monodispersed emulsion, it is preferable to grow a grain by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus.

The wider the grain size distribution of the seed crystal, the wider the grain size distribution of the grain nuclei. Therefore, in order to obtain a monodisperse emulsion, it is preferable to use an emulsion having a narrow grain size distribution at the seed crystal stage.

The silver halide grains as described above used in the silver halide photographic light-sensitive material of the present invention are described, for example, in TH James
Theory of the Photographic Process "4th edition, Macmil
Neutral method, acidic method, ammonia method, forward mixing, reverse mixing, double jet method, controlled-double jet method, conversion method, core described in the literature such as pages 38-104 of Lan Corporation (1977) It can be manufactured by applying a method such as a / shell method.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention. Known photographic additives include, for example, Research Disclosure RD shown in the table below.
-17643 and the compounds described in RD-18716.

The emulsion layer of the photosensitive material according to the present invention is subjected to a coupling reaction with an oxidized aromatic primary amine developer (for example, a -p-phenylenediamine derivative, an aminophenol derivative, etc.) in a light-emission development process, so that a dye is obtained. Is used. The dye-forming couplers are usually selected such that for each emulsion layer a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with the blue-sensitive emulsion layer containing a yellow dye-forming coupler and a green dye-forming coupler. A magenta dye-forming coupler is used in the light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared in a manner different from the above-mentioned combination depending on the purpose.

It is desirable that these dye-forming couplers have a group having 8 or more carbon atoms in the molecule, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce two molecules of silver ions, even if they are four-equivalent, in which four molecules of silver ions need to be reduced in order to form one molecule of dye. Either of two equivalents may be used. Dye-forming couplers are colored couplers having a color correcting effect and development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents by coupling with oxidized developing agents. Compounds that release photographically useful fragments, such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among them, couplers which release a development inhibitor with development to improve the sharpness of an image and the granularity of an image are called DIR couplers.

Instead of the DIR coupler, a DIR compound which mainly forms a colorless compound by coupling reaction with an oxidized form of the developing agent and releases a development inhibitor may be used.

The DIR couplers and DIR compounds used are those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and which are removed by the coupling reaction. (A timing DIR coupler and a timing DIR compound) in which an inhibitor is released by an intramolecular nucleophilic reaction, an intramolecular electron transfer reaction, or the like. Further, as the inhibitor, those having a diffusivity after release and those having a low diffusivity can be used alone or in combination depending on the application. The coupling reaction with the oxidized aromatic primary amine developer can be carried out by using a colorless coupler that does not form a dye (also referred to as a competitive coupler) in combination with the dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide-based couplers can be preferably used. Of these, benzoylacetanilide and pivaloylacetoanilide light compounds are advantageous.

Specific examples of the yellow light-emitting coupler that can be used include, for example, U.S. Pat.Nos. 2,875,057, 3,265,506, 3,408,194, and 3,5.
No. 51,155, No. 3,582,322, No. 3,725,072, No. 3,891,44
No. 5, West German Patent 1,547,868, West German Patent Application 2,219,917
No. 2,261,361, No. 2,414,006, British Patent 1,425,02
No. 0, JP-B-51-10783, JP-A-47-26133, JP-A-48-7
No. 3147, No. 50-6341, No. 50-87650, No. 50-123342
Nos. 50-130442, 51-21827, 51-102636
No. 52-82424, No. 52-115219, and No. 58-95346.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used.

Specific examples of magenta coloring couplers that can be used are, for example, U.S. Pat.Nos. 2,600,788, 2,983,608, 3,062,653,
3,127,269, 3,311,476, 3,419,391, 3,5
19,429, 3,558,319, 3,582,322, 3,615,50
No. 6, No. 3,834,908, No. 3,891,445, West German Patent 1,810,4
No. 64, West German Patent Application (OLS) 2,408,665, 2,417,945
No. 2,418,959, No. 2,424,467, JP-B-40-6031
JP-A-49-74027, JP-A-49-74028, JP-A-49-129538
No. 50-60233, No. 50-159336, No. 51-20826,
Nos. 51-26541, 52-42121, 52-58922, 53
-55122 and Japanese Patent Application No. 55-110943.

As the cyan dye-forming coupler, a known phenol or naphthol coupler can be used.

For example, a phenol coupler substituted with an alkyl group, an acylamino group, or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton,
Representative examples include a bi-equivalent naphthol coupler into which an oxygen atom is introduced as a leaving group.

Specific examples of the cyan coloring coupler that can be used include, for example, U.S. Patent No. 3,779,763, JP-A-58-98731, and JP-A-60-37557.
No. 2,895,826, No. 60-225155, No. 60-222
No. 853, No. 59-185335, U.S. Pat.No. 3,488,193, No. 60-185335
No. 2377448, No. 53-52423, No. 54-48237, No. 56-271
No. 47, JP-B No. 49-11572, JP-A No. 61-3142, 61-9652
No. 3, No. 61-39045, No. 61-50136, No. 61-9914
No. 1, No. 61-105545 and the like.

The silver halide photographic light-sensitive material of the present invention is produced by coating on a support having good flatness, good dimensional stability during the production process or processing and little dimensional change. As the support in this case, for example, a cellulose nitrate film, a cellulose ester film, a polyvinyl acetal film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, glass, paper, metal, polyolefin, for example, polyethylene, paper coated with polypropylene or the like. Can be used. These supports can be subjected to various surface treatments such as a hydrophilic treatment for the purpose of improving the adhesiveness with the nitrographic emulsion layer, for example, saponification treatment, corona discharge treatment, undercoating treatment, and set treatment. Are performed.

The silver halide photographic material of the present invention is described, for example, in Research Disclosure, No. 176, pp. 20-30 (RD-176).
Processing can be carried out using a known photographic processing method and processing solution described in 43).

This photographic processing method may be black-and-white photographic processing for obtaining a silver image or color photographic processing for obtaining a color image. Processing temperature applied to photographic processing is usually 18 ° C ~
Although the temperature is 50 ° C., the treatment can be performed at a temperature lower than 18 ° C. or at a temperature higher than 50 ° C.

Examples of the light-sensitive material to which the silver halide photographic light-sensitive material of the present invention can be applied include various color and black-and-white light-sensitive materials. For example, color negative materials for photography, color reversal film, color photographic paper, color positive film, color reversal photographic paper, direct positive, heat development, color photosensitive materials such as silver dibridge, and X-ray photography, squirrel, It can be used for black-and-white photographic light-sensitive materials such as for micro, general photography, and black and white photographic paper.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 According to a method similar to that described in JP-A-57-154232, silver iodobromide comprising silver halide grains having an average grain size of 0.4 μm (average silver iodide content: 8 mol%) ) Was prepared. [Em No. 1] After desalting, the emulsion prepared above was treated with the general formula [I],
Sensitizing dyes represented by (II) and (III)
2 as indicated.

In addition, the following dyes (Comparative D-1) outside the present invention were also added as comparative dyes.

Next, 4-fudroxy-6-methyl-1,3,3a, 7-tetrazaindene, sodium thiosulfate, chloroauric acid, and ammonia thiocyanate were added, and subjected to chemical thermogenesis and spectral sensitization under optimal conditions. did.

Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5 were used as stabilizers in each emulsion.
-Mercapto-tetrazole, saponin as a coating aid, and 1,2-bis (vinylsulfonyl) as a hardener
Ethane was added in an appropriate amount, and the following magenta coupler and AS-1 were added to a dispersion of a mixture of dodecyl gallate, tricresyl phosphate, ethyl acetate, sodium triisopropylnaphthalenesulfonate and gelatin.

The emulsion thus prepared was coated on a cellulose triacetate base support and dried to prepare a sample.
The obtained sample was allowed to stand naturally for 3 days as a fresh sample, and as a substitute test method for determining the raw preservability of the light-sensitive material and the desorption property of the sensitizing dye from silver halide, a temperature of 50% was used.
The sample was left standing for 3 days under constant temperature and humidity at 80 ° C. and a relative temperature of 80 ° C.

Next, after a 1/50 second wedge exposure was performed through a green filter, color negative development was performed as described below.

<Development conditions> Processing step (38 ° C) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixed 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds The composition of the processing solution used in the process is as follows.

Color developer composition: 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.8 g Sodium sulfite anhydrous 0.14 g Hydroxylamine 1/2 sulfate 1.98 g Sulfuric acid 0.74 mg Anhydrous potassium carbonate 28.85 g Anhydrous potassium hydrogen sulfate 3.46 g Anhydrous potassium sulfite 5.10 g Potassium bromide 1.16 g Potassium chloride 0.14 g Nitrilotriacetic acid trisodium salt (monohydrate) 1.20 g Potassium hydroxide 1.48 g I do.

Bleaching solution composition: Ethylene (III) ammonium salt of ethylenediaminetetraacetate 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Add water to 1 to make pH = 6.0 using aqueous ammonia.
Adjust to

Fixer composition: Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to 1 and adjust to pH = 6.0 with acetic acid.

Stabilizing solution composition: Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Make up to 1 by adding water.

The sensitivity of each of the obtained dye images was measured through a green filter to determine the sensitivity and fog.

It was determined from the exposure required to give an optical density of sensitivity "fog + 0.1". Table 1 below shows the results of the sensitometry.
And Table 2.

The sensitivity was relatively expressed with the sensitivity of Sample No. 1 being 100.

As is clear from the results of Tables 1 and 2, in the sample of the present invention in which the sensitizing dyes of the present invention represented by the general formulas [I], [II] and [III] are combined, two symmetric dyes are used. When used in combination with species, or in combination with a dye having a partial structure that is not common to the combination, it is more sensitive, and under severe conditions under high temperature and high humidity considered to be accompanied by elimination of the sensitizing dye It can be seen that there was little desensitization and excellent supersensitization was obtained.

Example 2 According to the method of Example 1, an emulsion for an upper layer
A core / shell type emulsion (Em No-2) having a thickness of 0.7 μm and an average silver iodide content of 8 mol% was prepared.

As the emulsion for the lower layer, the above-mentioned (Em No-1) was used to sensitize each to a different optimum point to prepare a multilayer color photosensitive material.

The structure of the upper and lower layers in the multilayer color film and various additives used therein are shown in the following table.

The coating amount in the table, for the silver halide and colloidal silver expressed as silver amount in units of g / m ² for the additive and gelatin expressed in g / m ^2.

The couplers are shown in moles per mole of silver halide in the same layer.

The obtained samples were treated in the same manner as in Example 1 and subjected to sensitometry, and the results are shown in Tables 3 and 4 below.

As can be seen from the results in Tables 3 and 4, the desensitization due to the elimination of the sensitizing dye when the layer was changed from a single layer to a multilayer was caused by two types of symmetric dyes and one type of asymmetric having a common partial structure. The problem can be solved by using a dye in combination. In addition, it was shown that the effect of preventing desensitization due to elimination of the sensitizing dye in the multilayer sample was greater not only in the single layer sample but also in the multilayer sample when the dye combination of the present invention was used.

Example 3 A cubic monodispersed silver iodobromide emulsion having an average particle size of 0.75 μm was prepared by a double jet method. The average silver iodide content of this emulsion was 2.0 mol%. After desalting, chemical ripening by gold and sulfur sensitization was carried out by a conventional method, and then the general formulas [I], [II] and [III] of the sensitizing dyes according to the present invention were prepared according to Tables 5 to 5 below.
6, and after reaching the highest sensitivity, 4-hydroxy-6-methyl 1,3,3a, 7-tetrazaindene was added as a stabilizer.

To each of the resulting high-sensitivity silver iodobromide emulsions were added a copolymer of styrene and maleic anhydride as a thickening agent and appropriate amounts of trimethylolpropane and diethylene glycol as wetting agents.

Then, an appropriate amount of sodium-isoamyl-N-decyl-sulfosuccinate as a coating aid and an appropriate amount of formalin as a hardener were added, and the mixture was uniformly coated on a polyethylene terephthalate support so that the silver amount was 3 g / m ² . .

The obtained sample was left as a storage test at 50 ° C. and 80% RH for 3 days, and an untreated fresh sample was prepared.

After exposing these samples with a KS-1 type centimeter [manufactured by Konica Corporation] based on the JIS method, using a KX-5000 automatic developing machine [manufactured by Konica Corporation] at 35 ° C. for 30 seconds with an XD-90 developer. Development was performed.

The results of sensitometry of the sample after fixing, washing and drying are shown in Tables 5 and 6 below.

In addition, the sensitivity in the table is the sensitivity of the fresh sample of (comparison).
Relative sensitivity values expressed as 100.

As is clear from the results of Tables 5 and 6, excellent photographic characteristics were obtained also when the present invention was applied to a black and white photographic material.

Example 4 A multilayer color light-sensitive material having the following composition was prepared on a cellulose acetate support having been subjected to a subbing process.

The coating amount in the table, for the silver halide and colloidal silver expressed as silver amount in units of g / m ² for the additive and gelatin expressed in g / m ^2.

The couplers are shown in moles per mole of silver halide in the same layer.

The obtained samples were treated in the same manner as in Example 2 and measured for sensitometry. The results are shown in Tables 7 and 8 below.

As can be seen from the results of Tables 7 and 8, the desensitization accompanying the elimination of the sensitizing dye when the layer was changed from a single layer to a multilayer was determined by two types of symmetric dyes and one type of asymmetric having a common partial structure. The problem can be solved by using a dye in combination.

In addition, it was shown that the effect of preventing desensitization due to elimination of the sensitizing dye in the multilayer sample was greater not only in the single-layer sample but also in the multilayer sample when the dye combination of the present invention was used.

[Effects of the Invention] According to the present invention, a high-sensitivity green-sensitive silver halide photographic light-sensitive material having good storability and preventing a decrease in sensitivity due to separation of a sensitizing dye from silver halide is obtained.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Hiroshi Otani 1 Sakuracho, Hino-shi, Tokyo Examiner in Konica Corporation Yuki Yamaguchi (56) Reference JP-A-63-197936 (JP, A) JP-A JP-A-52-23931 (JP, A) JP-A-59-78338 (JP, A) JP-A-62-27043 (JP, A) JP-A-1-210952 (JP, A) JP-A-2-123347 (JP) , A)

Claims (1)

(57) [Claims] 1. A silver halide emulsion layer coated on a support
Wherein at least one layer has the same left and right heterocyclic structure
Symmetric carbocyanines represented by general formulas [I] and [II]
At least one of each of the dyes
Represented by the following general formula [III] having one heterocyclic structure
Combination of at least one of asymmetric carbocyanine dyes
Halogenation characterized by supersensitization
Silver photographic photosensitive material. General formula [I]General formula (II)General formula (III)(Where Z¹Is a naphtho [2,3-d] oxazole ring
Represents a group of non-metallic atoms necessary for formation. Z^TwoIs naphtho [1,2-d] oxazole ring or naphtho
[2,1-d] oxazole ring Non-gold necessary to form the ring
Represents a group of genus atoms. Z^ThreeIs Z¹Synonymous with or Sterimol parameter L / B₁≦ 2.
Z having a substituent defined by 2¹And Z^FourIs Z^TwoSynonymous with
Or Sterimol parameter L / B₁Position defined by ≤ 2.2
Z having a substituent^TwoRepresents R¹, R^TwoIs the same or different alkyl group or substituted
Represents an alkyl group. L¹, L^TwoAnd L^ThreeRepresents a methine group or a substituted methine group. X Represents an anion and n represents 1 or 2. ]