JPS61272733A - Photographic element - Google Patents

Abstract

PURPOSE:To obtain a photographic element having photographic characteristics stable against heat and temp. by forming at least one silver halide emulsion layer on a support and incorporating a 5-membered ring having Te and N in the same ring or its salt in the element. CONSTITUTION:At least one silver halide emulsion layer is formed on the support to form the photographic element and it contains one of the compounds represented by formulae [I], [II], and [III] in which Y<-> is a counter ion, (p) is a positive integer for balancing ion charges, G10, G20, and G40 are each an atomic group for completing an aromatic nucleus to be fused, G11, G21, and G41 are each an atomic group for completing a hetero nucleus to be fused, R1 and R6 are H or an optionally substd. hydrocarbon group, and R3 is an optionally substd. hydrocarbon group. When the compd. is used as a fog inhibitor, it is preferred to add it to at least one of the constituent layers of a photosensitive material, preferably, to the silver halide emulsion layer generally in an amt. of 1X10<-6>-1X10<-3>mol per mol of silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to photographic elements, and more particularly to silver halide photographic elements containing a five-membered ring compound containing tellurium and nitrogen in the same ring, or a salt thereof. Regarding.

[Conventional technology]

Five-membered ring compounds containing oxygen, oxygen group elements such as selenium, and nitrogen in the same ring or their salts (chalcogenazoles) are used as sensitizing dyes, antifoggants, etc. in the field of silver halide photography. It has been widely used.

For example, photographic compounds having a structure in which two rings are fused to a chalcogenazole ring, a chalcogenazoline ring, etc. are disclosed in JP-A-47-9678, JP-A-59-102230, British Patent No. 587,434, and US Pat. 282,93
It is stated in No. 2.

However, the above-mentioned compounds have drawbacks such as a decrease in sensitivity and the occurrence of fogging due to the effects of heat and humidity during storage over time.

[Purpose of the invention]

A first object of the present invention is to obtain a photographic element which exhibits stable photographic properties against heat and humidity, and a second object is to obtain a photographic element with high sensitivity.

[Structure of the invention]

In order to overcome the drawbacks of the prior art, the present inventors have conducted various studies, and as a result, the object of the present invention was to provide at least one silver halide emulsion layer on a support and a layer of the following general formula [ 1]
, (II) or [1111], and led to the present invention.

General formula (1) General formula [■] General formula ([[[) In the formula, Y- represents a counter ion, p represents O or a positive integer for matching the ion charges, %GI@, G,. and G4° each represent an atomic group that completes the fused aromatic nucleus, GII, GII, and G41 each represent an atomic group that completes the fused heterocycle, and R1 and R3 each represent a hydrogen atom or a hydrocarbon that may be substituted. R1 represents an optionally substituted hydrocarbon moiety.

Hereinafter, the compounds of general formulas [I] to (II) will be explained in more detail.

G1゜, G,. Upper and G4゜ are respectively fused aromatic nuclei (
CII%G II and G41 each represent an atomic group that completes a fused heterocycle (such as 1,2-ethylene and 1,3-propylene), Y- represents a counter ion, p represents 0 or a positive integer selected to balance the ionic charge, R1 and R1 are each a hydrogen atom or a hydrocarbon moiety that may have a substituent (e.g. an alkyl and aryl), and R6 represents a hydrocarbon moiety that may have a substituent (for example, alkylidene).

In the general formulas CI) to (III) and the following formulas, G
- completed by tl, GII or G41, R
In addition to I, R*, and R1, further substituents (for example, alkyl groups such as methyl) can be introduced.

In general formulas (13, [''], and (If) and the following formulas, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an alkyl group, an aryl group, an alkylthio group, a cycloalkyl group, a carbamoyl group, an alkoxycarbonyl group) It is possible to introduce substituents such as

As an embodiment of the general formula (II), R2 can form a merocyanine dye represented by the following general formula (IV).

G in the formula. represents the atomic group that completes the fused aromatic nucleus, and C
at represents an atomic group that completes the fused heterocycle, E represents an acidic nucleus, L 1% L @ and RI each independently represent a methine bond, and B represents 0 or l.

A preferred compound of general formula (IV) is represented by general formula (V), where GIO1Gt+, E and n have the same meanings as in general formula [■]. The acidic nucleus E can take the form of any conventional merocyanine acidic nucleus. Typically, E consists of a methylene moiety attached, either directly or via a methine linkage, to a carbonyl, sulfo or cyano group at one resonance extreme.

Unlike the nucleus of cyanine dyes, the acidic nucleus E need not be a heterocycle, or even a ring.

Preferred form (where E can be represented by the following formula
: where l represents 0 or l, D is a cyano, sulfo or carbonyl group, and D' is methine-substituted etc., which in one form together with D represents carbon, nitrogen, oxygen and A 5- or 6-membered heterocyclic ring containing ring atoms selected from the group consisting of sulfur can be completed.

When E is an acyclic group, i.e. when D and D' are independent groups, E is selected from among groups such as malononitrile, alkylsulfonylacetonitrile, cyanomethyl benzofuranyl ketone or cyanomethyl phenyl ketone. You can choose. In the preferred ring form of E, D and D' together complete the following nucleus:
2-pyrazolin-5-one, vilazoliden-3,5-dione, imidacillin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazoline-4
-one, 2-oxazolin-5-one, 2-thioxazolidine-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2゜4-one dione, rhodanine, thiosilidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophene-3-1,1-dioxide, indoline-
2-one, indolin-3-one, indacillin-3-
2-oxoindasilinium, 3-oxoindasilinium, 5,7-thioxo6,7-cyhydrothiazolo(3,2-a)pyrimidine, cyclohexane-1,
3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbital acid, 2-thiobarbital acid, chroman-2,4-dione,
Indacilin-2-one or pyrido(1,2-a)pyrimidine-1,3-dione core. As substituents for this nucleus, common substituents for the ring can be considered.

The following general formula []] can form a cyanine dye represented by the following general formula [■] by Ro as an embodiment thereof.

General formula [■] In the formula, G4゜ represents an atomic group that completes the fused aromatic nucleus,
G41 represents an atomic group that completes the fused heterocycle, R8 represents an alkyl group, and L, SL! , L, and each represent a methine group, n represents 0.1 or 2, m represents 0 or l, and Q represents an atomic group that completes the nucleus of the heterocycle of the basic azolium salt or azinylidene. , Y- represents a counter anion, and p represents 0 or a positive integer to balance the ionic charges.

As is clear from the above formula, this cyanine dye is a type of quaternized tellurium azolium salt of formula (III), although the structure of the substituent R1 at the 2-position is complicated.

The tellurium azolium nucleus has already been described above. Although this nucleus could be characterized as a tellurium azolium nucleus or a chilua zolinidene nucleus, for convenience we will use the former nuclear designation, but for consistency we will refer to the remaining nuclei as aprinylidene or azinylidene nuclei.

In general, any conventional aprinylidene or azinylidene nucleus satisfying the formula [■] may be used in combination with the tellurium azolium nucleus; it is specifically contemplated that Q can be selected from: benzotelluriazolinylidene, naphtho. Tellurium azolinylidene, 2- or 4-pyridylidene, indacylylidene, 2- or 4
-quinolinylidene, l- or 3-indacylylidene,
Penzoquinolinylidene, thiazoloquinolinylidene, imidazoquinolinylidene, 3H-intolylidene, IH or 3H-benzintolylidene, oxazolinylidene,
Oxazolidinylidene, penzoxazolinylidene, naphthooxazolinylidene, oxadiazolinylidene, thiazolidinylidene, phenanthrothiazolinylidene, acenaphthothiazolinylidene, thiazolinylidene, penzothiazolinylidene, naphtho Thiazolinylidene, tetrahydropenzothiazolinylidene, dihydronaphthothiazolinylidene, thiazoxazolinylidene, selenazolidinylidene, selenium azolinylidene, penzoselen azolinylidene, naphthoselen azolinylidene, selenium adiazolinylidene, bila, zolylidene, indacylylidene,
Cores of imidazolidinylidene, penzimidazolinylidene, naphthoimidazolinylidene, diazolinylidene, tetrazolinylidene, and imidazoquinoxalinylidene.

This nucleus can be substituted in any conventional manner consistent with formula [■].

In a particularly preferred form, the cyanine dye of the present invention satisfying formula [■] is represented by the following general formula [■].

General formula [■] In the formula, G4°, G41, R8, n, Y- and p represent the same meanings as in the above general formula [■].

Q is a group of atoms that completes the basic apurinylidene or azinylidene nucleus, which may include a benzo or naphtho ring moiety.

In another preferred form, the cyanine dye used in the photographic elements of the invention can be represented by the general formula (IX) below.

General formula [) In the formula, G4゜ represents an atomic group that completes an aromatic group, and G41
represents an atomic group that completes the fused heterocycle, R1 represents an alkyl group, Ll, Ll, LslLa, R6 and R each independently represent a methyl group, n represents 0°1 or 2, and Otori represents 0 or l, Q represents an atomic group that completes the apriedene or azinylidene nucleus in the basic heterocyclic formula, and Y
- represents a counter anion, and p represents 0 or a positive integer for combining ionic charges.

Except for the form of the azolinylidene or azinylidene ring completed by Q, the various components of formula (IX) can be selected in the same way as described above for formula [■], so that
I won't explain it again. In its optimal form, Q in formula (IX)
is selected from among the cores of pyrrolilidene, intrilidene, carboazolilidene, benzintolylidene, pyrazolylidene, indasylylidene, and virolopyridinylidene. Again, the usual ring substituents corresponding to the formula ■] are contemplated.

Next, the above general formulas (1) and (II) used in the present invention
, (■), (IV), (V), (■), [■] and (IX) are listed below.
The compounds used in the present invention are not limited to these.

[Exemplary compounds of general formula m]

CI! .

[Exemplary compounds of general formula (n)]

[Exemplary compounds of general formula (I [[)] '(?); Ku) 'Anio/, PA71 [Exemplary compounds of general formula (1'/) and [v]] [General formula [■] and Exemplary compounds of [■]] (■-ta) [Exemplary compounds of general formula ([)] Compounds represented by the above general formula (III) used in the present invention are disclosed in JP-A-47-9678 and JP-A-60-784.
No. 45, UK No. 587.434, Zh,
0bsh, Khim, 32.857-9 (196
It can be synthesized according to the method described in 2) etc.

Also, the above general formula [■], (ff), (V), [■], [
The compounds used in the present invention represented by [■] and ([) are described, for example, in Journal of the American Chemical Society, Vol. 67, 1875-1889.
(194SXJ, Am, Ches, Soc,, 6 7
．． 1875-1889<1945)) or F.M. Herma, Cyanine, Dice and Related Compounds (1964 Inter Science.
Those skilled in the art can easily synthesize it by referring to the method described in Publishers, Inc.).

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

(Synthesis example) (1) 2.3-)limethylbenzotellazolium iodo salt (exemplified compound (I[-1)), 2-(3-hydroxybutyl)penzotellurazole 6
．． A solution of 1 g (2/100 mol) of pentachloroethane 60se was placed in a pressure tube. The system was cooled in a water bath and maintained at 0° C., and the inside of the system was purged with nitrogen, and 172 equivalents of trifluoromethanesulfonic anhydride was added dropwise and stirred under a nitrogen atmosphere. Subsequently, 1.6 g of pyridine was added, the tube was sealed tightly, the temperature was gradually returned to a normal temperature, and the mixture was further heated at 100°C.

The cooled leaching precipitate was collected by filtration, the crude product was dissolved in 25 ml of ethanol, 15 ml of ethanol in which 5 g of sodium iodide was dissolved was added, and the mixture was cooled and crystallized with stirring. The precipitate was collected by filtration and washed with acetone. Yield: 0.87 g Elemental analysis and nuclear magnetic resonance spectra were consistent with expectations.

(2) 5-(4-(l H-2,3-dihydropyrido
2゜1-b]penzotellazolyl]methylene-4-oxo-2-thioxo-1,3-4azolidin-3-yl acetic acid (exemplary compound ■-5) 4-acetanilide methylene-1,2,3 , 5.6 g of penzotellazolium iodo salt of 4-tetrahydropyrido (2,1-b) and 1.9 g of 3-carboxymethylrhodanine were dissolved in absolute ethanol ($ Om (l), triethylamine 2
g was added thereto, and the mixture was heated under reflux for 15 minutes.

Crystallization was performed by acidifying cold acetic acid, and the precipitate was collected by filtration and washed with ethanol.

Purification was performed by dissolving it in methanol containing triethylamine and crystallizing it under acidic acetic acid.

Yield 100g Melting point 300℃ or higher Absorption maximum wavelength in methanol solution 556na(3)bis-3,8-3
',10-trimethylenetelluracarbocyanine iodo salt (Exemplary Compound 1-6) 2.4 g of 3-trimethylenebenzotellazolium iodo salt and 1.5 g of orthoacetic acid ethyl ester were added to 30 liters of pyridine.

Triethylamine was added and the mixture was heated under reflux for 15 minutes to allow crystallization to occur.

The precipitate was collected by filtration and washed with ethanol to obtain 10 g of a crude product.

It was purified by repeated recrystallization from methanol.

Yield: 110.6g Melting point: 300°C or higher Maximum absorption wavelength in methanol: 627n When the compound of the present invention described above is used as an antifoggant, it is added to at least one layer, preferably a silver halide emulsion layer, of the constituent layers of a light-sensitive material. Ru.

The amount to be added is a value that should be changed as appropriate depending on the type of compound and the layer to which it is added, so it is difficult to define it unambiguously, but it is generally in the range of 10-" mol of LX to 1 mol of silver halide, and more The preferred range of addition amount is silver halide 1
3 moles of IXIG"6 to 1 x 10" per mole.

When the compound of the present invention is used as a sensitizing dye, tx to 'mol-5x t per mol of silver halide, respectively.
o-” moles, preferably IXIQ-’ moles to 2.5×
1O−3 mol, particularly preferably 4XlO−′ mol to 1×
It is contained in a silver halide photographic emulsion in a proportion of 10-3 moles.

The compounds used in the present invention can be added to the emulsion using methods well known in the art.

For example, these compounds can be directly dispersed in emulsions, or dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, or mixtures thereof, or diluted with water; Alternatively, the compound can be dissolved in water and added to the emulsion in the form of a solution, and the compound can be added to the emulsion at any time during the emulsion manufacturing process.
Preferably, during or after chemical ripening.

The dyes described above can be applied in any application in which otherwise corresponding dyes containing other chalcogen atoms are used. The dyes used as compounds of this invention are incorporated into silver halide photographic elements in a preferred application. The location and concentration of the dye depends on the photographically useful function sought to be achieved. Silver halide emulsion layer 1
Or when it imagewise absorbs actinic radiation that passes through 2 or more, thereby reducing the scattered radiation, the dye! or 2
It can be located behind the above silver halide emulsion layer. In other words, the dye can be used as an antihalation dye.

The compounds of the invention can be incorporated into interlayers or overcoats to function as filter dyes. When the compounds of the invention are used as dyes, they are incorporated directly into the silver halide emulsion. Dyes can increase photographic sharpness by blocking and absorbing actinic radiation that would otherwise be reflected between particles. In other words,
The compounds of the invention can take the form of interparticulate sorbents.

A highly preferred utility of the compounds of this invention as dyes is to increase the wavelength of the spectral response of silver halide grains to exposing radiation.

In such applications, the dye is typically adsorbed to the surface of the silver halide grains. Additionally, the dye can also function to reduce the sensitivity of the silver halide grains in the spectral region of inherent or native sensitivity. This can be a desirable feature in addition to spectral sensitization, or increases the difference between the sensitized and intrinsic sensitivity of the emulsion, as is desirable for minus-blue recording emulsions in color photography. This can be a desirable feature in combination with spectral sensitization. It is specifically contemplated that the dyes as compounds of this invention may be used as spectral sensitizers in both surface and internal latent image-forming emulsions.

The latter emulsion offers the advantage of allowing a more favorable dye concentration desensitization relationship, ie more dye is required to reach the desensitization level. When the compound dyes of this invention are used in combination with surface-fogged silver halide emulsions used in forming direct positive images, their substituents can be selected to increase electron capture. As mentioned above, ultraviolet, blue, green, red and infrared absorbing dyes according to the invention are contemplated. However, dyes with absorption maxima at wavelengths of 500 nm and longer are particularly advantageous.

The compounds of the invention need not necessarily be in the form of dyes. Numerous chalcogenazolium antifoggants and stabilizers are known in the art, and the compounds of this invention can be used as substitutes while still achieving the benefits of this invention.

Hydrazine and hydrazine derivatives (e.g. hydrazide and hydrazone alkyl) A nucleating agent in which the tellurium-containing heterocycle of the present invention is bonded directly or through an intervening bonding group to the nucleating moiety may also be used on the surface of internal latent image-forming silver halide grains. can be adsorbed to.

Additionally, hydrazines and their hydrazide derivatives are useful in surface latent image forming negative working emulsions to increase contrast to very high levels.

The photographic element of the present invention need only have at least one silver halide emulsion layer on a support, which may include cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, Examples include films made of semi-synthetic or synthetic polymers such as polyamide, flexible supports provided with reflective layers on these films, glass, metals, ceramics, and the like.

The silver halide emulsions (hereinafter simply referred to as silver halide emulsions) used in the photographic elements of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any conventional silver halide emulsions such as silver halide emulsions can be used.

Silver halide grains that may be used in the silver halide emulsion may be those 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 considering the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pus pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. When producing a silver halide emulsion, a silver halide solvent may 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 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
It can be carried out based on the method described in Losure) No. 17843.

Silver halide used in silver halide emulsions.

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

Further, 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 grain.

Furthermore, the silver halide grains used in silver halide emulsions may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or irregular crystal shapes such as spherical or plate shapes. It may be something that has.

In these particles, the (l G O) plane and the (111'
) Any surface ratio 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, particularly preferably 3 μm or less.

Silver halide emulsions having any grain size distribution may be used. 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 gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. 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. , also good. The silver halide emulsion of the present invention may be used during chemical ripening, at the end of chemical ripening, and for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of photographic elements, or to maintain stable photographic performance. Compounds known in the photographic industry as antifoggants or stabilizers may be added/or after the end of chemical ripening and before coating the silver halide emulsion. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but
Hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and synthetic woody polymeric substances such as single or copolymers can 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 of a photographic element using a silver halide emulsion and other hydrophilic colloid layers can be formed by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. Ii! It can be membraned.

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.

Plasticizers can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a photographic element employing a silver halide emulsion for the purpose of increasing flexibility.

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

The emulsion layer of the photographic element of the present invention contains pigments 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 8. 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 pallast group in the molecule, which makes the coupler non-diffusive and has a carbon number of 8 or more. 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 can be used as development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents, and chemical sensitizers by coupling with oxidized forms of developing agents. , spectral sensitizers, and desensitizers that release photographically distinct fragments 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 if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

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 that do not need to be adsorbed on the silver halide crystal surface, colored couplers, DIR Katsura r, DIR
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. By dissolving it in combination with an organic solvent and using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, a stirrer, homogenizer, colloid mill, flow jet mixer,
It may be emulsified and dispersed using a dispersion means such as an ultrasonic device, and then 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 fog preventive agents, ultraviolet absorbers, optical brighteners, etc. have 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 layer and between the l or 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 extraction antifogging 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. To prevent degradation of magenta dye-forming couplers etc. by formalin during storage of the photographic element, formalin scavengers can be used to add dyes and ultraviolet absorbers to the hydrophilic colloid layer in J-'aQ photographic elements. 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 (R'esearch D.
isaloaure) No. 17643 XXIrXB-D
The development retardant is a compound described in Section xxI, Section E of No. 1784.3. 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 anti-irradiation 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 may 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.

Also, ζ lubricant can be added to reduce sliding friction.
An antistatic agent can be added for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used as a hydrophilic colloid other than the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. It may be used in 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 after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., as required. , may be coated through one or more subbing layers to improve hardness, antihalation properties, 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.
re) It can be applied by the method described in No. 176H, 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 the above 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 the present 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 raw photographic element, a black and white development process is performed after exposure to form a silver image, and the dye is bleached using this as a bleaching catalyst.

Each processing step is usually carried out by immersing the photographic element in a processing solution, but the processing can also be carried out by other methods, such as a spray method in which the processing solution is supplied in the form of a spray, or by contacting it with a carrier impregnated with a processing group. Even if you use a web method, a method of viscous development processing, etc.

The black and white development process includes, for example, a development process, a fixing process, and a water washing process. Alternatively, the developing agent or its precursor may be incorporated into the photographic element and the developing process may be 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-fixing solution, or a monopass processing process can be carried out using a one-bath developing 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 carried out using an activator solution, or instead of the monopass 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 processing process - Water washing processing process - Supplementary color development processing process - Stop processing process - Bleaching processing process Constant fixation processing process / Monopass processing process / Activator processing process - Bleach-fixing processing process / Activator Asahi process - Bleach Asahi process Constant fixation treatment process In addition to these treatments, there is a method in which developed silver produced by color development is bleached with halogenesidine and then color development is performed again, and various intensification treatments ( It may be processed using a developing method that increases the amount of produced dye, such as amplifier processing).

〔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 chemically ripened by a gold sensitization method and a sulfur sensitization method. A silver iodobromide emulsion containing mol % was obtained. The average diameter of the silver halide grains contained in this emulsion was 0.6 μI. 0.60 mol of silver halide and 880 g of gelatin pine and goo are contained in 1 kg of this emulsion. Furthermore, 20a+12, a 1.0% by weight aqueous solution of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, was added for stabilization.

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 compound according to the present invention and the comparative compound were added and mixed and stirred. Coating aids and hardeners are added to each of these emulsions, and the finished emulsions are coated on a cellulose triacetate film base to a dry film thickness of 5 μm and a silver content of 50 mg/d@”, and dried to form a photosensitive material. A sample was obtained. A portion of this sample was left in a room adjusted to 50° C. and 80% relative humidity for 2 days.

In this way, the sample immediately after coating and the sample treated under the above-mentioned high temperature and high humidity conditions were examined using a tungsten light source.
A photosensitive material was used for exposure to light. After exposure, development was carried out at 20° C. for 3 minutes using a developer having the composition shown below, followed by stopping and fixing, followed by washing with water and drying to obtain a strip with a black and white image.

The density of each developed sample was measured using an optical densitometer to measure sensitivity and fog. The optical density reference point for determining the sensitivity was the fog +0.2 point.

Developer composition Metol 2g Anhydrous sodium sulfite 40g Hydroquinone 4g Sodium carbonate/l hydrate
Add 28g potassium bromide and 1g water to make tQ.

The results obtained are shown in Table 1. In addition, the sensitivity is test NO.
, 8 (comparative compound 1) Sensitivity of sample immediately after application (So)
It is a relative value with 100.

Comparative Compound - (1) Comparative Compound - (2) Comparative Compound - (3) As is clear from Table 1, the compound of the present invention exhibits better performance under high temperature and high humidity than the comparative compound. It can be seen that the increase in fog is small and the decrease in sensitivity is small, which is excellent.

In addition, the same tests as above were conducted on the compounds of general formulas (1) and (II), and both were found to be excellent, with a small increase in fog and a small decrease in sensitivity under high temperature and high humidity conditions. .

Example 2 A Tenshin silver emulsion containing 7 mol % of silver iodide was chemically ripened by a conventional method to obtain an average grain size of 1.0 μ■ and a silver amount of 0.6.
Emulsions of 0 mol/kg emulsion and gelatin 70 g/kg emulsion were obtained. 1 kg of this emulsion was heated to 40°C, and 500 g of an emulsion of cyan coupler D shown below was added thereto. The emulsion of coupler D was mixed with 100 g of coupler D and 300 ml of ethyl acetate.
2 and dibutyl phthalate 1001 were added and dissolved, sodium dodecylbenzenesulfonate was added, and the resulting mixture was emulsified and dispersed in 1 kg of a 10% gelatin/aqueous solution using a homogenizer. Predetermined amounts of the compound according to the present invention and a comparative compound were added to this emulsion, and the mixture was mixed and stirred.

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

20 m of a 1.0 wt% aqueous solution of tetrazaindene of 7-
e to stabilize, further coating aids, and i!
A coating agent was added and the finished emulsion was coated on a cellulose triacetate film base to achieve a silver content of 50 mg/da.
The sample was coated and dried to obtain a sample. This film sample was subjected to light wedge exposure using a sensitometer with a light source having a color temperature of 5400' and a red filter attached to the light source. After exposure, development was carried out according to the following formulation, and after bleaching and fixing, the density of the cyan color *a developed by drying was measured, and the sensitivity and fog were measured. The optical density reference point for determining the sensitivity was the fog +0.20 point.

After coating, the sample was left for 3 weeks in a room conditioned at 40°C and 651% relative humidity.The same exposure and development process as above was carried out, and the density of the cyan dye image was measured for the obtained sample. The fog was measured.

The results obtained are shown in Table 2. In addition, the sensitivity is Tess) NO
, 1B (comparative dye 4), the sensitivity of the sample (So
) is expressed as a relative value with 100.

Coupler D Development processing prescription ■, coupler image 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 for 3 minutes and 15 seconds The composition of the treatment 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 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate
Add 4.5g water to make 1e.

Bleach liquid ammonium chloride 160.0g ammonia water (28%) 26. Omt Ethylenediamine-Tetraacetic acid sodium iron salt 13Q, og Glacial acetic acid L4.0mN Add water to make IQ.

Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) L75.0ml 11 Sodium bisulfite 4.6g Add water to make 1e.

Add stabilizer formalin 8mN water to make ti2.

[Margin below]

Comparative Compound - (4) Comparative Compound - (5) Comparative Compound - (6) As is clear from Table 2, the compound of the present invention is more stable at high temperatures than the comparative compound. It can be seen that the increase in fog and the decrease in sensitivity under high humidity conditions are small, indicating that the film is excellent.

Margin Example 3 The following constituent layers were coated on polyethylene coated paper from the font side to the head to prepare a sample of a multilayer color photosensitive material.

First layer...Blue-sensitive emulsion layer Blue-sensitive silver chlorobromide emulsion layer (containing 90 mol% silver bromide) contains the following yellow coupler dissolved and dispersed in 400 g of gelatin and dibutyl phthalate per mol of silver halide. contains 0.2 mol per mol of silver halide, and the amount of silver is 400
mg/m''.

Second layer: Intermediate layer This is a gelatin layer containing 2.5-di-t-octylhydroquinone and is coated to a gelatin weight of 1.5 g/+s''.

Third layer...green-sensitive emulsion layer The green-sensitive silver chlorobromide emulsion layer (containing 80 mol% silver bromo) is
500 g of gelatin per mol of silver halide and 0.2 mol of the following magenta coupler dissolved and dispersed in dibutyl phthalate per mol of silver halide, 2.5-di-
0.05 mol of t-octylhydroquinone per mol of magenta coupler, 1.4-di-octyloxy-2,
Contains 0.3 mol of 5-di-amylbenzene per mol of magenta coupler, and has a silver content of 500 B.
/m”.

4th layer: 2,5-di-t dissolved and dispersed in intermediate layer dibutyl phthalate
-30 B/ta” of octylhydroquinone and 0.7 g of 2-(benzotriazol-2-yl)-4,6-di-t-butylphenol as a UV absorber.
/e A gelatin layer containing 1.
The layer was coated to give a weight of 6 g/m''.

Fifth layer: Red-sensitive emulsion layer A red-sensitive silver chlorobromide emulsion layer ( Silver bromide containing 80 mol %) contains 500 g of gelatin per mol of silver halide and 0.2 mol of the following cyan coupler dissolved and dispersed in dibutyl phthalate per mol of silver halide, and the amount of silver is 500 g.
This is a layer coated to give a concentration of 100 mg/a”.

6th layer: Intermediate layer A gelatin layer containing 0.4 g/s" of the above-mentioned ultraviolet absorber dissolved and dispersed in dibutyl phthalate. A layer coated with gelatin at a rate of 1.5 g/w+". be.

Seventh layer: Protective layer A gelatin layer coated at a thickness of 1.5 g/m''.

(yellow coupler) Cσ (magenta coupler) Q (cyan coupler) The silver halide emulsions in each of the above photosensitive layers are
-7772, chemically sensitized using sodium thiosulfate pentahydrate, and 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene was added, as well as a hardener and coating aid.

After coating, a sample was prepared and left in a room adjusted to 40° C. and 65% relative humidity for 3 weeks.

These samples were subjected to light wedge exposure using a photosensitive layer having a light source with a color temperature of 5400' and a red filter attached to the light source. After exposure, the following processing was performed, the density of the colored dye image was measured, and the sensitivity and fog were measured. The optical density standard for determining the sensitivity was a point of Gaburi +0.20.

The results obtained are shown in Table 3. In addition, the sensitivity is test No.
, 24 (comparative dye 7) sensitivity (Jo) of the sample immediately after application
is expressed as a relative value with 1θ0.

Standard treatment process 1m (processing temperature and processing time) [1] Color development 38℃ 3 minutes 30 seconds [2] Bleaching person
33℃ 1 minute 30 seconds [3] Washing treatment 25-30℃
3 minutes [4] Drying 75-80℃ Approximately 2 minutes Processing liquid composition (color development tank liquid) Benzyl alcohol 15ml Ethylene diglycol 15ml Q Potassium sulfite
2.08 potassium bromide
0.7g potassium chloride
0.2g potassium carbonate
30.0g hydroxylamine sulfate 3,
0g polyphosphoric acid (TPPS) 2.5
g3-Methyl-4-amino-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (4,4'-diaminostilbenzsulfoninic acid derivative) 1 g potassium hydroxide
2.0. Add P water to bring the pH to 112.
Adjust to 1o, 20.

(Bleach-fixing tank solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (7
0% solution) l 00 ra (1 ammonium sulfite (
Adjust the pH to 7.1 with 27.5 mff of potassium carbonate or glacial acetic acid, add water and bring the total volume to IQ.
shall be.

Comparative Compound (7) Comparative Compound (8) As is clear from Table 3, the compound of the present invention exhibits a smaller increase in fog under high temperature and high humidity than the comparative compound, and also exhibits a decrease in sensitivity. It's small and you can tell it's great.

Patent applicant: Roku Konishi Photo Industry Co., Ltd. Agent: Nobu Sakaguchi, patent attorney (Sho procedure amendment written form) September 26, 1985

Claims (1)

[Scope of Claims] A photographic element characterized by having at least one silver halide emulsion layer on a support and a compound represented by the following general formula [I], [II] or [III]. 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.▼ [In the formula, Y ^- represents a counter ion, p represents 0 or a positive integer to match the ion charge, G_1_0, G
_1_0 and G_4_0 represent the atomic groups that complete the fused aromatic nucleus, respectively, and G_1_1, G_2_1 and G_4
_1 represents the atomic group that completes the fused heterocycle, R
_1 and R_3 each represent a hydrogen atom or a hydrocarbon moiety that may be substituted, and R_6 represents a hydrocarbon moiety that may be substituted. ]