JPS61281235A - Photographic element - Google Patents

Abstract

PURPOSE:To form a photographic element spectrally sensitized and enhanced in sensitivity without increase of fog during raw storage under high temp. and high humidity by incorporating a combination of 2 kinds of specified dyes differ ent from each other. CONSTITUTION:A silver halide emulsion layer contains at least one of the trimethine cyanine sensitizing dyes represented by formula I and II, and at least one of the trimethine cyanine sensitizing dyes represented by formulae III and IV. The dye of formula I, II, III, or IV is used, especially preferably, in an amt. of 5X10<-6>-1X10<-3>mol per mol of silver halide to be used for the emulsion, and preferably, in a (III or IV)/(I or II) molar ratio of 1:20-20:1.

Description

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

[Conventional technology]

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. is called supersensitization. Various combinations of sensitizing dyes have been proposed for the purpose of supersensitization.

However, it is also known that the sensitizing dyes used in combination are required to be extremely selective with respect to each other, and that it is extremely difficult to predict the effects of the sensitizing dyes from their chemical structures.

On the other hand, if two or more types of sensitizing dyes are combined to perform supersensitization, the spectral sensitivity in a specific spectral sensitizing wavelength range may decrease, fog may increase, or during or after the production of photographic elements. 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. 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 a photographic element which is supersensitized by a novel combination of at least two different dyes, has high sensitivity, and is fog-free.

Another object of the present invention is to provide a photographic element having a spectrally sensitized silver halide emulsion layer that exhibits no increase in fog during raw storage of the photographic element, particularly during raw storage at high temperatures and high humidity. be.

[Summary of the invention]

As a result of various studies, the present inventors have determined that the above object is achieved by providing a photographic element having at least one silver 10-genide emulsion layer on a support, in which the silver 10-genide emulsion layer has the following general formula: Contains a combination of at least one sensitizing dye represented by (1) or (II) and at least one sensitizing dye represented by general formula (I[[) or (IV)] It was discovered that this can be achieved by a photographic element having the following characteristics, leading to the present invention.

General formula CI) R5 General formula [■] General formula (I [I] General formula (1%') In the formula, R1 and R1 are (i) each a hydrogen atom or an optionally substituted monovalent group; , at least one of which is an optionally substituted alkyl group or aryl group, and (ii) a group of atoms that jointly complete a ring fused to a ring containing a tellurium atom and a nitrogen atom, and R, Ra, and R4 represents a hydrocarbon group which may be independently substituted, and may be used in conjunction with R3 to complete a 5- to 6-membered fused heterocycle.

E represents an acidic nucleus, Lt and R represent a methine bond which may each be independently substituted, n represents 0, l or 2, and Q represents a nitrogen-containing 5 which may be further fused with a ring. Represents a group necessary to form a member ring.

X represents an oxygen atom or a sulfur atom, and Rs and R* are both hydrogen atoms, or together represent an atomic group necessary to complete an aromatic fused ring.

Examples of the alkyl group represented by Rt and Rs include a methyl group, ethyl group, propyl group, butyl group, and examples of the aryl group include a phenyl group and a naphthyl group.

Preferred rings to be fused to the ring containing a tellurium atom and a nitrogen atom completed by Rt and R2 are aromatic 5-
It is a 6-membered ring, and representative examples include 5- to 6-membered rings such as benzene, naphthalene, thiophene, benzothiophene, furan, 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, such as chlorine and bromine atoms, 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, etc.), alkoxy group (e.g., methoxy group, ethoxy group, β-methoxyethoxy group, γ-carboxypropyloxy group, etc.), aryloxy group (e.g. phenoxy group, p-chlorophenoxy group, etc.), human mixaryl group (e.g. p-hydroxyphenyl group, hydroxyphenyl group, 2-hydroxynaphthyl group, etc.), amino group (e.g. dimethyl amino 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 (eg, ethoxycarbonyl group), and alkylthio group (eg, methylthio group, etc.).

As the hydrocarbon group of R, Rs, Ra, preferably,
Unsubstituted alkyl groups (e.g. methyl, ethyl, isobutyl, etc.), substituted alkyl groups, aryl groups (e.g. phenyl, etc.), substituted aryl groups, aralkyl groups (e.g. benzyl, phenethyl, etc.), allyl groups, hetero cyclic group (
pyridyl, benzothiazolyl, etc.), optimally substituted alkyl or aryl groups containing 1 to 8 carbon atoms.

Substituents include sulfo group, sulfato group, carboxy group, hydroxy group, carbamoyl group, sulfamoyl group,
Representative groups include a cyano group, a succinimino group, a trimethylsilyl group, an alkoxy group, and a sulfo-substituted alkoxy group.

Specifically, sulfomethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, sulfophenyl group, sulfatomethyl group, sulfatoethyl group, sulfatopropyl group, 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, carbamoylphenyl group, sulfur Representative groups include famoylethyl group, cyanoethyl group, cyanopropyl group, iminoethyl succinate group, iminopropyl succinate group, trimethylsilylethyl group, methoxyethyl group, methoxypropyl group, and sulfoethoxyethyl group.

The aromatic fused ring formed jointly by Rs and Rs is a benzene ring, which includes a nitrogen atom such as chloro and bromine, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, and an ethoxy group. or an alkoxy group such as a propoxy group.

Examples of the 5- to 6-membered fused heterocycle formed by R5 and R5 include the following.

In case of general formula CI) In case of general formula (II) In case of general formula (I [I) The acidic nucleus E can take the form of any common merocyanine acidic nucleus.

When E is an acyclic group, Ra, Rh% Re and Rd are each a -valent substituent, and an alkyl group (e.g. methyl group, ethyl group, octyl group, dodecyl group, C-octyl group, etc.) ), aryl groups (for example, p-tolyl group, phenyl group, etc.), or heterocyclic groups (for example, benzofuryl group, etc.).

When E is a cyclic group In the formula, R has the same meaning as the symbol R in the general formula (Ill).

The following rings are preferable as the nitrogen-containing 5-membered ring in which Q is completed (expressed as a group).

Penzotelluriazolinidene, naphthotelluriazolinidene, naphthotellurium azolinidene, 3H-indolylidene,
lH or 3H-Benzintrilidene, oxazolinylidene, oxazolidinylidene, penzoxazolinylidene, naphthoxazolinylidene, oxadiazolinylidene, thiazolidinylidene, phenanthrothiazolinylidene, acenaphthothi Azolinylidene, thiazolinylidene, penzothiazolinylidene, naphthothiazolinylidene,
Tetrahydropenzothiazolinylidene, dihydronaphthothiazolinylidene, thiazoxazolinylidene, selenium azolinylidene, selenium azolinylidene, penzoselen azolinylidene, naphthoselen azolinylidene, selenium asia I linylidene, Tellurium azolinylidene, naphthotellurium azonylidene, birazolinylidene, imidazolinylidene, imidazolidinylidene, penzimidazolinylidene, naphthoimidazolinylidene, diazolinylidene,
Tetrazolinylidene.

These rings may be further substituted.

Preferred sensitizing dyes of the general formula [V]
, [Vrl, [■] are sensitizing dyes.

General formula [■] RISR, , R1, n and E represent f& as in the above general formula CI].

R(1) represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aralkyl group, or a cyano group, or represents an atomic group that forms a 5- to 6-membered ring together with R1. Further, R(t) and RO) represent a hydrogen atom and an alkyl group, respectively.

R(4) is a hydrogen atom, alkyl (e.g., methyl, ethyl, etc.), alkoxy (e.g., methoxy, nidoxy, etc.), aryloxy (e.g., phenoxy group), aryl (e.g., phenyl group), aralkyl (e.g., benzyl group) and cyano group.

R(4) and R1 may jointly form a 5- to 6-membered ring.

R(!1), R(0) and R(7) are hydrogen atoms, alkyl (e.g. methyl, ethyl, propyl, etc.), aralgyl (e.g. benzici, phenethyl, etc.), aryl (e.g. phenyl) ), heterocycles (e.g., chenyl, furyl, etc.), alkyloxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy), cyano groups, amino (e.g., dimethylamino, anilino, etc.) ), alkylthio (eg, methylthio group), arylthio (eg, phenylthio group) groups, and acidic nuclei. However, R(4), R(s), R<・)
,RC? ) are not all hydrogen atoms.

k is 0 or 1.

Preferred sensitizing dyes of general formula (n) are of general formula [■]
, (IX) and (X).

General formula [■] R, R3, Qsn and X are synonymous with general formula (III).

R, Rs, Ql and X are synonymous with general formula (U), and R
1), R'') and R'' have the same meanings as the same symbols in general formula (VI).

General formula [X] R, R3, Ql and X are synonymous with general formula (I [), and ++-4 formula (
Vll) The same symbol as teno is the same as s.

Preferred compounds of general formula (I[I) are [■], [■],
(XnI]).

General formula (XI) R1, R5, R8 and n represent the same meanings as in the above general formula [I[I].

General formula α0 Rs, R6, R6 and E have the same meanings as in general formula (III), and R(I), R(1) and R(3) have the same meanings as the same symbols in general formula [■].

General formula (XI[[) KR5, Rs%R, and E are synonymous with general formula (I[[), R(4), R('), R(phantom, R(?n, and k is synonymous with the same symbol in the general formula [■].

Preferred compounds of general formula (■) are (XIV), CXV)
, (XVI).

General formula (XIV) R4, R6, Ro and n represent the same meanings as in the above general formula (IV).

General formula (XV) R4, R5, R6 and E have the same meanings as in general formula (II/), and R(+), R'') and R(3)l have the same meanings as the same symbols in general formula (M). It is.

General formula (XVI) R4, R5, R6 and E are synonymous with general formula (ff), R(4), R(s), R(0), R'' and cFk+,
*General formula (Vll) teno 1: Synonymous with symbol.

Examples of sensitizing dyes used in the photographic element of the present invention are shown above.
The sensitizing dye of the present invention is not limited to the following dyes.

Exemplary compounds of general formulas [I] and (II) cans CH-CHISO3K CI(act(*03O3Na (Cut)ssOJ (CHI)4S03Na (CHI)*SOJa (cn, ノ45LJ3tl (UHtGkh)tsuNC).

C.L. tHs (cut)asoiNa CH, CH, OSO, Na (CHJ 3S03K C.I.H.

r14. .

(CHt)asOaK CJs CHtel(*OSOaNa (Cut)4SOJ C,H.

CH.

and H3 Ha (Cut)asO+■ (Cut)ssOJa (CH,CH,O), (C)11), SO,Na(CH
, CH, *(CH り JOsK (CHgetltO)g(CHt).5OaKtHi 薯CtHs (CH,), SO, H CH, CH, CHSO3 to CI.

(COx)4SOJa ■ CJ4SOslla CH, CH=Cut CH! CHtCoOHn:t CH*CH@05OsNa , = 1C CJs n=1 (CH*)ssOaK n=1CH*CHt
OHnyot CJs 1=1 C mountain n=1 C・■・nn=2 CtH・. =2 CJ@ (Cut)tsOsNa CtHa CHtCHzCH8OaK CH3 Exemplary compounds of general formulas (■) and (ff) Js CHzCH*03OsNa SO31'1 (CHz)x 0sNa (cuJ+5osl(・N(ctu-)).

(CH,),SO,H 0Hs (CH,CHto)ICIItC112S03NaCT
ItCHtO8OsNa CH,C1,C) I-SO, to CH3C,H.

The sensitizing dye of the present invention can be prepared by referring to the following patents and documents.

British Patent Nos. 625,245, 654,690, 841,119, Buddhist Patent No. 757.767, U.S. Patent No. 1,846,302, 2,345°094, 2,369 , No. 646, No. 2,378,783,
2.385,815, 2,478,366, 2,610.121, 2.238,231, 2
, No. 213,995, No. 2.503,776, No. 2.
Specifications of No. 734,900, Japanese Patent Application Laid-open Nos. 47-9678 and 60-78445, Journal Op.
The American Chemical Society, Volume 67, 1
875-1889 (1945), F.

M. Harma, Cyanine Soybeans and Related Counties (published by Inter Science Publishers, 1964) East Line, vol. 68, 191-19
4 (1948) etc.

Next, specific synthesis examples will be shown, but other compounds represented by the above general formula can also be synthesized according to the following synthesis method.

Synthesis Example 1 2-(5-(2-(5-fluoro-3-methyl-2(3
H)-Benzotelazolidene)ethylidene)4-oxo-2-thioxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (Exemplary Compound 7) 2-acetanilidevinyl-5-fluoro-3-methylbenzotel 2.89% of lazolium trifluoromethanesulfonate and 0.959% of 3-carboxymethylcordanine were added to 3% of absolute ethanol.
Dissolve in 0ml>), add triethylamine 29 and add 20
Rinse under high heat for a minute.

The reaction solution is allowed to cool, and then sufficiently cooled in an ice-water bath to undergo zeta crystallization. The crude product is purified by repeated recrystallization from methanol. Yield O, absorption maximum wavelength in 69 citanol solution 547 nm.

Synthesis Example 2 5-(4-(IH-2,3-dihydropyride [2゜1
-b]penzotellazolyl]methylene-4-oxo-2
-thioxo-1,3-thiazolidin-3-yl acetic acid (exemplified compound 30) 4-acetanilide methylene-1,2,3,4-tetrahydropyrido (2,1-b) penzotellazolium iodo salt 5, 69 and 3-carboxymethylrhodanine 1.
99 was dissolved in 60 ml of absolute ethanol, triethylamine 29 was added thereto, and the mixture was heated under reflux for 15 minutes. After cooling, the mixture was acidified with acetic acid to cause crystallization, and the precipitate was collected by filtration and washed with ethanol. Purification was carried out by dissolving it in methanol containing triethylamine and acidifying it with acetic acid for crystallization. Yield 1.49, melting point 3
00℃ or higher, absorption maximum wavelength in methanol solution 556
nap.

Synthesis Example 3 2-(5-(2-(3-methyl-2(3H)cheno(2
,3-d)tellazoliden)ethylidene)-4-oxo-2-thioxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (Exemplary Compound 53)2-acetanilidevinyl-3-methyl-cheno(2,3 -d) 2.6 g of tellrazolium trifluoromethanesulfonate and 3-
1.29 of β-sulfoethylrhodanine was dissolved in 50 mQ of absolute ethanol, 29 of triethylamine was added, and the mixture was heated under reflux for 15 minutes. The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol. Yield 0.859, absorption maximum wavelength in methanol solution 562
nl11° Synthesis Example 4 4-(2-(5,6-sihydro2H,4H-tellazolo(5,4,3-i,j)quinoline-2-ylidene)
ethylidene]-5-oxo2-thioxo-1,3-thiazolidin-1-yl acetic acid (Exemplary Compound 75) 2-acetanilidevinyl-5,6-sihydro4H-
Tellazolo (5,4,3-i,j)quinolinium chloride 4.69 and 3-carboxymethylrhodanine 1.9
Dissolve g in 50 mQ of absolute ethanol, add triethylamine 29 and heat under reflux for 15 minutes. Let the reaction solution cool,
Further, the mixture is sufficiently cooled in a water bath to cause crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol.

amt, 4g, absorption maximum wavelength in methanol solution 550
nm.

Synthesis Example 5 2-(5-2-(3-methyl-4-phenyl-2(3H
) tellurazoliden) ethylidene) 4-year-old xo-2-thioxo-1,3-thiazolidin-3-yl) ethanesulfonic acid (Exemplary Compound 104) 2-acetamidovinyl-3
-Methyl-4-phenyltellazolium trifluoromethanesulfonate (2.99 g) and 3-β-sulfoethylrhodanine (1.2 g) are dissolved in 30 ml of absolute ethanol, 2 g of triethylamine is added, and the mixture is heated under reflux for 15 minutes.

The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated product is collected by filtration. The crude product is purified by repeated recrystallization from methanol. Absorption maximum wavelength in methanol solution 546 nff1° Synthesis example 6 5-(2-(3-ethyl-6-methyl-2(3f()penzothiazolidene)ethylidene-3-phenyl-2 −
Thioterazolidine-2,4-dione (Exemplary Compound 1
2B) 2-(2-acetanilide vinyl)-3-ethyl-6-
Methylbenzothiazolium iodo salt 4.59 and 3-phenyl-2-thiotelazolidine-2°4-dione 29
and dissolved in 30 ml (l) of ethanol.

Add triethylamine 29 and heat under reflux for 10 minutes, then cool. The precipitated crude product is collected by filtration and washed with ethanol.

Recrystallize from methanol to obtain orange-red crystals. Yield 1.
29, absorption maximum wavelength in methanol solution 531 nm.

Synthesis Example 7 5-(4-(3-ethyl-5-methyl-2(3H)tellazolidene)-2-methyl-2-butenylidene)-4-
Oxo-2-thioxo-1,3-thiazolidin-3-yl acetic acid (Exemplary Compound 141) 2-(3-acetanilidomethylene-2-butenyl)-3-ethyl-5-methylbenzotellazolium iodo salt 5.99 and 1.99 ml of 3-carboxymethylrhodanine are added to 80 ml of ethanol.

After adding 3 g of triethylamine and heating under reflux for 30 minutes, the mixture was cooled with water and precipitated as acetic acid. The crude product is heated and dissolved in methanol containing triethylamine, cooled and acidified with acetic acid to crystallize. Collect by filtration and wash with ethanol to remove the target substance.
．． Got 2 layers. Maximum absorption wavelength in methanol solution 6081
11a Above, typical synthesis examples of the sensitizing dyes represented by the general formulas CI) and (I[) according to the present invention have been described. Ha, F.
It can be synthesized with reference to "The Cyanine Dice and Related Compounds" by M. Palmer (Interscience Publishers, New York, 1964).

The above general formula [I] or (If) or [E] or [■]
The trimethine cyanine sensitizing dye according to the present invention represented by
moles, preferably lXl0-@mol to 2.5xlO-'
mole, particularly preferably 5X10@mol-1X10-'. The usage ratio of the dye of general formula (I[I) or (■) to the dye of general formula (1) or (ff) is a molar ratio!
:20-20:1 is preferable.

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 photosensitive material manufacturing process, it is generally preferable to add it to the emulsion during the second ripening of the silver halide emulsion or immediately after the second ripening. .

The trimethine cyanine sensitizing dye according to the present invention includes one or more of the dyes of the general formula CI) or (I[) and the general formula (CI) or (I[)].
It can be used in combination with one or more of the dyes III) or [■], and in combination with other styryl dyes, etc., for spectral sensitization or superchromatic sensitization.

The combination of sensitizing dyes according to the present invention has the above-mentioned excellent properties, and it is possible to obtain a photographic element having a silver halide emulsion layer with high sensitivity and no increase in fog during raw storage. In particular, it is not only useful as an excellent sensitizing dye for color photosensitive materials, but also for various photographic elements,
For example, it can be applied to black and white photographic elements, various photographic elements for plate making, and even color photographic elements containing colored dyes produced by silver dye bleaching.

The photographic element of the present invention need only have at least one silver halide emulsion layer on a support, which includes α-
Paper laminated with olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene), etc.
Flexible reflective supports such as synthetic paper, 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 provided on these films. flexible support, glass, metal,
Includes pottery etc.

The silver halide emulsions used in the photographic elements of this invention include:
Any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide.

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 particles may be grown all at once, or may be grown after seed particles are created. 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. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling p■ and I)Ag in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

During production of the silver halide emulsion of the present invention, it is possible to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains by using a silver halide solvent as necessary. can.

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 a reduction sensitizing liquid can be applied inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disc
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, (10G)
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. Emulsions with a wide grain size distribution may be used, or emulsions with a narrow grain size distribution may be used alone or in combination.

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 a precious metal compound of gold and silver can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide emulsions of this invention include steps in the manufacturing of photographic elements;
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, monomers, etc. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as mono- 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 two hardeners that crosslink binder (or protective colloid) molecules and increase film strength. By using the above, hardening can be achieved. Hardeners can be added to the processing solution in amounts that will harden the photographic element to the extent that it is not necessary to add a hardener to the processing solution; however, 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 poorly soluble synthetic polymer for the purpose of improving dimensional stability. be able to. The emulsion layer of the photographic element of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-)12-diamine derivatives, aminophenol derivatives, etc.) during color development. Dye-forming couplers are used that form dyes. 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, photographic elements may be created using different combinations than those described above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include coupling with the oxidized form of the developing agent (
Thus, development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers, etc. Compounds that release photographically useful fragments can be included. These dye-forming couplers may be used in combination with colored couplers that have a color correction effect or DIR couplers that release a development inhibitor during development and improve image sharpness and image graininess. 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 if the color turbidity is not noticeable, a different type of dye may be used. Instead of the aDIR coupler, which may form a dye, a DIR compound may be used which, together with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to form a colorless compound and at the same time release a development inhibitor. good.

A colorless coupler that undergoes a coupling reaction with an oxidized 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 cast inhibitors, 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. Various methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water-soluble one as necessary. Dissolve using an organic solvent and emulsify using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After being dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color cast preventive agents, ultraviolet absorbers, optical brighteners, etc. contain acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

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. In addition, a color cast inhibitor can be used to prevent graininess from becoming noticeable.

The color fog preventive agent 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 photographic elements of this invention to prevent degradation of the dye image.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photographic element of the present invention contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photographic element 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. Compounds that can be preferably used as development accelerators are listed in Research Disclosure.
Closure) No. 17643, xxt section B-D, and the development retardant is a compound described in xxI of No. 17643.
It is a compound described in 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 may contain polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, 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.

In the photographic element of the present invention, an optical brightener can be used for the purpose of emphasizing the whiteness of the white background and making the coloration 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. Dyes may be contained in these layers and/or in the emulsion layers that are leached or bleached from the photographic element during processing.

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 photographic element, improving the ease of writing, and preventing the photographic elements from sticking together.

Furthermore, a lubricant can be added to reduce sliding friction, and an antistatic agent can be added to prevent static electricity. The antistatic agent may be used in the antistatic layer on the side where the emulsion of the support is laminated, and the hydrophilic layer other than the emulsion layer on the side where the emulsion layer is laminated with respect to the emulsion layer and/or the support. It may also be used in colloid layers.

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.).

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.

Thickeners may be used in coating the photographic elements of this invention to improve coating properties. Also, for example, as a hardening agent,
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 emulsion layers and other hydrophilic colloid layers were prepared by Research Disclosure.
e) It can be applied by the method described in No. 17643, xv, A, and dried by the method described in B of the same.

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 phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays, alpha rays, etc. Any of these 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 of a variety of development processes can be used to develop the photographic elements of this invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose. If an image is to be created by the reversal method, a black and white negative development process is first performed, and then a color development process is performed by applying white exposure or processing with a bath containing a fogging agent. Alternatively, a silver dye bleaching method may be used in which a dye is contained in the photographic element, a black and white development process is performed after exposure to form a silver image, and this is used as a bleaching catalyst to bleach the dye.

Each processing step is usually carried out by immersing the photographic element in a processing solution, but other methods are also available, such as a spray method in which the processing solution is supplied in the form of a spray, or by contacting the photographic element with a carrier impregnated with the processing solution. A web method, a method of performing 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. It is also possible to use a stone in which a developing agent or its precursor is incorporated into the photographic element and the developing process is carried out using only an alkaline solution. A development process using a lithium developer as a developer may also be performed.

The color development process includes a color development process, a bleaching process, a fixing process, and if necessary, a water washing process, or a stabilization process accompanied by water washing. Instead of the processing step using −
A bleach-fixing process can be carried out using a bath bleach-fix solution, or a monobath process can be carried out using a one-bath development, bleach-fixing solution that allows color development, bleaching and fixing to be carried out in one bath. You can also do it.

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 processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the photographic element and the development process is performed using an activator solution, or instead of the monobath process. The activator treatment, bleaching, and fixing treatments may be performed 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 coloring 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-fix process / Activator process - Bleach-fix process - Activator treatment process - bleaching process constant fixation treatment process In addition to these treatments, there is a method in which the developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again, and the method described in JP-A-58-15489 Processing may be performed using a developing method that increases the amount of dye produced, such as the various intensification treatments (amplification treatments) described above.

〔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 Silver halide grains were precipitated by a double jet method, physically ripened by a conventional method, desalted, and further chemically ripened by a gold sensitization method and a sulfur sensitization method to obtain 7 mol % of silver iodide.
A silver iodobromide emulsion containing . The average diameter of the silver halide grains contained in this emulsion was 0.7 μI. 0.60 mol of silver halide and 880 g of gelatin binder are contained in 1 kg of this emulsion.

Ikg of this emulsion was weighed into a pot and heated to 40°C to dissolve it. Then, predetermined amounts of methanol solutions of a combination of sensitizing dyes according to the present invention and a single sensitizing dye for comparison were added and mixed and stirred.

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

20+e of 1.0% by weight aqueous solution of 7-tetrazaindene
Add ! Cellulose triacetate was added to the finished emulsion of m-, which was stirred by adding 1Od of a 1% aqueous solution of hydroxy-3.5-dichlorotriazine sodium salt and 1OmN of a 1.0% aqueous solution of dodecylbenzenesulfonic acid sodium salt. Dry film thickness on film base is 6
A sample of the photosensitive material was obtained by coating and drying so as to give a thickness of .mu.m.

This sample was cut into strips.

One is to use a sensitometer with a light source with a color temperature of 5400', attach a blue filter to the light source, and perform light wedge exposure.
Light wedge exposure was performed using a yellow filter as 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 for determining the sensitivity was the fog +0.20 point.

Developer composition Metol 2g anhydrous sodium sulfite 40g hydroquinone
4g sodium carbonate/l hydrate 2a
g Potassium bromide Add 1g water to make 1e.

The results obtained are shown in Tables 1-4. Note that the sensitivity is a relative value based on 100 as the respective sensitivities when a sample strip of Test) No. to which only the sensitizing color of general formula (I) or (II) was added was exposed to blue light and negative blue light.

As is clear from Tables 1 to 4, the combination of dyes of the present invention provides a remarkable supersensitizing effect both in blue exposure and in minus blue exposure.

Example 2 A silver iodobromide emulsion containing 5 mol% of silver iodide was chemically ripened by a conventional method to obtain an average grain size of 0.9 μm and a silver content of 0.6.
Emulsions of 0 mol/Kg emulsion and gelatin 70 g/Kg emulsion were obtained. Ikg of this emulsion was heated to 40°C, and 480g of an emulsion of cyan coupler A shown below was added. The emulsion of coupler A is prepared by adding and dissolving 300 mQ of ethyl acetate and 100a+12 dibutyl phthalate to 100g of coupler A.
Sodium dodecylbenzenesulfonate was added and emulsified and dispersed in 1 kg of a 10% aqueous gelatin solution using a homogenizer.

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-1,3,3a,7-
Add 20ml of a 1.0% aqueous solution of tetrazaindene, add 20ml of a 1% aqueous solution of l-hydroxy-3,5-dichlorotriazine sodium salt, and add 1.0ml of a 1% aqueous solution of dodecylbenzenesulfonic acid sodium salt. 10ml of 0% by weight aqueous solution was added and stirred. This completed emulsion was coated on a cellulose triacetate film base at a coated silver amount of 6/m'' and dried to obtain a sample.The film sample was developed according to the following recipe without exposure, bleached, After fixing, the density of the cyan image that was dried and developed was measured (Fo).

After coating, the sample was stored at 45° C. and 75% RH for two weeks and subjected to the same phenomenon treatment without exposure, and the density of the obtained cyan image was measured (Ft).

Table 5 shows the values of F+-Fo.

Coupler A ;) Js Development processing method 1 Color development 3 minutes 15 seconds (38℃) 2 Drifting
White 6 minutes 30 seconds 3 Water i5! 3 minutes 15 seconds 4 Fixing 6 minutes 30 seconds 5 Washing 3 minutes 15 seconds 6 Stable 3
The composition of the processing liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate
30.0g potassium bromide 1.
4g Hydroxylamine sulfate 2.484-(N
-Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5 g Water was added to make lσ.

Bleach solution Ammonium bromide 160.0 g Aqueous ammonia (28%) 25.0 m (ethylenediamine-tetraacetic acid sodium iron salt 130, Og Glacial acetic acid 14.0 mff Add water to make 1Q.

Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (7
0%) 175.0m12 Sodium bisulfite
Add 4.0g water to make 1Q.

Stabilizing liquid formalin 8ml12 Add water to 1
12.

Table 5 As is clear from Table 5, the combination of dyes of the present invention can provide photographic elements that exhibit less increase in fog when stored under high temperature and high humidity conditions.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent attorney Nobuo Sakaguchi Showa procedure amendment (method) September 26, 1985 Patent application No. 123699, filed in 1985 2 Name of the invention Photographic element 3 Person making the amendment Relationship to the case Applicant Name (127) Konishiroku Photo Industry Co., Ltd. 4 Agent 160 Address 5th Floor, 2nd Building, 7-10-11 Nishi-Shinjuku, Shinjuku-ku, Tokyo Date of Amendment Order 1985 August 27th 6 Number of inventions increased by amendment 7 Specification subject to amendment (full text)

Claims (1)

[Scope of Claims] A photographic element having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains a sensitizing dye represented by the following general formula [I] or [II]. and at least one sensitizing dye represented by formula [III] or [IV] in combination. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 are (i) each a hydrogen atom or an optionally substituted monovalent group, and at least one is an optionally substituted alkyl group or aryl group. (ii) is a group of atoms that together complete a ring fused to a ring containing a tellurium atom and a nitrogen atom, and R, R_3, and R_4 each independently represent an optionally substituted hydrocarbon group; show. R_3 is L_1
may be used to complete a 5- to 6-membered fused heterocycle. E represents an acidic nucleus, L_1 and L_2 each represent a methine bond that may be independently substituted, and n is 0, 1 or 2.
, and Q represents a group necessary to form a nitrogen-containing 5-membered ring which may be further fused. X represents an oxygen atom or a sulfur atom, and R_5 and R_6 are both hydrogen atoms or together represent an atomic group necessary to complete an aromatic fused ring.