JPS6041036A - Photosensitive silver halide meterial - Google Patents

Abstract

PURPOSE:To increase the sensitivity of a photosensitive silver halide material and to prevent fog by incorporating a specified sensitizing dye into a silver halide emulsion layer of the material having the layer on the support. CONSTITUTION:A sensitizing dye represented by formula I or II is incorporated into a silver halide emulsion layer. By incorporating the dye, the photosensitive wavelength range of the emulsion layer is extended, and an image free from fog can be formed with high sensitivity. In the formulae, Z1 is O, S or Se; D1 is a group of atoms required to form an oxazole ring or an oxazoline ring; each of R1, R4 and W1-W4 is H, alkyl or the like; each of R2, R3, R5 and R6 is alkyl; W1 and W2, W2 and W3, and W3 and W4 may bond to each other to form each ring; each of X1<-> and W2<-> is an anion; each of Z2 and Z3 is S or Se; each of D2 and D3 is a group of atoms required to form a thiazole ring, a selenazole ring or the like; each of m and n is 1 or 2; and when the sensitizing dye forms an inner salt, each of m and n is 1.

Description

Detailed Description of the Invention [Field of Application] The invention is directed to a silver halide photographic light-sensitive phase material (hereinafter referred to as It is a silver halide photographic emulsion N that has particularly high spectral sensitivity in the green sensitive region.
The present invention relates to a photosensitive material having the following characteristics.

[Prior art]

As is well known, when a sensitizing dye is added to a silver halide emulsion, the wavelength range to which the silver halide emulsion is sensitive is expanded and the emulsion is optically sensitized. When spectrally sensitizing a silver halide emulsion, it is known that if one or more sensitizing dyes are used in combination with the sensitizing dye, the efficiency of spectral sensitization increases significantly and high sensitivity can be obtained. The effect is called supersensitization. Various combinations of sensitizing dyes have been proposed for the purpose of supersensitization.

However, it is also known that the groups of sensitizing dyes used in combination require a remarkable selectivity with respect to each other, and that it is extremely difficult to predict the effects from the chemical structure of the sensitizing dyes.

On the other hand, when supersensitization is performed by combining two or more types of sensitizing dyes, the spectral sensitivity in a specific spectral sensitization wavelength range is reduced, the fog increases, and during and after the production of the photosensitive dye. Deterioration of stability over time such as decreased sensitivity and increased fog during storage before exposure (hereinafter referred to as raw storage), and deterioration of stability of latent images after exposure (photography) until development often occur. Delaying the purpose of supersensitization by using a combination of sensitizing dyes without such adverse effects is one of the important issues in the technology of manufacturing photosensitive materials.

[Purpose of the invention]

An object of the present invention is to provide a photosensitive material that is supersensitized by a novel combination of two different dyes, has high sensitivity, and does not cause fogging.

Another object of the present invention is to provide a photographic material having a spectrally sensitized silver halide emulsion layer that does not cause a decrease in sensitivity or an increase in fog during raw storage of the photographic material, particularly during raw storage under high temperature and high humidity conditions. It is about providing.

[Summary of the invention]

As a result of various studies, the present inventors have determined that, in a light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer has the following general formula (1). ) and the general formula ([[D]) The present invention has been achieved by a light-sensitive material characterized by containing at least one type of sensitizing dye represented by D.'-General formula D w .

General formula (■ In the general formula (1), zl represents an acid atom, a sulfur atom or a td selenium atom, Dl represents an atomic group necessary to form an oxazole ring or an oxazoline ring,
R1 represents a hydrogen atom, an alkyl group, or an allyl group, R2, oJ, R5IJ, and Jc each represent an alkyl group, and Wl, W2, W, and WII each represent a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group. group, aryol group, carboxyl group, alkoxycarbonyl group,
Aryl leoquine carbonyl group, nitro group, hydroxy group, cyano group, amine group, anruamino group, sulfonylamine 7 group, acyloxy group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group - * Represents a heterocyclic group , Wl and W2, W2 and W3, or W3 and Wl may be connected to each other to form a monkey.

Xl (3 represents an anion, n] represents 1 or 2. However, when the sensitizing dye represented by the general formula (1) forms an inner salt, m represents 1.

In the general formula (II), z2 and Z each represent a sulfur atom or a selenium atom, and D2 and D3 each represent a thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring or naphthoselenazole ring. R11 represents a hydrogen atom, an alkyl group or an aryl group, and R5 and R6 each represent an alkyl group.

°x2° represents an anion, and nt! it or 2, and when the sensitizing dye represented by the general formula (fD) forms an inner salt, n represents 1.

In addition, it is preferable that the carbon number of the alkyl group in general formula (D and (omega)) is 1-6.

[Structure of the invention]

To explain the present invention in more detail, Bl in general formula (1) is preferably an alkyl group or an aryl group,
Alkyl groups include methyl group, ethyl group, propyl group,
It represents butyl group, benzyl group, phenethyl group, etc.
An alkyl group having 1 to 6 carbon atoms is preferred. Examples of the aryl group include a phenyl group and an I)-)lyl group.

General formula ([Bu in D represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group and aryl group include those mentioned above for R1.

R2, R5, R5 and R6 in general formulas (eye) and (ll) each represent an alkyl group, and also include an alkyl group normally used in cyanine dyes. Specifically, for example, in addition to alkyl groups without substituents (methyl group, ethyl group, butyl group, etc.), hydroxyalkyl groups (2-hydroxyethyl group, 4-hydroxyalkyl), acetoxyalkyl groups (2- acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (2-methoxyethyl group, 2-ethoxyethyl group, etc.), carboxyl alkyl group (2-carboxyether group, 3-carboxypropyl group, p-carboxylate group, etc.) quinbenzyl group, etc.), carbamoyl alkyl group (carbamoylmethyl group, carbamoylethyl group, etc.), sulfoalkyl group (2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy73- sulfopropyl group, p-sulfoalkyl group, etc.), aralkyl group (benzyl group, phenylethyl group, etc.), sulfamoylalkyl group (sulfamoylethyl group, etc.)

Said Wl, W2. ．． Details Fi of the groups or atoms represented by W, 3 and W1+ are as follows.

First, the alkyl group preferably has 1 to 6 carbon atoms, and may be linear, branched, or cyclic, and may be saturated or unsaturated. It may also have a substituent, and specific examples of alkyl groups include methyl group, ethyl group, 1so-furoyl group, cyclohexyl group, allyl group,
Examples include trifluoromethyl group, hydroxyethyl group, acetoxymethyl group, carboxymethyl group, and ethoxycarbonylmethyl group.

Next, the alkoxy group preferably has 1 to 6 carbon atoms, and may have a substituent. Specific examples of the alkoxy group include a metquine group, a 1so-propoxy group, a chloroethoxy group, etc. =i I can do Western H'.

Examples of the aryl group include phenyl group, naphthyl group,
Examples of the alkoxycarbonyl group include an ethoxycarbonyl group and a butoxycarbonyl group, and examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

Examples of the amino group include amide 7 group, alkylamino 7 group, arylamino group, dilinked amino group, and specific examples include methylamino group, diethylamine group, anilino group, and the like.

Examples of the acylamino group include an acetamido group and a benzamide group.

Examples of the sulfonylamino group include an alkylsulfonylamino group and an arylsulfonylamino group, and specific examples include a methanesulfonamide group and a benzenesulfonamide group.

Examples of the acyloxy group include an acetoxy group and a pentyloxy group.

Examples of the carbamoyl group include a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, a di-substituted carbamoyl group, and specifically a methylcarbamoyl group, a phenylcarbamoyl group, and the like.

Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a di-substituted sulfamoyl group, and specifically, an ethylsulfamoyl group, a dimethylsulfamoyl group, and a phenylcarbamoyl group. Can be mentioned.

Examples include sulfonyl groups, alkylsulfonyl groups, arylsulfonyl groups, and sulfonyl groups, specifically methanesulfonyl groups, cyclohexanesulfonyl groups, henzenesulfonyl groups, p-toluenesulfonyl groups, and hyridine. Examples include a sulfonyl group, a t-piperidinesulfonyl group, and an N-morpholinosulfonyl group.

Examples of the acyl group include acetyl group, benzoyl group,
Examples include l-piperidinocarbonyl group and N-morpholinocarbonyl group.

As a heterocyclic group, for example, benzomexazoυ
Examples include a benzothiazolyl group, a piperidino group, a morpholino group, a sacuniimide group, a furyl group, and a chenyl group.

Next, the aforementioned Tooshi, wl and W2. W2 and w3 and/
Alternatively, w5 and wg can each form a ring, but examples of rings that can be formed include the naphthalene ring 1 formed with the benzene ring substituted by Wl-WI+, -quinoline ring, benzothiophene ring, iso Examples include a benzofuran ring, an indole ring, a chroman ring, and a tetrahydroquinoline ring.

1. These rings further include substituents such as alkyl groups, halogen atoms, aryl groups, carboxy groups, alkoxycarbonyl groups, alkoxy groups, nitro groups, hydroxy groups, cyano groups, amino groups, acylamino groups, and sulfonylamino groups. , an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, a heterocyclic group, and the like may be substituted.

Dl in the general formula (+) represents an atomic group necessary to form an oxazole ring or an oxazoline ring, and these rings may further have a substituent. Examples of substituents include halogen atoms, alkyl groups, aryl groups, carboxyl groups, alkoxycarbonyl groups, hydroxy groups, alkoxy groups, nitro groups, cyano groups, amino groups, acylamino groups, sulfonylamino groups, acyloxy groups, and carbamoyl groups. group, sulfamoyl group, sulfonyl group, acyl group, heterocyclic group, and the like. Examples of the heterocyclic nucleus containing the oxazole ring or oxazoline ring formed by Dl in the general formula (1) are oxazole, 4-methyloxazole, 5-methyloxutuzole, 4-phenyloxazole, 4,5-dimethyl Examples include oxazole, 5-phenyloxazole, 45-diphenyloxazole, oxazoline, 4-methyloxazoline, 4,4-dimethyloxazoline, and the like.

General formula ([D2 and D3 in D represent an atomic group necessary to form a thiazole ring, benzothiazole ring, naphthothiazole ring, selenanol ring, benzoselenazole ring, or naphthoselenazole ring; may provide a replacement fund to history.

Examples of the substituent include the same substituents as those for the oxazole ring and oxazoline ring described above.

Examples of the heterocyclic nucleus formed by D2 and D3 of the general formula (ID) including theazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, and naphthoselenazole are thianol, 4-methylthiazole , 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4.5-dimethylthiazole, 4.5-2 phenylthiazole, benzothiazole) 5-chlorobenzothiazole, 5-methylbenzothiazole, 6- Chlorbenzothiazole, 6-methylpenzig azole, 5-carboxybenzothiazole, 5-ethoxycarpolbenzotheazole, 5-phenoquinecarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-phenylbenzothiazole, 4-
Metquin benzothiazole, 5-methquin benzothiazole, 6-methoxybenzothiazole, 5,6-simethoxybenzotheazole, 5,6-methylenecyoxybenzothiazole, 5,6-dimethylbenzothiazole, 5
-benzoylbenzothiazole, 5-dimethylcarbamoylbenzotheazole, 6-acetylaminobenzothiazole, nut [tz-d]thiazole, nut [z,
t-d]thiazole, Nando[2,3-a]thiazole, 5-methoxynaphtho[1°2-d]thiazole, 8-
Methoxynaphtho[2,1-d]thiazole, 7-methoxynaphtho[2,1-d]thiazole, selenazole, 4
-Methylselenazole, 4-phenylselenazole, benzoselenazole, 5-chlorobenzoselenazole, 5
-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-phenylbenzothiazole, naphthol:
1. z-d]selenazole, naphtho[2,1-d coselenazole, naphtho[2,3-d]selenazole, and the like.

The argon represented by Xle and x2e are those commonly used in arne dyes, such as chloride ion, bromide ion, iodide ion, thionean σ beion, imen sulfate, perchlorate ion, p-tono1enesulfonate ion, These include boron tetrafluoride ion, methyl sulfate ion, and ethyl sulfate ion.

m and nq each represent l or 2, and when the sensitizing dye represented by formula (1) or C) forms an inner salt, it is 〇.

Typical examples of sensitizing dyes used in the present invention are listed below, but the sensitizing dyes used in the present invention are not limited to these.

[Specific examples of compounds represented by the general formula (+)] -1 -3 -4 -5 ■-8 cto4e -10 Q [-11 2it5 C2Hq011 1θ ■-12・-13 ■-15 -16 17 l -19 1-20 [Specific example of the f compound represented by the general formula ([0]) l-
3 cl' 1-4 "-7 "-10 ff-11 n-12 -13 1 [-' l 4 ff-15 Next, a typical synthesis example of the above r-hyde compound will be described.

Synthesis example 1 (synthesis of exemplified arsenic compound 1-1) (t-1) Compound Th (Dt= 3.9 gs (arsenic compound (II) e
4.5g! : While stirring a mixture of 80+aJ of methanol at room temperature, 3.0 g of hetriethylamine was added. After stirring at a constant temperature for 30 minutes, the mixture was heated and stirred at a bath temperature of 100° C. for 1 hour. The anti-mixture was concentrated, purified by column, and solidified with acetone. This was recrystallized from isopropanol and red WJ
Exemplary compound 1-1 of colored crystals obtained f-0A cH30H
Id 522 n rrrThKufko.

ax Above, increase KJ related to the present invention, f4. Basic 6
However, the sensitized color represented by the general formula (ID
"F's and Fists Related Compound" Inmesa 1 Ensbaburinoso 1'-10, Newric, l 9
64) '4 S 2a' V and write the synthesis. Further, the sensitized color stop represented by the general formula (1) can also be synthesized with reference to the above-mentioned literature.

Accepted by the above general formula (1) or (11) 1L7)
The trimethenine sensitized color according to the present invention is...a
1 mole of M1 used in the silver gunnide emulsion is I x 10 mole ν2.5X10 mole, particularly preferably expanded 5. It is used in a proportion of xto'' mol to l
) is preferably used in a molar ratio of 1:20 to 20:1.

When adding the above-mentioned sensitizing dye to the silver halide emulsion, the dye may be directly dispersed in the above-mentioned emulsion, or it may be dissolved in a suitable solvent such as methanol, ethanol, dimethylformamide, etc. alone or in combination with VC. It may be added to the emulsion after that.

Although it can be added at any time during the photosensitive material manufacturing process, it is generally added to the silver halide emulsion during the second ripening or immediately after the second ripening. is preferred.

The trimethine cyanine sensitizing dye according to the present invention is a combination of one or more dyes of the general formula (1) and one or more dyes of the general formula (ID), as well as other styryl dyes, etc. It can be used for spectral sensitization and superchromatic sensitization.

The silver halide emulsion used in the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halogen salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as ceratin. It is made by mixing. The silver halide may be any of the silver halides used in ordinary photosensitive materials such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chlorobromide, and silver chloroiodobromide.
・Silver rocoonide can be used.

These silver halide emulsions are produced according to known and commonly used methods (for example, the lump or tuple jet method, the controlled double jet method, etc.). Furthermore, two or more types of silver halide emulsions formed separately may be mixed. Historically, even though the crystal structure of silver halide grains is uniform inside, there are grains that have a layered structure with different interior and exterior structures, 'R9+N19 convergence emulsions, Litzmann emulsions, and covered grain emulsions. Alternatively, it may be optically or chemically fogged in advance. Further, either a type in which the latent image is mainly formed on the surface or an internal latent image type in which the latent image is formed in the particle 21 portion may be used. These silver halide emulsions can be prepared by various generally accepted methods such as an ammonia method, a neutral method, and an acid method. Further, the type of silver halide, the content and mixing ratio of silver halide, average grain size, size distribution, etc. are appropriately selected depending on the type of silver halide emulsion and the intended use.

These methods are described in Chim by P. Glafkides.
ieet Physique Photography
que (Paul Monta1, 1967)
, G.F., Duff in Pi1oto-grap
hic Emulsion Chemistry (T
he Focalpresa, 1966), V.
L, Zelikman etal HMking
and Coating PhotographicE
Mulsion (The Focal Press, 1964), etc.

In order to prepare the light-sensitive material of the present invention, -silver halide is dispersed in a suitable secondary colloid and coated on a suitable support to form a silver halide emulsion layer. The capture colloid used in the layer structure of the photosensitive layer and other auxiliary layers, such as the intermediate layer, capture layer, and filter layer, is generally alkali-processed gelatin, and finely processed gelatin, derivative gelatin, and colloids thereof. Examples include solid albumin, cellulose derivatives, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, and these may be used alone or in combination.

The above halogenated emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers include gold sensitizers (potassium aurithiocyanate, ammonium chloroparadate, potassium chlorobratate), sulfur sensitizers (
They are broadly classified into four types: selenium sensitizers (active and inactive selenium compounds, etc.), and reduction sensitizers (ml tin salt, polyamines, etc.). / The silver halide emulsion can be chemically sensitized using these sensitizers alone or in combination as appropriate.

These chemical sensitization methods are described, for example, in US Pat. No. 1.574.
No. 944, No. 1.623,499, No. 2.410゜6
No. 89, No. 2.448, No. 0.60, No. 2.399. (
183 No. 1, 2.642.361, Mukai 2.487,
No. 850, No. 2.518,698, No. 1.623,4
No. 99, No. 1602.592, etc. Other sensitizers such as polyalkylene oxide compounds can also be used.

In addition, various other additives may be added to the above-mentioned silver dinitide emulsion]
You can add wo. For example, aldehydes such as formaldehyde, halogenated fatty acids such as mucobromic acid, hardening agents such as epoxy compounds, active halogen compounds, active vinyl compounds, ethyleneimine compounds, saponins, nonionic surfactants, cationic interfaces, etc. Active agents, anionic surfactants, surfactants such as amphoteric active agents, azoles, heteromercapto compounds such as 1-phenyl-5-mercaptotetrazole, 4-hydroxy-6=methyl-1, 3,3a, 7-thitrazaindene and other anti-capri agents or stabilizers such as benzenethiosulfonic acid and pensene sulfinic acid, glycerin separate aqueous dispersions (property improvers such as latex), 5-
Pyrazolone-based magenta sword), afluacetanilide-based yellow cuff.

dye image-forming couplers and colored couplers such as cyan or naphthol thread cyan couplers;
Couplers such as combing couplers, development inhibitor releasing couplers (DIR couplers), dibutyl phthalate, t-11 phenyl phosphate, and tricresyl for improving image sharpness and graininess and adjusting gradation. dispersants which are also used as coupler solvents such as phosphate, N,N-diethyl laurylamide, ethyl acetate, butyl acetate, chloroform, methanol, ultraviolet absorbers such as benzotriazoles, triazines, benzphenone thread compounds, etc.; Substituted hydroquinone M, p-alkoxyphenols, 6-chromanols, 6,6'
Various photographic additives, such as anti-staining agents and anti-fading agents such as 2.2'-Shilochroman and their alkoxylic derivatives, and brightening agents such as stilbene-based, triazine-based, oxazole-based, or coumarin-based brighteners. may be added.

The silver halide emulsion according to the present invention has good flatness,
It is then fabricated on a support that has good dimensional stability and little dimensional change during the M manufacturing process or treatment. Examples of the support in this case include cellulose nitrate film, cellulose ester film, polyvinyl acecool film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass, paper, metal,
Holimelefin, such as polyethylene, polypropylene/
It is possible to use paper, etc. that has been deformed and torn. These supports can be subjected to surface treatments such as various hydrophilic treatments for the purpose of improving adhesion with the silver halide emulsion layer.
For example, Kun conversion treatment, corona release treatment, subtraction treatment,
Processing such as setting processing is performed.

The photosensitive dye of this 94 basically consists of a support and a photosensitive emulsion J.
,, 7; Auxiliary R' may be appropriately combined and layered.

The present invention can also be applied to multi-layer color A and pigments in which light-sensitive emulsion layers having at least two different molecular abhorrences are coated on a support.

The above-mentioned multilayer color-sensitive °0 material usually has a structure in which at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer are each formed on a support in order from the support side. The order can be arbitrarily selected as necessary. It is standard practice to include cyan cuffler 7 in the red-sensitive emulsion layer, magenta coupler in the green-sensitive emulsion layer, and IX low cuffler in the blue-sensitive emulsion layer, but depending on the case. The two records may be included by different combinations.

The silver halide copy 1b emulsion of the present invention contains a water-soluble dye dye for use as a filter dye, to prevent irradiation, and for various other purposes. Such dyes include oxonol dyes and hemioxy dyes. Included are nol dyes, styryl dyes, melo-7-anine dyes, noanine dyes, and azo dyes. Among these, oxonol dyes, hemi-oxonol dyes (F) and o-melonanine dyes are useful.

Exposure for obtaining a photographic image may be carried out using a conventional method. That is, any of the various known light sources can be used, such as a natural YS tungsten electric lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a charcoal mark lamp, a xenon flash lamp, and a cathode ray tube flying spot. Exposure times include not only exposure times of 1/1000 seconds to 1 second that are normally used with cameras, but also shorter exposures of 1/1000 seconds, such as exposures of 1/1 x 10 to 1/1 x 10 seconds using a key lζ non-flash lamp or cathode ray tube. or a longer exposure of 1 second can be used.The spectral composition of the light used for exposure can be adjusted with a color filter as necessary.Laser light can also be used for exposure. Alternatively, it may be exposed to light emitted from a phosphor excited by rays, XN, r-rays, αm, or the like.

The photosensitive material of the present invention can be used, for example, in Research Disclosure, No. 176, pages 20 to 30 (RD-17643).
) The treatment can be performed using the known treatment method and treatment liquid described in .

This photographic processing method may be a black-and-white photographic process to obtain a silver image f, or a galactic photographic process to obtain a dye image. The processing temperature applied for photographic processing is usually 18℃
~50°C, but treatment is possible at temperatures lower than 18°C and even at temperatures above 50°C.

The developer used in black-and-white photographic processing can contain conventionally known developing agents. As a developing agent,
dihydroxybenzenes (e.g. hydroquinone),
3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and U.S. Pat.
Heterocyclic compounds such as those described in No. 872 in which a 1.2.3.4-tetrahydroginoline ring and an intrene ring are condensed can be used alone or in combination. The developing solution also contains known preservatives, alkaline agents, PI buffers, antifoggants, etc., and, if necessary, solubilizing agents, color swelling agents, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like.

The photosensitive phase material of the present invention can be subjected to a so-called "lith type" development process. What is “Squirrel type” development processing? Ship 2
For photographic reproduction of image edges or halftone dots of halftones and halftones, dihydroxybenzenes are usually used as developing agents, and the developing process is carried out at low ion temperature. Act 1. f, refers to processing (details in Mason [Photographic Brosetschinken Chemistry J (1966) pp. 163-165)
(described on page).

As a constant liquid, one with a commonly used composition can be used.

As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain water bathing aluminum salt as a hardening agent.

This method can be applied when forming a pigment layer.

Negative-positive method (for example, “Journal of the
5oci-eth of Motion Pictu
re and TeievisionEngineer
s, vol. 61 (1953), pp. 667-701), a negative silver image is produced by developing with a developer containing black and white developing agents, followed by at least one brief exposure or A color reversal method in which a dye-positive image is obtained by carrying out other suitable capri processing and subsequent color development; a dye-containing photographic emulsion layer is exposed and developed to produce a silver
A silver dye nickel silver method is used to form an image and use this as a bleaching catalyst to darken the dye.

Color developers generally consist of an aqueous alkaline solution containing a color developing agent. The color developing agent is a known primary aromatic amine developing agent, such as phenyl-1/diamines (e.g. 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-nonal-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-β-methquine ethylaniline, etc.) can be used.

In addition to this, Photog by F. A. Mason
rapicProcessing Chemistry
22 of y (Focal Press, 1966)
pp. 6-229, U.S. Patent No. 2゜193.015, No. 2
．． 592.364, JP-A-11848-'64933, etc. may be used.

Color developer additives also include alkali metal sulfites, carbonates, phosphates and pH additives such as bromides, iodides and inorganic antifoggants, &74'
I] fttll agent or antifoggant may be included. In addition, if necessary, water softeners, preservatives such as hydroxylamine, type 1 solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive Coupler, fogging agent such as sodium polyhydride, auxiliary developer such as 1-phenyl-3-vilasolidone, viscosity imparting agent], U.S. Pat.
, 083, 723, an antioxidant described in OLS No. 2.622.950, and the like.

The emulsion layer after color development is usually bleached.

Liquid port processing may be performed simultaneously with fixing processing, or may be performed separately. Suke Hakuge and 1 ~ Tetsu ■, Kobal B
IV), chromium (■), copper (polyvalent total compound such as [D, peracids, quinones, nitrone compounds, etc. are used. For example, ferricyanide compound, dichromate, iron l) or cobal Organic complex salts of l-(IV), such as ethylenediami/VM acetic acid, nitrilotriacetic acid, 1°3-
Aminopolycarboxylic acids such as diamino-2-gropanoltetraacetic acid, complex salts of isic acids such as citric acid, tartaric acid, and malic acid; persulfur rlN salts, permancanate dinitronephenol, and the like can be used. Of these, potassium ferrinanide, iron ethylenediaminetetraacetate (to)
Particularly useful are sodium and ferrous ammonium ethylenediaminetetraacetate. Ethylenediamine 4 ferrous iron 0
Complex salts can be used in independent whitening liquids, -m-sukehaku liquids, and -yu-yakuhaku foot-wearing liquids.

For bleaching or bleach-fixing solutions, see U.S. Patent No. 3,042.5.
No. 20, No. 3.241.966, Special Publication No. 45-850
In addition to the bleaching accelerators described in No. 6, No. 11145-8836, and the thiol compounds described in JP-A No. 53-65732, yuzu additive R4 can also be added.

For the purpose of improving sensitivity, increasing contrast, or promoting development, silver oxide emulsions may contain conductors such as polyalkylene oxide or its ethers, esters, and amines, thioether compounds, etc. Thiomorpholines, quaternary ammonium salt compounds 1-urethane dicenters,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent No. 2.400.53
No. 2, No. 2.423.549, No. 2.716,062
No. 3,617゜280, Mukai No. 3,772,021, No. 3,808,003, British Patent No. 1.488,99
Those described in No. 1 etc. can be used.

The combination of trimethencyanine sensitizing dyes according to the present invention has the above-mentioned excellent properties, and provides an electrically sensitive material having a green-sensitive silver halide emulsion layer with high sensitivity and good shelf life. Therefore, it is not only useful as an excellent green-sensitizing dye for color photosensitive materials, but also for various photosensitive materials, such as black and white photosensitive materials, various photosensitive materials for plate making, and even silver dye bleaching methods. It can also be applied to color photosensitive materials containing colored dyes.

〔Example〕

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

Example 1 Silver dihalide grains were precipitated by a double jet method, physically ripened by a conventional method, desalted, and chemically ripened by a gold sensitization method and a sulfur sensitization method. A silver iodobromide emulsion containing mole qb was obtained. The average diameter of the silver halide grains contained in this emulsion was 0.6 μm. This milk All I Ky contains 0.60 mol of silver halide and 880 g of seratin binder.

This emulsion was weighed out on a 1K7 scale and heated to 4°C to dissolve. Sufficient amounts of methanol solutions of the sensitizing dye according to the present invention and the comparative sensitizing color chart were added and mixed and stirred.

4-hydroxy-6-methyl-1,3,3a.

2 of a 1.0 hil% aqueous solution of 7-chitrazaindene.
Add 10 g of an aqueous solution of 11 g of l-hydroxy-3,5-dichlorotriazine sodium salt, and then add 10 g of a 1,0 g aqueous solution of l-hydroxy-3,5-dichlorotriazine sodium salt.
10ml of the aqueous solution was added and stirred.

This completed emulsion was coated on a cellulose triacetate film base so that the dry film fg- was 5 μm and dried to obtain a photosensitive phase material sample. This sample was cut into strithopus.

For the first part, a light wedge exposure was carried out using a photosensitive 8" with a light source with a color temperature of 5400° and a yellow filter attached to the light source.

After exposure, the film was developed at 20° C. for 3 minutes using a developer having the composition shown below, stopped, washed with water, and dried to obtain a black and white image of the A1 foot. The density of each processed sample was measured using an optical densitometer, and sensitivity and fog were all measured. The optical density reference point that determined the sensitivity was fog +0.2.
It was set as 0 point.

Developer composition and results obtained are shown in Table 1. In addition, the sensitivity is Vsu)N
This is a relative value assuming that the sensitivity of al is '1100.

1 Dye for margin comparison Dye for human comparison Dye B Dye for comparison Dye C As is clear from Table 1, the supersensitizing effect of the colored wood combination of the present invention is superior to that of known dye combinations).
It can be seen that supersensitization can be achieved while suppressing the occurrence of color fog.

Example 2 A silver iodobromide emulsion containing 7 moles of silver iodide was chemically ripened by the calendar method to obtain an average grain size of 1.0 μm and a silver content of 0.0 μm.
Emulsions of 60 mol/noodle emulsion and 70 mol/gelatin of noodle emulsion were obtained. This emulsion IKf was heated to 40°C, and 500 g f of the following emulsion of macenta coupler D was added.
0〇- and Jipte Lid L/-) 100m! Add and dissolve, add sodium dodecylbenzenesulfonate,
The material obtained by emulsifying and dispersing it in I kg of a 10% aqueous gelatin solution using a homogenizer was used. To this emulsion were added predetermined amounts of methanol solutions of the sensitizing dye according to the present invention and the comparative sensitizing dye, and the mixture was mixed and stirred.

Furthermore, 4-hydroxy-6-methyl-t, 3,38°7-
20 mJ'1 of a 1.0 weight coefficient aqueous solution of Citrazaindene
7JO, processed 20 m7! of a 1 weight aqueous solution of sodium salt of 1-hydroxy-3,5-dichlorotriazine, and further processed 1.
Add 0 ml of 10-ml Dangerous Aqueous Solution and stir. This completed emulsion was coated on a cellulose triacetate film base with a VC coating amount of 5 g/wl and dried to obtain a sample. This film test f-) was heated to 5400
A sensitometer with a °K light source was used, and a green filter was attached to the light source for wedge exposure. After exposure, development was carried out according to the following formulation, and after fixation, the total density of the magenta color image that was developed after drying was measured. The optical 6 degree reference point for determining the sensitivity was the fog +0.20 point. Immediately after coating, the sensitivity of the sample was subjected to color development treatment and was evaluated as So.
The sensitivity of the sample obtained after 3 weeks of raw storage and treatment at 5% RH was 81.

Table 2 shows the values of 81/SOX 100 (%).

Coupler D t Development processing prescription ■ Color development 3 minutes 15 seconds (38 “C) 2 Mark white 6 minutes 30 seconds 3 Washing with water 3 minutes 15 seconds 4 Fixing 6 minutes 30 seconds 5 Washing with water 3 minutes 15 seconds 6 Stable 3 The composition of the processing liquid used in each step is as follows.

As is clear from Table 2, the dye combination of the present invention exhibits less sensitivity loss after storage of raw samples, that is, it has excellent raw storage stability, compared to known dye combinations. I understand that.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Nobuaki Sakaguchi (1 other person)

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer has the following general formula ([) and general formula ( [)
An iron halide photographic material, characterized in that it contains at least one sensitizing dye represented by ↑. General formula (D 1 General formula ([D In the general formula (D, zl#, l represents an oxygen atom, a sulfur atom, or a selenium atom, and Dl represents an atomic group necessary to form an oxazole ring or an oxazoline ring. , R1 represents a water bulk atom, an alkyl group or an aryl group, R2 and R5 each represent an alkyl group, W
l, W2, W3 and Wll are each a hydrogen atom,
Alkyl group, -, rogene atom, alkoxy group, aryl group, carboxyl group, alkoxycarbonyl group, aryluogynecarbonyl group, nitro group, hydroxy group, anno group, amino group, acylamino group, sulfonylamino group, acyloxy group, carbamoyl group group, sulfamoyl group, sulfonyl group, acyl group, or a heterocycle X;
Wl and W2. W2 and W3 and/or W3 and WU may be linked to each other to form a ring. Xl (' represents an anion, mtj:it or 2. However, when the sensitizing dye represented by the above general formula 〇) forms an inner salt, it represents mal. Z2 and z5 each represent a sulfur atom or a selenium atom, D2 and D3 each represent a thiazole ring,
Represents an atomic group necessary to form a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, or a naphthoselenazole ring, R11 each represents a hydrogen atom, an alkyl group, or an aryl group, R
5 and R6 each represent an alkyl group. X20 represents an anion, .icl represents 2, and when the sensitizing dye represented by the above general formula (D forms the same molecule, n represents 1.