JPS61279851A - Photographic element - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to eliminate occurrence of fog by incorporating a specified N- and O-contg. heterocyclic sensitizing dye and a specified N- and O-contg. heterocyclic sensitizing dye in a silver halide emulsion. CONSTITUTION:The silver halide emulsion high in sensitivity spectrally sensitizable without occurrence of fog can be obtained by incorporating a combination of sensitizing dyes represented by formula I and II in which R1, R2, R3, and R4 are each H, alkyl, or aryl, and each of R1 and R2, R3 and R4 may form a 5- or 6-membered aromatic ring; each of R5, R6 is substituted to a quaternary ammonium N; each of R5 and R2, R6 and R4, R5 and R7, and R9 may form a hetero ring; each of R7, R9 is H, alkyl, aryl, cyano, or the like; each of R7 and R9 may form a 5- or 6-membered ring; R8 is H, alkyl, aryl, heterocyclic, cyano, or the like; Y<-> is an anion; and p is O or a positive integer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "photosensitive material") which is spectrally sensitized with at least two types of sensitizing dyes that mutually exhibit supersensitizing effects. The invention relates to a photographic element having a silver halide photographic emulsion layer with enhanced spectral sensitivity, particularly in the red-sensitive region.

[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. Various combinations of sensitizing dyes have been proposed for the purpose of zero supersensitization, which is called supersensitization.

However, it is known that the sensitizing dyes used in combination are required to be highly selective to each other, and that it is extremely difficult to predict the effect of C from the chemical structure of the sensitizing dye.

On the other hand, if two or more types of sensitizing dyes are used in combination to perform supersensitization, the spectral sensitivity in a specific spectral sensitizing wavelength range may actually decrease, fog may increase, or during the production of light-sensitive materials or before exposure after production. During storage (hereinafter referred to as "raw storage"), deterioration of stability over time such as decreased sensitivity and increased fog, and deterioration of stability of latent images from exposure (imaging) to development often occur. Achieving the purpose of supersensitization using a combination of sensitizing dyes without such adverse effects is one of the important challenges in the art of manufacturing photographic elements.

[Purpose of the invention]

It is an object of the present invention to provide photographic elements which are supersensitized by a novel combination of at least two different dyes and which are highly sensitive and fog-free.

Another object of the present invention is to provide a photographic element having a spectrally sensitized silver halide emulsion layer that does not exhibit a decrease in sensitivity or an increase in fog during raw storage of the light-sensitive material, especially during raw storage at high temperatures and high humidity. It is about providing.

[Summary of the invention]

As a result of various studies, the present inventors have determined that the above object is achieved by using the following general formula (1) and the general formula The present inventors have discovered that the present invention can be achieved by a photographic element characterized by containing at least one sensitizing dye represented by formula (II).

General formula (I) (r > p General formula (II) General formula (1), (If), in the formula R1 and R,
and R1 and R4 each jointly represent a group of atoms completing an aromatic 5- to 6-membered ring which may be substituted, or R1R2, R3 and R4 are each a hydrogen atom.

It represents an alkyl group or an aryl group, and Ro and R2 cannot be hydrogen atoms at the same time.

R3 and R, independently represent quaternized substituents, and R6 and R2 and R& and R9 may jointly complete a 5- to 6-membered fused heterocycle.

Furthermore, R3 and R1 and R4 and R1 may work together to complete a 5- to 6-membered fused heterocycle.

R1 and R9 are hydrogen atoms, alkyl, and alkoxy.

It represents each group of aryloxy, aryl, aralkyl and cyano, and R1 and R9 may jointly form a 5- to 6-membered ring. R11 is a hydrogen atom, alkyl, or acylkyl.

Aryl, heterocycle, cyano, substituted amino, alkylthio, marylthio, alkoxy.

Represents each aryloxy group and an acidic nucleus.

Y- represents a counter anion, and P represents 0 or a positive integer for combining ionic charges. G is oxygen and sulfur.

and selenium.

R1+ Examples of the alkyl group represented by Rz, Rs, or R include a methyl group, an ethyl group, and a propyl group.

Examples of the butyl group include a phenyl group and a naphthyl group.

Aromatic 5 completed by R1 and R3 or R3 and R4
~6-membered rings include, for example, benzene and naphthalene.

Typical examples include 5- to 6-membered rings such as thiophene, benzothiophenefuran, benzofuran, and pyridine.
is not necessarily fused directly to the heterocycle to which it is bonded, but may be fused via a non-aromatic ring.

These 5- to 6-membered aromatic rings may be substituted.

Examples of substituents include halogen atoms (for example, atoms such as chlorine and bromine), hydroxy groups, hydroxyalkyl groups (for example, hydroxyethyl groups, hydroxypropyl groups, etc.), alkyl groups (for example, methyl groups, ethyl groups, isopropyl groups, t-butyl group, etc.), aryl group (e.g., phenyl group), alkoxy group (e.g., methoxy group, ethoxy group, β-methoxyethoxy group, γ-carboxypropyloxy group, etc.), aryloxy group ( For example, phenoxy group, p-chlorophenoxy group, etc.), hydroxyaryl group (for example, p-hydroxyphenyl group,
Tobidroxyphenyl group. 2-hydroxynaphthyl group), amino group (e.g., dimethylamino group, diethylamino group, etc.), cycloalkyl group (e.g., cyclohexyl group), cyano group, carbamoyl group (e.g., carbamoyl group).

N,N-pentamethylenecarbamoyl group, N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, etc.), alkoxycarbonyl group (e.g. ethoxycarbonyl group), alkylthio group (e.g. methylthio group), etc. The basics are given.

In one preferred form, and Rh are substituted hydrocarbons containing 1 to 8 carbon atoms (eg, alkyl or aryl groups).

Representative examples of the substituent include sulfo group, sulfato group, carboxy group, hydroxycarbamoyl group, sulfamoyl group, cyano group, succinimino group, trimethylsilyl group, alkoxy group, and sulfo-substituted alkoxy group.

Specifically, sulfomethyl group and sulfoethyl group.

Sulfopropyl group, sulfobutyl group, sulfophenyl group, sulfatomethyl group, sulfatoethyl group, sulfatopropyl, sulfatobutyl group.

Sulfatophenyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, carboxybutyl group, carboxyphenyl group, hydroxyethyl group, hydroxypropyl group, carbamoylmethyl group, carbamoylethyl group, carbamoylpropyl group, carbamoylbutyl group, carbamoyl Representative groups include phenyl group, sulfamoylethyl group, cyanoethyl group, cyanopropyl group, iminoethyl succinate group, iminopropyl succinate group, trimethylsilylethyl group, methoxyethyl group, methoxypropyl group, and sulfoethoxyethyl group. It is.

R1 and R3 are hydrogen atoms, alkyl (e.g. methyl,
ethyl, etc.), alkoxy (eg, methoxy, ethoxy, etc.), aryloxy (eg, phenoxy), aryl (eg, phenyl), aralkyl (eg, benzyl), and cyano.

R1 and R9 may jointly form a 5- to 6-membered ring.

R8 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl,
groups such as propyl), aralkyl (e.g. benzyl, phenethyl, etc.), aryl (e.g. phenyl),
Heterocycles (e.g. chenyl).

(furyl, etc.), cyano, substituted amino (e.g., dimethylamino, anilino, etc.), alkylthio (e.g., methylthio group), alkoxy (e.g., methoxy group),
Represents each group such as aryloxy (for example, phenoxy group), arylthio (for example, phenylthio group), and an acidic nucleus.

G represents oxygen, sulfur, and selenium.

The acidic nucleus represented by R1 can take the form of any conventional merocyanine acidic nucleus.

Representative examples where the acidic nucleus is an acyclic group are shown below.

In the formula, R'', R', R' and R4 each represent a -valent substituent, such as an alkyl group (e.g. methyl group, ethyl group, octyl group, dodecyl group, 5ec-octyl group, etc.), an aryl group (e.g. PJ (lyl group, phenyl group, etc.), or a heterocyclic group (eg, benzofuryl group, etc.).

Representative examples where the acidic nucleus is a cyclic group are shown below.

O00 You can choose from.

Examples of the nitrogen-containing heterocyclic group necessary to form the cyanine dye represented by R in general formula (1) are shown below. (Substituents that these rings may have will be described later.) General formula〔! ], examples of the nitrogen-containing heterocyclic group represented by R and necessary to form a cyanine dye are shown below (the substituents that these rings may have will be described later). Examples of the nitrogen-containing heterocyclic group necessary to form the cyanine dye represented by R7S are shown below. (The substituents that these rings may have will be described later.) R%
In t's general formula (If), examples of nitrogen-containing heterocyclic groups necessary to form a cyanine dye represented by R& are shown below (substituents that these rings may have will be described later). ) These nitrogen-containing heterocycles have any substituent on the ring (for example, an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, an alkylthio group such as a methylthio group or an ethylthio group, or a phenyl group). , aryl groups such as tolyl group, phenoxy group, etc.
Heterocyclic groups such as ruoxy group, chenyl group, benzothiazolyl group, pyridyl group, halogen atoms such as carolo atom, chloro atom, bromine atom, amino groups such as N,N-diethylamino group, acetylamino group, methoxycarbonyl group,
Alkoxycarbonyl groups such as ethoxycarbonyl groups, cyano groups, N,N-dimethylcarbamoyl groups, carbamoyl groups, N,N-dimethylsulfamoyl groups, sulfamoyl groups, nitro groups, trifluoromethyl groups, hydroxy groups, methylsulfonyl groups etc.), D,
M. Sturmer, “Synthesis and Properties of Cyanine and Related Dyes in Heterocyclic Compounds,” Vol. 30 (1977)
(Synthesis and Properties
of CyaninesandRe1ated 0
yes in Chemistry of Heter
cyclic compounds 30 (19
77)), F. M. Herm, Cyanine Soybeans and Related Compounds (1964, published by Inter Science Publishers), etc.

The counter anion is one, Y- is a halogen atom (chloro,
Representative examples include anions such as bromine and iodine atoms) and sulfonic acids (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.).

The object of the present invention is achieved by at least one sensitizing dye represented by the general formula CI) and the sensitizing dye represented by the general formula (It), and a compound represented by the following general formula (III) may also coexist. If so, the effects of the present invention will be even greater.

General formula (III) (Y-)p where RI+ Rt, R3, RI, R5+ Rh,
RI, R11, RI Y - and p are represented by the general formula (1
), and the same thing can be exemplified.

Examples of the nitrogen-containing heterocyclic group necessary to form the cyanine dye represented by the general formula (l[[) are shown below.

I SRS Rs Rs
Examples of the nitrogen-containing heterocyclic group represented by pyro in general formula (11) and necessary to form a cyanine dye are shown below.

In the compound represented by the general formula (I[[), the nitrogen-containing heterocycle may have the same substituent as the heterocycle in the general formula (1).

Exemplary compounds of the present invention are shown below, but are not limited thereto.

NO03 N004 SO2゜NO, 5 NO, 6 SO3゜SO3゜NO, 1O No, 11 No, 12 No, 13 NO, 15 Br” NO0116 No, 17 No, 18 No, 19 lh Drunkness NO, 21 1;tHs( tl wealth) 350 go NO, 22 No, 23 rO No, 25 (・ 1,: No, 27
:・rg NO, 28 No1 4 No, 3O NO, 31 No, 32 No, 33 NO, 34 No, 35 No, 36 No, 37 No, 38 NO, 4O No, 41 No, 42 NO, 43 No, 45 NO, 46 No, 47 NO, 48 (shi2ha5υknee
(CHg)zsOsH-N(CtHs)sN
O,49:.

NO, 5O NO, 51 NO, 52 No, 53 No, 54 NO, 56 NO, 57 S03- Me>5
ttNo, 58 No, 59 No, 6O NO, 61 No, 62 No, 63 No, 64 No, 65 No, 66 No, 67 NO069 1; Is 15r9
L; HzL; l required NO, 70 So.

No, 71 No, 72 50s.

No, 73 HzOH No, 75 sO? NO, 76 No, 77 NO278 NO, 79 NO, 81 L; Zn2 (CH
II) aSOs-NO, 82 No, 83 No, 84 No, 85 NO, 86 1IJ... 9'° □l□::)] Hs (CHJ tSIJs- NO, 91 NO092 No, 93 Add,.

No.96 No.97 NO, 100 No, 101 No, 102 No, 103 No, 104 No, 105 NO, 106 ■ SOs.

1)・′・.

503el□,, :, - □ NO, 112 NO1113 No, 114 NO, 115 No, 116 No, 117 SO3゜ NO, 120 CH.

No. 121. , 122
"j '1,' NO, 123 NO, 124 NO1125 No, 126 No, 127 °1 (CHJ tso3- NO, 13O No, 131 No, 132 NO, 133 50m.

[1 NO, 1351 ['I NO, 1361 NO, 137 No, 138 No, 139 The sensitizing dye represented by the general formula (1) or [I cyanine soybean
and Related Compounds'' (Interscience Publications, New York, 1964).

The sensitizing dye of general formula (II) of the present invention is disclosed in the following patent.

It can be synthesized by referring to literature.

British Patent No. 625245, British Patent No. 654690, British Patent No. 84
No. 1119 French Patent No. 757767, US Patent No. 18
No. 46302 No. 1 No. 2345094, No. 2369646
No. 2378783.

No. 2385815, No. 2478366, No. 2610
No. 121.

No. 2238231, No. 2213995, No. 2503
No. 776.

Specifications of No. 2734900, JP-A-47-9678
issue.

Publications No. 60-78445, Journal of the American Chemical Society, Volume 67.

1B75-1889 (1945), by F.M. Herma, Cyanine Soybean Andrelated.
Compound (published by Inter Science Publishers in 1964), Pharmaceutical Journal, Volume 68, 191-194 (1
94B) Next, a specific synthesis example of the sensitizing dye of the general formula (n) will be shown, but other compounds represented by the general formula [■] can also be synthesized according to the following synthesis method.

[Synthesis Example 1] 3-(2-(3-(5,6-sihydro28.4H-
Tellazolo(5,4,3-i,j)quinolin-2-ylidene)-1-propenyl)-1-naphtho(1,2-d
) Thiazolio] Propanesulfonic acid inner salt (Exemplary compound NO63) 5.6-Sihydro-2-methyl-4H-
3.2 g of Tellazolo (5,4°3-i,j) quinolinium chloride was suspended in 30 ml of acetic anhydride, 3.8 g of diphenylformamidine was added, and the mixture was heated under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried.

Yield: 3.3 g Dissolve 2.3 g of the crude product in 20 ml of 1 cresol.
1.6 g of -(2-methyl-1-naphtho(1,2-d)thiazolio)propanesulfonic acid inner salt and 2.0 g of triethylamine are added, and the mixture is heated and stirred at 110°C for 20 minutes.

After cooling, dilute the supernatant with isopropyl ether.
Abandon "r, a・7ゞ1'4 addition 77 Stirring crystallization 81・
; The precipitate is filtered and washed with ethanol. The crude product is purified by repeated recrystallization from chloroform and methanol (1:1).

Yield 0.56g Melting point 300℃ or higher
i′ Maximum absorption wavelength in methanol solution 6
07 ncm Jiζ C Ega 2. i; 5-chloro-3,5,10-1-limethyl-3'-sulfoprobyl teratia luposyanine inner salt [Example □゛Kanamono NO67), 1 2,3,5-trimethyk<:/ Zoterazoliu L-Triff :)';fo J 97XJL/+
Heptaacid 4°2' and u3-ts-z o o-, □12
-(2Methylthio-r-propenyl)-3-trizothiazoli, 1o) Add 3.8g of propanesulfonic acid inner salt to 130m of pyridine.4. Ega7. A, a. Add 8 r40”c
・Stir at 11 l. The precipitated dye is collected by filtration and methano
(Wash with 1'j -l.
□": 0.47 g of the desired product was obtained by recrystallization and purification from a mixed solution of 2.2.3.3-tetrafluoropropanol and methanol.

Maximum absorption wavelength in methanol solution 595 na+ [Synthesis Example 3] Anhydro-3'-ethyl-3-(2-(3-2 sulfopropyloxy)ethyl)-tellulathiacarbocyanine hydroxide [Exemplary compound NO62] 2-hydroxy 1.9 g of ethyl trifluoromethane sulfonate and 1.2 g of propane sultone were mixed and heated on an oil bath at 120°C for 1 hour, and then allowed to cool to form a viscous mixture containing 2.4 g of 2-methylbenzotellurazole and 20 m of chloroform. j! After heating, stirring, and refluxing for 2 hours, ether was added to the reaction mixture, which was allowed to cool, to cause precipitation. The supernatant was removed by decantation, and 4.5 g of 2-(2-acetanilide vinyl)-3-ethylbenzothiazolium iodide, 20 tal of dimethylformamide, and 1.5 g of triethylamine were added and reacted at 60°C for 2 hours. . After cooling, ether was added to the reaction mixture to precipitate the product, which was isolated by filtration and recrystallized from methanol.

Yield 1.5g Methanol λwax 5B1nm [Synthesis Example 4] 2-(5-chloro-2-(3-(3-methyl-4-phenyl-2(3H)tellazoliden)-1-propenylidene)-3-penzoxa 13.5 g of 2-methyl-4-phenyltetrazole (zolio)ethanesulfonic acid inner salt (exemplary compound N0a8) was dissolved in 801 Il of dichloromethane, 9.0 g of methyltrifluoromethanesulfone (methyltrifluoromethanesulfone) was added, the solution was sealed, and the mixture was left to stand at room temperature for one week.

The precipitated crystals are collected by filtration and then suspended in acetic anhydride 120a+1.

Add 19.6 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, dilute with isopropyl ether, collect the precipitate by filtration, and add ethyl acetate 1
Wash and dry.

Yield 15.1g 2.9g of the crude product was dissolved in 20ta 1 of Tocresol and 1.4g of 2-(5-chloro-2-methyl-3-benzooxazolio)ethanesulfonic acid inner salt and 1g of triethylamine were added. Heat and stir at 110'C for 15 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize. The precipitate is collected by filtration and washed with ethanol.

It was purified by recrystallization from a mixed solvent of chloroform-methanol (1:2).

Obtained MO, 54 g Maximum absorption wavelength in methanol solution 601 nn + [Synthesis Example 5] Anhydro 3- (2-(3-(5-fluoro-3-methyl 2-(3H)penzotellazolidene) small propnyl)-5 -Methoxy-3-penzoselenazolio]propanesulfonic acid inner salt (Exemplary Compound No. 096) 13.1 g of 5-fluoro-2-methylbenzotellazole was dissolved in 100 ml of dichloromethane, and methyl drift
j ■ Add 9.0 g of fluoromethanesulfonate, tightly stopper it, and leave it at room temperature.
Leave at I'1 for 2 weeks. 1: The precipitated crystals are collected by filtration and then suspended in 100 ml of acetic anhydride. Add 19.6 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried.

Yield: 8.3 g Dissolve 2.8 g of the crude product in 2 liters of 1 cresol,
1.7 g of (5-methoxy-2-methyl-3-penzoselenazolio)propanesulfonic acid inner salt and 2 g of triethylamine are added, and the mixture is heated and stirred at 110° C. for 15 minutes.

After cooling, add 9 tbsp 1 ml 1-chill to dilute.
□,.

Discard the clear liquid. Acetone is added and the mixture is stirred for crystallization, and the precipitate is collected by filtration and washed with ethanol.

Purification was performed by recrystallization from a mixed solvent of chloroform-methanol (1:2). □ :'・Yield 0.51g
+'1 Maximum absorption wavelength in methanol solution: 599no+'The silver halide emulsion used in the photographic element of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver halides. Any material used in conventional silver halide emulsions, such as silver chloride, can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The grains may be grown all at once or after forming seed grains. You can let it grow. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be added sequentially and simultaneously while controlling the PH+ Pag in the mixing tank. This method allows crystal formation Silver halide grains with regular grain size and nearly uniform grain size can be obtained.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

In the process of forming and/or growing the grains, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing). A metal ion is added using at least one selected from complex salts containing
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

The silver halide emulsion may be freed from unnecessary soluble salts after the growth of silver halide grains has finished, or may be left in the silver halide emulsion. Disc
(Losure) No. 17643.

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

Silver halide grains used in silver halide emulsions may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or irregular crystal shapes such as spherical or plate shapes. It can be something you have. In these particles, (100)
Any ratio between the plane and the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 μm or less, and particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion with a wide grain size distribution may be used, or an emulsion with a narrow grain size distribution may be used alone or in combination of several types. good.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

In the present invention, the silver germide emulsion contains
:]1; Capri during the manufacturing process, storage, or photo processing.
□゛'' or to keep photographic performance stable: During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied □゛＄ ゝ゛$XJiJ%′″#°゛″″Buri″″l″4 swords″Katouchi 1□・.

Compounds known as
[As a binder (or protective colloid) for silver halide emulsions, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single or copolymers may also be used.

When gelatin is used as a binder for a silver halide emulsion, the jelly strength of the gelatin is not limited, but it is preferably 250 g or more (value measured by baggy method).

The photographic emulsion layer and other hydrophilic colloid layers of photographic elements using the silver halide emulsion of the present invention contain one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a photographic element using the silver halide emulsion of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the photographic element using the silver halide emulsion of the present invention contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. can be done.

The emulsion layer of the photographic element of the present invention contains dyes that undergo a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-) unilene diamine derivatives, aminophenol derivatives, etc.) during color development processing. A dye-forming coupler is used that forms .

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, a silver halide color photographic light-sensitive material may be produced using a method different from the above combination.

It is desirable for these dye-forming couplers to have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Either the 4-equivalent type, in which the S ion of S ion needs to be reduced, or the 2-equivalent type, in which only two molecules of silver ions need to be reduced, may be used. Dye-forming couplers can be combined with the oxidized form of a developing agent to produce development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral sensitizers and desensitizers, can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or D that releases development inhibitors during development to improve image sharpness and image graininess.
An IR coupler may also be used. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but the color turbidity is 1@x
fsftb゛*-estm″-) f, 1W4(D@M
@*tct4.

It can be anything. In place of the DIR coupler, use the corresponding turnip.
A DIR compound which undergoes a coupling reaction with the oxidized developing agent with or in combination with the toler to produce a colorless compound and at the same time releases a development inhibitor may be used.

A colorless coupler that undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate depending on the situation. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
If necessary, a low boiling point and/or water-soluble organic solvent is used in combination with the above high boiling point organic solvent to dissolve the solution, and a hydrophilic binder such as a gelatin solution is mixed with a surfactant using a stirrer.
After emulsifying and dispersing using a dispersion means such as a homogenizer, colloid mill, flow jet mixer, or ultrasonic device,
6 The dispersion may be added to the desired hydrophilic colloid layer, or a step of removing the low-boiling organic solvent simultaneously with the dispersion may be included.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent whitening agents, etc. have acid groups such as carboxylic acid or sulfonic acid, an alkaline aqueous solution is used. It can also be introduced into hydrophilic colloids as a hydrophilic colloid.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the photographic element of the present invention, causing color turbidity and deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

Image stabilizers can be used in the silver halide photographic elements of this invention to prevent degradation of the dye image.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the photographic element of the present invention contain an ultraviolet absorber in order to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

Formalin scavengers can be used to prevent degradation of magenta dye-forming couplers and the like by formalin during storage of the photographic element.

In the photographic elements of this invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a mordant such as a cationic polymer.

Compounds that change developability, such as development accelerators and development retardants, and bleach accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the photographic elements of the present invention. Which compound can be preferably used as a development accelerator according to Research Disclosure? -(Research D
isclosure) Section XXI B-D of No. 17463
The development retardant is a compound described in Section XXI of No. 17643, Section E. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The photographic emulsion layer of the photographic element of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urethane derivatives, urea derivatives, imidazole derivatives, and the like.

A fluorescent brightener can be used in the photographic element of the present invention for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable.

Photographic elements of the present invention can be provided with auxiliary layers such as filter layers, antihalation layers, and/or antiirradiation layers. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the photographic element of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to reduce the sliding friction of the photosensitive material.

Antistatic agents can be added to the photographic elements of this invention for antistatic purposes. The antistatic agent is applied to the milk of the support, 8, 8, 6, 3, ・"゛emulsion layer and/or other than the emulsion layer on the side where the emulsion layer is laminated to the support. It may also be used as a protective colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the photographic elements of this invention may include coatability-improving, antistatic, slippery-improving,
Various surfactants can be used for the purpose of emulsification dispersion, prevention of adhesion, and improvement of photographic properties (development acceleration, film hardening, sensitization, etc.).

Supports used in the photographic elements of this invention include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc., and reflective layers on these films. Includes flexible supports, glass, metal, ceramics, etc.

The photographic element of the present invention can be produced directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., as necessary, or to improve the adhesion, antistatic property, dimensional stability, abrasion resistance, etc. of the support surface. It may be applied through one or more subbing layers to improve hardness, antihalation, frictional properties, and/or other properties.

In coating the photographic elements of the present invention, thickeners may be used to improve coatability, such as hardeners, etc.
For substances that have a fast reactivity and may cause gelation before coating if added to the coating solution in advance, it is preferable to mix them using a static mixer or the like immediately before coating.

In preparing the photographic elements of this invention, the silver halide emulsions and other protective colloid layers are prepared according to Research Disclosure.
) Coated by the method described in No. 17463, XV, A, and B
It can be dried by the method described in .

The photographic elements of this invention can be exposed with electromagnetic radiation in the region of the spectrum to which the constituent emulsion layers are sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Light emitted from a phosphor excited by mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beam, χ ray, γ ray, α ray, etc. Any known light source can be used.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

Any known method can be used for developing the photographic element of the present invention. Depending on the purpose, this development process may be either a process to form a silver image (black and white development process) or a process to form a color image.If the image is created using the reversal method, the black and white negative is first developed. The photosensitive material is then exposed to white light or processed with a bath containing a fogging agent to perform color development. Silver dye bleaching may be used, in which an image is created and the image is used as a bleaching catalyst to bleach the dye.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods, such as a spray method in which the processing solution is supplied in the form of a spray, or contact with a carrier impregnated with the processing solution, are also used. A web method, a method of viscous development processing, etc. may be used.

The black and white development process includes, for example, a development process, a fixing process, and a water washing process. Alternatively, a developing agent or its precursor may be incorporated into the sensitive material, and the developing process may be carried out using only an alkaline solution.

A development process using a lithium developer as a developer may be performed.

Self-processing process, fixing process, water washing process as necessary
As a two-color development process, a color development process, a processing process, or a stabilization process accompanied by water washing is performed, but instead of a process using a bleach solution and a process using a fixer, a one-bath process is performed. It is also possible to carry out the bleach-fixing process using a bleach-fix solution, or it is possible to perform color development, bleaching, and fixing in one step.
It is also possible to carry out a monobath processing step using a one-bath development bleach-fix processing solution that can be carried out in a bath.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, an activator treatment step in which a color developing agent or its precursor is contained in the material and development is performed with an activator solution may be performed instead of the color development treatment step, or an activator treatment step may be performed in place of the monobath treatment. The beta treatment, bleaching and fixing treatments may be carried out simultaneously. Representative treatments among these treatments are shown below. (These treatments are performed as a final step, for example, either a water washing process or a stabilization process accompanied by a water washing process.) Color development process - Bleaching process Constant fixation process Color development process - Bleach-fixing process/Pre-hardening process - Neutralizing process - Color development process - Stop-fixing process - Washing process - Bleaching process Constant coloring process - Washing process - Post-hardening process/Color development Development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process / Monobath process / Activator process - Bleach-fixing process / Activator process - Bleach process Constant fixation Processing process In addition to these treatments, there is a method in which developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again, and various intensification treatments (amplification treatments) described in JP-A-58-154839. A developing method that increases the amount of dye produced may be used.

The trimethine cyanine sensitizing dye according to the present invention represented by the above general formula (I) or (If) or (II) has an amount of 5X10-' mole to 5X10 mole per mole of silver halide used in the silver halide emulsion. −'Mole,
Preferably lXl0-' mol to 2.5 x 10-3 mol,
Particularly preferably, the molar ratio of the dye of general formula (n) or general formula (III) to 5X10-'mol-1X10-' is preferably 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 an appropriate solvent such as methanol, ethanol, dimethylformamide, etc. alone or in combination. It may be added to the emulsion after that.

Although it can be added at any time during the manufacturing process of the light-sensitive material, it is generally preferable to add it to the silver halide emulsion during the second ripening or immediately after the second ripening.

The trimethine cyanine sensitizing dye according to the present invention includes one or more dyes of general formula (1), one or two or more dyes of general formula (n), and preferably a dye of general formula (III). It can be used in combination with other styryl dyes, etc., in combination with one or more of them, and can be used for spectral sensitization or superchromatic sensitization.

〔Example〕

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

□ □ Example 1
: Precipitation of silver halide grains by double jet method □R″i'rfLits＊'ll;tD
Male e,l'1m11M*L・7 ．Silver halide grains contained in this emulsion
) had an average diameter of 0.5μ・7. This emulsion 1 to 8
Middle: 'E! *0. 60'e tL
t (7) /, O 'y' y(Eilil & fff
't f 7/, 47 1 piece 880g
Contains.

1 kg of this emulsion was weighed into a pot and heated to 40°C to dissolve it. Then, predetermined amounts of methanol solutions of the sensitizing dyes as shown in Table 1 were added and mixed and stirred.

Furthermore, 4-hydroxy-6-methyl-1.3.3a,7-
Tetra: Add 2011 of a 1.0% by weight aqueous solution of Zaindene, 1-hydroxy-3.5-dichlorotriazine sodium 3. 1 □ 0 engineering 1 o. ,. picture,
Step 9, A2: 1On+1 of a 1.0% by weight aqueous solution of sodium nylbenzenesulfonic acid salt was added and stirred. This finished emulsion was coated on a cellulose triacetate film base with a dry film thickness of 5 μl and an amount of silver of 45 aeg/d.
A sample of the light-sensitive material was obtained by coating and drying the film to give a thickness of 1.

This sample was cut into strips.

One of them was a light wedge exposure using a photosensitive needle with a light source with a color temperature of 5400'K and a red filter attached to the light source. After exposure, development was carried out at 20° C. for 3 minutes using a developer having the composition shown below, stopped, fixed, washed with water, and dried to obtain strips having a predetermined black and white image. The density of each processed sample was measured using an optical densitometer to measure sensitivity and fog. The optical density reference point that determined the sensitivity was fog +0.2.
It was set as 0 point.

Developer composition The results obtained are shown in Table 1.The sensitivity is shown in Table 1.
It is a relative value with the sensitivity of 100.

As is clear from Table 1, the supersensitizing effect of the dye combination of the present invention is superior to that of known dye combinations.
Moreover, it can be seen that supersensitization can be performed while suppressing the occurrence of dust.

Example 2 A silver iodobromide emulsion containing 6 mol % of silver iodide was chemically ripened by a conventional method to obtain an average grain size of 1.1 μm.

Silver salt 0.60 mol/Kg emulsion, gelatin 70g/Kg
An emulsion of emulsion was obtained. Ikg of this emulsion was heated to 40°C, and 500g of an emulsion of magenta coupler D shown below was added thereto. The emulsion of coupler D is prepared by adding 100 g of coupler D to 300 mj! of ethyl acetate. and dibutyl phthalate 100m
1 was added to dissolve the mixture, sodium dodecylbenzenesulfonate was added, and the resulting mixture was emulsified and dispersed in a 10% aqueous gelatin solution IK using a homogenizer. To this emulsion, predetermined amounts of methanol solutions of sensitizing dyes as shown in Table 2 were added, and the mixture was mixed and stirred.

Furthermore, 4-hydroxy-6-methyl-1,3,3a, 7.
- 20rs of a 1.0% by weight aqueous solution of tetrazaindene
It was added, 20+++1 of a 1% aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was added, and 10111 of a 1.0% aqueous solution of dodecylbenzenesulfonic acid sodium salt was further added and stirred. This completed emulsion was coated on a cellulose triacetate film base so that the coated silver amount was 50 mg/d@*, and dried to obtain a sample. Color temperature 5
A photosensitive needle with a light source at 400° was used, and a red filter was attached to the light source for light simulated exposure. After exposure, development was carried out according to the following formulation, bleached, fixed, and dried, and the density of the developed magenta color image was measured. The optical density reference point for determining the sensitivity was the fog +0.20 point.

Immediately after coating, the sensitivity of the sample obtained by color development processing is S,
The sensitivity of the sample obtained after application and storage at 38° C. and 70% RH for 3 weeks and subsequent processing was defined as S.

Table 2 shows the values of S+/So X100 (%).

H Development processing prescription 1, color development 3 minutes 15 seconds (38℃) 2
, bleaching 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, stabilization 3 minutes 15 seconds The composition of the processing solution used in each step is as follows. It is something.

Color developer Bleach solution Fixer Stabilizer Table 2 A: Immediately after application KB: 3B℃ShaseiKintoguchi 0% and 3 years agoMakiNori t# As is clear from Table 2,
The dye combination of the present invention is 1, compared to the dye combination of the comparative example,
It can be seen that there is little decrease in sensitivity and little increase in capri after storage of raw samples, that is, excellent raw storage stability.

Agent Patent attorney Toru Takatsuki Procedural amendment dated June 15, 1985 Mr. Manabu Shiga, Commissioner of the Patent Office ■, Indication of the case Patent application filed on June 5, 1985 (4) 3, Case of the person making the amendment Relationship with Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4゜ Representative Voluntary action 6. Detailed explanation of the invention in the specification to be amended (1) "An acidic nucleus" on page 16, line 5 of the specification t- "An acidic nucleus does not matter whether it is cyclic or acyclic.Next, a typical example of an acidic nucleus is shown in one limit resonance structure.An acidic nucleus" is corrected.

(2) Correct "dye" in lines 2 and 3 on page 27 to read "at least one dye."

(3) Same, pages 52-55, A10? -411
The chemical formula described as 8 is corrected as follows.

m108 e SOl cliff 110 f6ill 114 0zHs e(4H@ ■ 118
”□ That's all □ Procedure Principal Fusho (method) % formula % 1. Indication of the case 1985 Patent Application No. 121848 2. Name of the invention Photographic element 3. Person making the amendment Relationship to the case Address of the patent applicant 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Konishiroku Photo Industry Co., Ltd. 4, Agent

Claims (1)

[Scope of Claims] It is characterized by containing a combination of at least one sensitizing dye represented by the following general formula [I] and at least one sensitizing dye represented by the following general formula [II]. photo elements. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In general formula [I] and general formula [II], R_1 in the formula
and R_2 and R_3 and R_4 each jointly represent a group of atoms completing an optionally substituted aromatic 5- to 6-membered ring, or R_1, R_2, R_3 and R_4 each represent a hydrogen atom, an alkyl group or an aryl group. , and R_1 and R_2 cannot be hydrogen atoms at the same time. R_5 and R_6 independently represent quaternized substituents, R
_5 and R_2 and R_6 and R_4 may jointly complete a 5- to 6-membered fused heterocycle. Furthermore, R_5 and R_7 and R_6 and R_9 may jointly complete a 5- to 6-membered fused heterocycle. R_7 and R_9 represent a hydrogen atom, alkyl, alkoxy, aryloxy, aryl, aralkyl, and cyano groups, and R_7 and R_9 may jointly form a 5- to 6-membered ring. R_8 is a hydrogen atom, alkyl, aralkyl, aryl,
Represents a heterocycle, cyano, substituted amino, alkylthio, arylthio, alkoxy, aryloxy group, or acidic nucleus. Y^- represents a counter anion. P represents 0 or a positive integer for combining ionic charges. G represents oxygen, sulfur and selenium.