JPS61277942A - Photographic element - Google Patents

Abstract

PURPOSE:To obtain a photographic element high in sensitivity, prevented from pressure desensitization and pressure fogging, that is, good in pressure characteristics, and capable of forming a high-quality image by incorporating a compound having a 5-membered hetero ring contg. N=C-Te as a ring constituent in the photographic element. CONSTITUTION:A silver halide emulsion layer contains flat grains each having, preferably, a diameter of the circumscibed circle of the flat crystal of 1.0-6.0mum and an aspect ratio, that is, a ratio of the diameter of the thickness, that is, the distance between the 2 parallel faces of the crystal, of >=3, preferably, 8-20. The photographic element also contains the compound having a 5-mem bered hetero ring contg. N=C-Te as ring constituent, and this compound is embodies by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Objects of the Invention (Field of Industrial Application) This invention relates to photographic elements, and more particularly to improving the pressure characteristics of photographic elements having tabular silver halide grains.

(Prior art) Silver halide emulsions having tabular silver halide grains are known as a technology for achieving higher sensitivity and higher image quality in silver halide photographic materials. It is also known to be applied to photographic materials.

For example, JP-A-58-113930 discloses a multilayer color photographic material having a dye-forming unit having a two-layer structure including an emulsion layer having tabular grains with an aspect ratio of 8:1 or more in the upper layer. No. 58-113934 discloses a multilayer color photographic material using silver iodobromide or silver bromide emulsions with tabular grains having an aspect ratio of 8=1 or more in the green-sensitive layer and the red-sensitive layer, and JP-A No. 58-1139. No. 113927 discloses a multilayer color photographic material containing plate-like grains in which the central region has a lower silver iodide content than the annular region and an aspect ratio of 8:1 or more. discloses a silver halide photographic material containing tabular silver halide grains having an aspect ratio of 3=1 or more and a specific sensitizing dye and which can be applied to color applications.

However, the photographic properties of photographic elements having silver halide emulsions containing tabular silver halide grains such as those described above are susceptible to various stresses applied during handling of the material, and the effects of conventional pressures are reduced. as a means of incorporating plasticizers into the photographic element;
A method of reducing the silver halide/gelatin ratio is known, but sensitivity to pressure decreases (pressure desensitization).
, or it becomes easy to fog due to pressure (pressure fog in January,
At present, there are no satisfactory measures. Therefore, there is a need for a photographic element with high sensitivity, high image quality, and no pressure problems or pressure capri, that is, good pressure characteristics.

OBJECTS OF THE INVENTION It is an object of the invention to provide a photographic element with high sensitivity, high image quality, and improved pressure characteristics.

(2) Structure of the invention - The purpose of the present invention Φ is to have an aspect ratio of 3=1 or more, and mainly (111
) A photographic element having a silver halide emulsion layer containing tabular grains consisting of planes, the photographic element further comprising a five-membered heterocyclic nucleus having nitrogen atoms and tellurium atoms as layer constituent atoms, sandwiching a carbon atom therebetween. This was achieved by a photographic element characterized by containing a compound.

The photographic element of the present invention has an aspect ratio of 3:1 or more, and the tabular grains contained in the silver halide emulsion layer containing tabular grains mainly consisting of (111) planes have an aspect ratio (diameter/thickness ratio) is 3 or more, preferably the aspect ratio is 5 or more, particularly preferably 8 to 20
It is. The diameter here is the diameter of the circumscribed circle of the particle, preferably 0.5 to 10 μm, more preferably 1.0 to 6 μm.
It is 0 μm. Thickness is the distance between two parallel faces in a tabular crystal.

The silver halide composition of the tabular grains is a composition consisting essentially of silver iodobromide with a silver iodide content of 0.5 to 10 mol%, and the silver chloride content is less than 1 mol%. It is desirable that the composition distribution of silver iodide be uniform, but the composition may be different between the outer part of the grain and the inner part.An example of such an emulsion is disclosed in JP-A-58-113927. The disclosed tabular emulsion has a high silver iodide content in the outer part, and an emulsion having the opposite structure, that is, an emulsion in which the outer part has a low silver iodide content, is also preferably used. More preferred are emulsions whose outer portions have low iodine.

If the outer part has high iodide content, the silver iodide content in the center part is 0.
~5 mol % silver iodobromide, the silver iodide content in the outer part is at least 1 mol % higher than in the center, and the silver iodide content is 4 to 20 mol % is preferably used.

Such a silver halide emulsion is disclosed in JP-A-58-1139.
It was obtained by the method of Publication No. 27, and the particle structure was J, 1.
Goldstein and B.

"X-ray analysis in Williams rTEM/ATFM"
, scanning electron microscopy (
1977) No. 1 [P, 651].

In addition, tabular grains having a low iodide content in the outer part have a silver iodide content of 0 to 5 mol% in the outer part and 4 to 20 mol% in the central region. Such an emulsion, which is preferably silver bromide, can be produced by changing the composition of the halide solution added as described in JP-A-58-113927, but the nucleation part is controlled by changing the silver iodide content. It is preferable to keep it at 2 mol% or less. The halogen composition of such an emulsion can also be analyzed by the method described above. A tabular twinned grain consisting of (111) planes is one that has an external plane that is parallel to each other and one or more twinned planes that are parallel to that plane. ” Coronasha (1979) provides a detailed classification.

In addition, the tabular silver iodobromide grains have first and second opposing parallel major faces, a central region extending between the two major faces, and at least one lateral region extending between the two major faces. It is preferable that the particle has an outer region that is displaced in the direction (parallel to the main plane) and has an internal structure in which the iodide content in the central region is different from the iodide content in the extra-nuclear region. More preferred among these are grains having an internal structure in which the iodide content in the outer region is lower than the iodide content in the central region. Preferably, the composition distribution is such that the outer region surrounds the central region so as to form a ring in the lateral direction.

Note that the change in iodine content in the boundary layer between the central region and the outer region may have a sharp boundary surface, or may change continuously without necessarily having a clear boundary.

In the layer containing the tabular silver halide grains of the present invention, the tabular grains are present in a weight ratio of 4 to all silver halide grains in the layer.
It is preferably present in an amount of 0% or more, particularly 60% or more.

The tabular silver halide grains according to the present invention may be polydisperse or monodisperse, but monodisperse is more preferable.

Preferably, monodispersity is such that the variation coefficient of the particle size distribution (this particle size is defined as the diameter of the circumscribed circle of the particle as described above) is 25% or less.

As a method for preparing an emulsion consisting of monodisperse tabular grains, methods described in JP-A-51-39027, JP-A-54-118823 and JP-A-55-211143 can be used.

In addition, as a preferred method for obtaining an emulsion consisting of monodisperse tabular grains, the grains consisting of multiple twins are physically ripened in the presence of a silver halide solvent to form a seed population consisting of monodisperse spherical grains. A method can be used to create and then grow this. More preferably, a tetrazaindene compound is present during the growth of tabular grains to increase the proportion of tabular grains and to improve monodispersity.

When tabular grains are mixed with other silver halide grains, they are preferably used as a highly sensitive silver halide emulsion, and have the same color sensitivity and have two or more silver halide emulsion layers. In a silver halide multilayer photographic material, it is preferably used in a silver halide emulsion layer that requires higher sensitivity.

Emulsions containing tabular silver halide grains according to the present invention are disclosed in JP-A-52-153428 and JP-A-58-5542.
No. 6, No. 58-113928, No. 58-113927
It can also be produced using the method described in No. 1, etc., or with reference to this method.

The tabular grains of the present invention may be doped with various metal salts or metal complex salts at the time of silver halide precipitate formation, during grain growth, or after the completion of growth. For example, gold, platinum, palladium, iridium, rhodium, bismuth, Metal salts or complex salts such as cadmium, copper, etc. and combinations thereof can be applied. In addition, in the method for producing an emulsion containing the above-mentioned particles, the Tardel water washing method, dialysis method, or coagulation precipitation method, which is commonly used in general emulsions, can be appropriately used as a means for desalting.

Furthermore, the above silver halide emulsion may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers.
For example, stannous salts, polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzthiazole methyl chloride, etc., or, for example, ruthenium, rhodium, iridium. Chemical sensitization can be carried out by using water-soluble salt sensitizers such as ammonium chlorovaladate, potassium chloroaurate, and sodium chloroparadite alone or in combination as appropriate.

The compound such as the sensitizing dye according to the present invention is a compound having a 5-membered heterocyclic nucleus having a nitrogen atom and a tellurium atom as layer constituent atoms with a carbon atom in between. Various structures can be taken depending on the bonding state of , but representative examples include those having a tellurazole ring nucleus, a telluriazoline ring nucleus, a tellurium azolium ring nucleus, and a tellurium azolinium ring nucleus.

Among these, the following general formulas [1] to (IV
).

General formula (I) R.

General formula (II) R.

General formula (II) R+ R-tomi General formula ([V) R.

Ry (Y -)p In the formula, R8 and R 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, and , each is preferably a hydrogen atom or an optionally substituted alkyl group or an aryl group, and at least one is an optionally substituted alkyl group or an aryl group.

or (ii) A group of atoms that together complete a ring (preferably 5 to 6 members) fused to a ring containing tellurium and nitrogen, preferably an aromatic group fused directly to the ring containing tellurium and nitrogen. A group of atoms completing an aromatic ring fused to a ring or a non-aromatic ring fused to the tellurium- and nitrogen-containing ring.

Rs and R6 each represent a hydrogen atom or an optionally substituted hydrocarbon moiety, R4 represents a hydrogen atom, an optionally substituted hydrocarbon moiety, or an amino group, Rs represents an optionally substituted hydrocarbon moiety, R, represents a hydrogen atom or a quaternized substituent, Y- represents a counter ion, and p represents 0 or a positive integer for matching ionic charges.

R1 and R7 may cooperate with R2 to complete a 5- to 6-membered fused heterocycle.

R2 may join with R4 or R1 to complete a fused heterocycle (preferably 5-6ji).

R1 may cooperate with R7 to complete a fused heterocycle (preferably 5-6 membered).

Y- representing a counter ion includes a halogen atom (chloro, bromine, iodine, etc.) and a sulfonic acid (methanesulfonic acid).

Representative anions include trifluoromethanesulfonic acid and p-)luenesulfonic acid.

The ring completed by Ro and R2 is, for example, benzene, naphthalene, thiophene, benzothiophenefuran,
Aromatic 5- to 6-membered rings such as benzofuran and pyridine are representative.

These rings may be substituted. Examples of substituents include hydroxy, hydroxyalkyl groups (e.g., hydroxyethyl, hydroxypropyl, etc.), alkyl groups (e.g., methyl, ethyl, isopropyl, t-butyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, β-methoxyethoxy.

T-carboxypropyloxy and other groups), aryloxy (e.g. phenoxy, oki-chlorophenoxy and other groups), aryl groups (e.g. 11-)lyl, phenyl,
m-hydroxyphenyl, p-hydroxyphenyl, 2
-Hydroxynaphthyl, etc.), halogen atoms (e.g. chloro, fluorine, etc.).

bromine, etc.), trifluoromethyl group, amino group (e.g., dimethylamino group, diethylamino group, etc.), cycloalkyl group (e.g., cyclohexyl group), cyano group, carbamoyl group (e.g., carbamoyl, N,
Examples include N-dimethylcarbamoyl (N, N-diethylcarbamoyl, etc.), alkoxycarbonyl groups (eg, ethoxycarbonyl group), and alkylthio groups (eg, methylthio group).

Also, R7 and Rx, Rt and R1, R3 and Ra, Rx and R2
Examples of rings in which are bonded and fused with a tellurium-containing heterocycle include the following.

R1 is preferably an aryl group, an alkyl group, an alkenyl group, or an alkynyl group, each of which may be substituted, R4 is preferably an aliphatic hydrocarbon, which may be substituted, and RS is preferably an aliphatic hydrocarbon, which may be substituted. R1 is preferably an optionally substituted aliphatic hydrocarbon.

The above description of general formulas (1) to (rV) is the same for each general formula described below.

The tellurium azolium and derivatives tellurazole, telluriazoline, and tellurium azolinium compounds present in photographic elements can be applied to various known uses of the corresponding compounds in silver halide photography while still achieving the effects of the present invention. .

In a particularly contemplated photographically useful form, tellurium azolium compounds can be used as dyes containing at least one elementary nucleus composed of a tellurium azolium ring. Since the tellurium azolium ring preferably forms part of the chromophore, it is in the form of a tellurium azolium ring at one resonance extreme and rearranges to a tellurium azolylidene ring at the second resonance extreme.

In a particularly preferred form when used as a dye, at least one of the sensitizing dyes of the invention is a polymethine dye containing a tellurium azolium ring. Such dyes include cyanine and merocyanine dyes. The dye can contain two nuclei linked through a methine linkage, which is most commonly present. These dyes are sometimes simple (si+*
ple) cyanine or merocyanine, complex (
complex) distinguishes them from those containing three or more nuclei called cyanine or merocyanine dyes. In addition to the above, for use in photographic elements of the invention,
These polymethine dyes can take the form of hemicyanine, styryl, neomycin, azacyanine, and allopolarcyanine dyes. Such dyes are direct analogs of conventional dyes in these classes, the difference being the presence of a divalent tellurium atom in at least one chalcogen azolium nucleus instead of another divalent chalcogen. It is.

General formula (II) can form a merocyanine dye represented by the following general formula (V) by Rs.

In the R, I R formula, R+, Rz, and R1 have the same meanings as in the general formula [■], and the same ones are exemplified. Furthermore, R1 can be used in conjunction with LI to complete a 5- to 6-membered fused heterocycle. good.

E represents an acidic nucleus, Ll and L2 each represent a methine bond which may be substituted vertically, and n is 0.1 or 2.
represents.

Examples of fused heterocycles formed by R1 and R1 include the following.

The acidic nucleus E represented by E in the general formula (V) and the following formulas can take the form of any ordinary merocyanine acidic nucleus.

When E is an acyclic group, R'', R', Rc and R- are each a -valent substituent, and an alkyl group (for example, a methyl group).

Examples thereof include ethyl group, octyl group, dodecyl group, 5ec-octyl group, etc.), aryl group (eg, ρtolyl group, phenyl group, etc.), and heterocyclic group (eg, benzofuryl group, etc.).

When E is a cyclic group, R.H. You can choose from etc.

Preferred compounds of general formula (V) are general formula (VI) CVI
') (Vl").

General formula (Vl) R++Rz+R31n and E represent the same meanings as in the above general formula (V).

General formula [■'] R (3) Rr, Rr-Rx, and E are synonymous with general formula (V), and R
Tl> is a hydrogen atom, an alkyl group, or an alkoxy group.

Aryloxy group, aryl group, aralkyl group.

and a cyano group, or a group of atoms that together with R1 form a 5- to 6-membered ring. Also R”'.

R(3) each has 8 hydrogen atoms and an alkyl group.

General formula [■“] HcoR,, R,, R,, E is synonymous with general formula [■], and R
(4) is a hydrogen atom, alkyl (for example, each group such as methyl or ethyl), or alkoxy (for example, methoxy).

groups such as ethoxy), aryloxy (e.g. phenoxy group), aryl (e.g. phenyl group), aralkyl (e.g.
For example, benzyl groups) and cyano groups are included.

R(4) and R2 may jointly form a 5- to 6-membered ring.

R (81, R (&) and R ()) are hydrogen atoms, alkyl (e.g. methyl, ethyl, propyl, etc.), aralkyl (e.g. benzici, phenethyl, etc.), aryl (e.g. phenyl), Heterocycle (for example, chenyl, furyl, etc.), alkyloxy (for example, methoxy, ethoxy, etc.), aryloxo (for example, phenoxy), cyano group, amino (for example, dimethylamino, anilino, etc.), It represents alkyloxy, alkylthio (for example, methylthio group), arylthio (for example, phenylthio group) groups, and an acidic nucleus. However, R(4)p
ill, RC67, R1) are not all hydrogen atoms.

k is 0 or 1.

k is 0 or 1.

In a particularly preferred form, the compounds of the invention are cyanine dyes. These dyes can be symmetrical, so that they contain at least two identical tellurium azolium nuclei, or they can be asymmetrical, in which case the nuclei can each be a different tellurium azolium nucleus, or they can contain at least one tellurium azolium nucleus. tellurium azolium core and one or more conventional basic heterocyclic cyanine dye cores. The cores are linked via methine bonds, which can consist of a single methine group or a chain of methine groups.

As mentioned above, the tellurium azolium ring can produce absorption shifts due to bathochromic effects, so fewer methine groups can be used to absorb longer wavelength electromagnetic radiation. However, methine linkages of up to 13 or more consecutive methine groups can be incorporated into the dye if desired.

The general formula (rV) can form a cyanine dye represented by the general formula [rooster] by R6.

General formula [■] R8 represents a quaternized substituent, and R1 may cooperate with L1 to complete a 5- to 6-membered fused heterocycle.

Ll+ Ll1 L3. La and Ri each independently optionally substituted methine group, n is 0.1 or 2, m is O or l, and Q is an atomic group completing the nucleus of the basic azolinylidene or azinylidene heterocycle. , yp have the same meaning as general formula (rV).

Moreover, the substituents LI· to L may be combined to form a ring.

R? Examples of the fused heterocycle formed by combining with R1 or R include the following.

In the general formula [■] and the formulas below, in an optimal form R7 and R8 are substituted hydrocarbons containing 1 to 6 carbon atoms (eg, alkyl or aryl groups).

Representative substituents include sulfo, sulfato, carboxy, hydroxycarbamoyl, cyano, succinimino, trimethylsilyl, alkoxy, and sulfo-substituted alkoxy.

Specifically, sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfophenyl, sulfatomethyl, sulfatoethyl, sulfatopropyl, sulfatobutyl, sulfatophenyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyphenyl. , hydroxyethyl, hydroxypropyl, carbamoylmethyl, carbamoylethyl.

Representative groups include carbamoylpropyl, carbamoylbutyl, carbamoylphenyl, cyanoethyl, cyanopropyl, iminoethyl succinate, iminopropyl succinate, trimethylsilylethyl, methoxyethyl, methoxypropyl, and sulfoethoxyethyl.

As is clear from the above formula, this cyanine dye is a type of quaternized tellurium azolium salt of formula (IV), although the structure of the substituent R6 at the 2-position is complex.

The tellurium azolium nucleus has already been described above.

Although this nucleus could be characterized as a tellurium azolium nucleus or a tellurium azolinylidene nucleus, for convenience we will use the former designation, but for consistency we will refer to the remaining nuclei as azolinylidene or azinylidene nuclei.

Generally, any azolinylidene or azinylidene nucleus satisfying formula [■] can be used in combination with the tellurium azolium nucleus. It is particularly contemplated that Q can be selected from: benzotellurium azolinylidene, naphthotellurium aprinylidene, 2- or 4-pyridylidene, imidazopyridylidene, 2- or 4-quinolinylidene.

l- or 3-isoquinolinylidene, penzoquinolinylidene, thiazoloquinolinylidene, imidazoquinolinylidene, 3H-intolylidene, IH or 3H-benzintolylidene, oxazolinylidene, oxazolidinylidene, Penzoxazolinylidene.

naphthooxazolinylidene, oxadiazolinylidene,
Thiazolidinylidene, phenanthrothiazolinylidene,
Acenaphthothiazolinylidene, thiazolinylidene, penzothiazolinylidene, naphthothiazolinylidene, tetrahydrobenzothiazolinylidene, dihydronaphthothiazolinylidene, thiadioxazolinylidene, selenium azolidinylidene, selenium azolinylidene Liden, penzoselenazolinylidene, naphthoselenazolinylidene, selenium adiaprinylidene, birazolylidene, imidazolinylidene, imidazolidinylidene, penzimidazolinylidene,
The naphthoimidazolinylidene, diazolinylidene, tetrazolinylidene, and imidazoquinoxalinylidene cores can be substituted in any conventional manner consistent with formula [■]. Rs can, for example, be any conventional quaternized group and can be selected from any of the various forms of R7 described above.

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

General formula (IX) In the formula, Rl*R2+n*mHY- and p represent the same meanings as in the above general formula [■].

R7 and R1 are independently optionally substituted alkyl and aryl groups, respectively, and Q is a group of atoms completing the basic azolinidene or azilinidene nucleus, which may include a benzo or naph1 ring moiety.

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

(XI).

General formula (X) General formula (XI) In the formula, R,, RZ, R1, R4, Q, Y-, M and P have the same meanings as in the above general formula [■].

R(II) to R (161 are each a hydrogen atom, alkyl (e.g., methyl, ethyl, propyl, etc.), aralkyl (e.g., benzyl, phenethyl, etc.), ring (e.g., phenyl), heterocycle (e.g. groups such as chenyl, furyl, etc.), alkyloxy (e.g., methoxy, ethoxy, etc.), fururoxy (e.g., phenoxy group), cyano group, amino (e.g., dimethylamino, anilino, etc. groups), alkyloxy, It represents alkylthio (eg, methylthio group), arylthio (eg, phenylthio group) groups, and an acidic nucleus.

n゛ represents 0 or kn'' represents 1 or 2. However, 1
When +n#≦2, R(il) ,, R(+ +11
and Rta-+ Not all of Ra+ are hydrogen atoms.

R3° and Ro are hydrogen atoms, alkyl (for example, methyl, ethyl, etc. groups), °? Rukoxy (e.g. methoxy,
ethoxy and the like), aryloxy (for example, phenoxy group), aryl (for example, phenyl group), aralkyl (for example, benzyl group), and cyano group.

Rta and R11 may jointly form a 5- to 6-membered ring #R1! represents a hydrogen atom or an alkyl group (for example, a methyl group), and R13 represents a hydrogen atom or an alkyl group (for example, a methyl group).

In another preferred form, the cyanine dye used in the photographic element of the present invention is represented by the following general formula [χ■] in addition to the general formula [■].

General formula (XIII) R+ and R7 are synonymous with general formula (IV), and R? +R
11l L+ ””Ls+ Y −+p+ m,
n has the same meaning as the general formula [■].

Examples of the ring that R1 may form with R2 or R2 include those described in the general formula [■].

With the exception of the form of the apriedene or azinylidene ring completed by Q, the various components of formula (Xn[) can be selected in the same manner as described above for formula [■].

In an optimal form, Q of the formula [χ■] is selected from among the nuclei of pyrrolilidene, intrilidene, carboazolilidene, benzintolylidene, pyrazolylidene, indasylylidene, and pyrrolopyridinylidene.

Again, common ring substituents consistent with formula (Xltl) are contemplated.

R1 and R3 optimally represent substituted alkyl and aryl substituents, respectively, as described above.

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
It can be located behind the above silver halide emulsion layer. In other words, the dye can be used as an anti-haleysilane dye.

The compounds of the invention can be incorporated into interlayers or overcoats to function as filter dyes. In a preferred application 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 has a more favorable dye concentration desensitization relationship, i.e.
Requiring more dye to reach desensitization levels, the dyes as compounds of the present invention offer the advantage of allowing zero surface fog when used directly to form positive images in silver halide emulsions. When used in combination with , those 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 rv and longer are particularly advantageous.

The compounds of the invention need not necessarily be in the form of dyes. A large number of chalcogenazolium anticaprylants and stabilizers are known in the art, and the corresponding tellurium-containing compounds can usually be used as substitutes. A particularly useful class of compounds for photographic purposes is the class of compounds represented by formula (■) above, in which R6 is an alkynyl substituent and R6 is a methyl substituent.

Such a compound can be represented by the following general formula (Xl'l/).

General formula (X IV) In the formula, R1 and R2 represent an atomic group completing an optionally substituted aromatic 5- to 6-membered ring, or R, and R2
represents a hydrogen atom or an aryl group, and at least one of them is an aryl group.

R1 is preferably an alkynyl group having 3 to 5 carbon atoms, and most preferably propargyl or 2-butynyl.

R14 is preferably a hydrogen atom or a substituent having a Panot sigma value more positive than -0.2 determined from electron-withdrawing properties.

Corresponding compounds, which differ only in the presence of different chalcogen atoms, are known to be very useful as the properties agent. Therefore, these compounds can be used in combination with internal latent image-forming emulsions to directly form positive images. Therefore, the generator is advantageously present in the photographic element prior to imagewise exposure.

It can be adsorbed onto the surface of silver halide grains.

It is preferable to include an adsorption-promoting moiety as a substituent in the compound of the present invention. Useful adsorption-promoting groups include thioamide groups, such as oxythioamide groups, dithioamide groups, and thiourido groups. Corresponding compounds without adsorption promoting moieties are described in U.S. Patent No. 4.115.1.
The compound of formula (XIV) disclosed in No. 22 can also be used to increase photographic sensitivity. In this case, a compound for removal is adsorbed onto the surface of the light-sensitive silver halide grains in the surface latent image forming emulsion, and preferably this compound contains a thioamide group.

It is often desirable to adsorb hydrazide and hydrazine derivatives (eg, hydrazide and hydrazone alkyl) nucleating agents to the surface of internal latent image-forming silver halide grains. To achieve this, it is known to introduce chalcogenazolium rings into the nucleating agent to promote particle adsorption. In some embodiments, the compounds used in the photographic elements of the present invention can be in the form of tellurium azolium ring moieties of the various forms described above that are attached to the hydrazino or its derivative nucleating moiety, either directly or through an intervening linking group. can. For example, the compounds used in the photographic elements of the present invention are described in the Re5earch Discl.
osure, Vol, 176. 1978 12
May, Item 7626, and U.S. Patent No. 3.
It differs from No. 759,901, No. 3,854,956, and No. 1,150,993 only in that a divalent tellurium atom is present in the ring instead of the chalcogen disclosed therein. be able to.

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

U.S. Pat. No. 4,272,614 teaches the incorporation of such contrast-enhancing additives containing heterocyclic nuclei forming 5- or 6-membered rings with carbon, oxygen, sulfur, selenium, and nitrogen. teaching.

The specific ring structures disclosed are generally similar to those previously described as useful as cyanine dye nuclei. In particular, the cores of tellurium azolium salts and derivatives used in the practice of this invention may be substituted for the cores of the corresponding ercogenazolium and derivatives thereof disclosed as useful in U.S. Pat. No. 4,272,614. It is conceivable that it could be used.

Therefore, the compound of the present invention can be used as a contrast-enhancing additive of hydrazine and its derivatives while exhibiting the effects of the present invention.
In particular, hydrazide contrast-enhancing additives containing a tellurium azolium salt or a derivatized volume thereof in addition to a moiety of hydrazide or its derivatives are used in surface latent image markings to increase the contrast to very high levels, such as levels suitable for squirrels. It is conceivable to increase it to

In yet another embodiment, the compounds of the present invention can be used to promote latent image retention while still achieving the effects of the present invention. A useful group of latent image-retaining additives that are useful in photographic elements according to the present invention include Re5earch D
laclosure, Vol. 239. 1984 3
May, 1tem, 23925, except that the compounds used in the photographic elements of the present invention contain divalent tellurium atoms in place of the divalent atoms of oxygen, sulfur, and selenium disclosed in said document. Although there are differences in the inclusion of atoms in the ring, they can be accommodated. In a preferred embodiment, the latent image-retaining additive used in the practice of the present invention can be represented by the general formula (XV) below as a special version of the general formula CI[I].

General formula (XV) In the formula, R3 and R2 have the same meaning as the general formula (I[I),
RI5 is hydrogen or a methyl group, Z is -CHlN- or -N- and I R16Rl6 RI6 is hydrogen or an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms.

Specific examples of the tellurium-containing compound according to the present invention are shown below.

o.

Oli 0 work〒,
Engineering 0: E E = Engineering ω Ba :e! S::Cm:e 工 工(J
g
CuO -ko ■ Lo - ~ t'Q
Moaning 1-111++T++
'1 View :a :e :e:c agony agony --111 -four agony agony N
%-1l +-11-1 g :Ouu -knee agony cq +q
w to -1C,H.

CriH.

0H.

〇H,C0OH CH Snow CH, OH so,e C,H.

CHs　　eN (CHI)s 80s e CHICH1801Nm (CH2)4803Na CH, C, H.

Hs (CH180 lNm CB, C'H, CH30 Snow K Hs CHICH10801Na 9 3
CH, CH, 80s
e80.8, 104 A^ 〒1 L; 113 C, H.

CH Snow CH=CH! CB, CH, 80, K C mushroom H.

C1H45O1Na CH snow C0OH C, Hs CH.

(:,l(,!l=1 C Goose H@ C4H@n C, H@ 80, to C) 1tt C spirit H.

For C4 zHa C's H.

(CH2) 480BNm 0Hs CH.

(CH,)4 01Na C,H.

CH, CH.

C Snow H.

CH.

T.

CH.

CH.

0gNm Ward C snow H6 CH.

80,e (CHI) 1801 Nm C, H40H L; F.

213
CHICH snow OHCH3CH
2QC, H mouth 80. H (CHI CHI0)1 CH2CH280HN&21
B C! H.

C! H40CH.

The compounds of the present invention can be obtained by referring to the following patents and documents.

British Patent No. 587,434, British Patent No. 625,245, British Patent No. 654.690, British Patent No. 841,119, Buddhist Patent No. 7
57,767, U.S. Patent No. 1,846.302, U.S. Patent No. 2,228,156, U.S. Patent No. 2,345,094, U.S. Patent No. 2
, 369.646, 2.378,783, 2.
385.815, 2.478.366, 2.6
No. 10,121, No. 2,238,231, No. 2,21
No. 3.995, No. 2,503,776, No. 2,734
, 900, JP-A-47-9678, JP-A No. 6
Publications No. 0-78445, Journal of the American Chemical Society, Volume 67, 1875
-1889 (1945), (J, Chem.

Soc, 6e, 1875-1889 (1945)
, Volume 127.

532 3 (1925), (J, Che II
l, Soc, Sat 11°532-3 (1925),
1963, 5712-5717 (J, Chew,
See, 1963.5712-5717) F.
M. Harma, Cyanine Soybean and Related Compounder (Published by Inter Science Publishers, 1964) Pharmaceutical Journal, Volume 68, 191-1
94 (1948) Zh, 0bsh, Khim,...
32. 857-9 (1962).

Llkrain, Kjm+ Zhur,, 2 Sat.
744-9 (1955) 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 (Synthesis Example) 5.6-sihydro-2-methyl-4H-tellazolo (5
,4,3-i,j) Quinolinium chloride salt (Exemplary Compound 39) N-acetyl-1,2°3. in 100 mf of benzene.
18.7 g of 4-tetrahydroquinoline and 27 g of tellurium tetrachloride were mixed and heated under reflux for 3 hours.

Thereafter, the heating solvent is distilled off in an oil bath at 110°C.

Disperse the evaporation residue in 200ml of methanol and
g of aqueous sodium hydroxide solution is added to make a homogeneous solution.

Attach a cooling tube and slowly add sodium borohydride powder under a nitrogen atmosphere until the solution becomes colorless.

Next, add 5Qm of concentrated hydrochloric acid while cooling the container by immersing it in an ice water bath.
j! is added to make it strongly acidic and crystallize. The crude product was repeatedly recrystallized from methanol to obtain 4.3 g of colorless crystals.

Elemental analysis and nuclear magnetic resonance spectra are consistent with expectations.

Synthesis Example 2 4-(2-(5,6-sihydro-2H,4H-tellazolo(5,4,3-4,j)quinoline-2-ylidene)ethylidene-5-okyly2-thioxo-1,3-thiazolidine- 1-yl acetic acid (exemplified compound 45) 2-acetanilide vinyl-5,6-sihydro 4H-
4.6 g of Tellazolo (5,4,3-4,j) quinolinium chloride and 1.9 g of 3-carboxymethylrhodanine
Dissolve g in 50 mjl of absolute ethanol, add 2 g of triethylamine, 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 precipitate is collected by filtration. The crude product is purified by repeated recrystallization from methanol Yield: 1.4 g Maximum absorption wavelength in memethanol solution: 55 Q nm Synthesis Example 3 3-(2-(3-(5,6-Sihydro 2H).

4H-tellazolo(5,4,3-i,j)quinoline-2
-ylidene)-1-propenyl)-1-naphtho(1,2
-d) Thiazolio]propanesulfonic acid inner salt (Exemplary compound 58) 5.6-Sihydro2-methyl-4H-tellazolo (5
, 4, 3-i, j) 3.2 g of quinolinium chloride and 30 mj of acetic anhydride! , add 3.8 g of diphenylformamidine, and heat under reflux for 10 minutes. After cooling, dilute with isopropyl ether and collect the precipitate by filtration.
Wash with ethyl acetate and dry. Yield 3.3
g 2.3 g of the crude product was dissolved in m-cresol 20I111, and 1.6 g of 3-(2-methyl-1-naphtho[1,2-d]thiazolio)propanesulfonic acid inner salt and 2.0 g of triethylamine were added. In addition, heat and stir at 110° C. for 20 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize, collect the precipitate by filtration and wash with ethanol. The crude product was purified by repeated recrystallization from chlorophomethanol (1:1).

Yield: 0.56 g Melting point: 300°C or higher Absorption maximum wavelength in methanol solution: 607 nm Synthesis Example 4 2-Methyl-4-phenyltellazole (Exemplary Compound 6
7) Completely replace the inside of the reaction vessel with nitrogen and add 18 g of dehydrated acetonitrile and 20 g of α-bromoacetophenone.
Add g. Add 2.5 times of phosphorus oxychloride and replace the system with nitrogen again. Hydrogenated tellurium (J, Am,
The reaction is carried out by heating on a water bath through Che+s, Soc, U., 429 (1949).

The reaction solution is subjected to steam distillation to remove unreacted components.

Subsequently, the remaining Uta reaction solution is made alkaline and subjected to steam distillation again to distill out the basic components. The aqueous phase is extracted with ether and dried using anhydrous magnesium.

Distill the ether phase to obtain a viscous yellow oil. Crystallize from isopropanol to obtain a colorless prism product. Yield: 311.4 g, melting point: 56-61°C Synthesis Example 5 2-(5-2-(3-methyl-4) -phenyl-2(3
H) Tellurazoliden)ethylidene)4-oxo-2-thioxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (Exemplary Compound 83) 2-acetamidovinyl-3
2.9 g of methyl-4-phenyltellazolium trifluoromethanesulfonate and 1.2 g of 3-β-sulfoethylrhodanine 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 left to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitator is collected by filtration. The crude product is purified by repeated recrystallization from methanol. Yield: 0.81 g Maximum absorption wavelength in methanol solution: 546 nm Synthesis Example 6 2-(5-chloro-2-(3-(3-methyl-4-phenyl-2) (3H) tellurazolidene)-1-probenylidene)-3-benzoxazolio)ethanesulfonic acid inner salt (exemplary compound 94) 13.5 g of 2-methyl-4-phenyltetrazole was added to dichloromethane 80e+4! 9.0 g of methyl trifluoromethanesulfonate dissolved in
Add, seal, and leave at room temperature for one week.

The precipitated crystals are collected by filtration and then suspended in 120 ml of acetic anhydride.

Add 19.6 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried. Yield: 15.1 g 2.9 g of the crude product was dissolved in 20 sJ of m-cresol, and 1.4 g of 2-(5-chloro-2-methyl-3-penzooxazolio)ethanesulfonic acid inner salt and 1 g of triethylamine were dissolved. In addition, heat and stir at 110° C. for 15 minutes.

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

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

Yield 0.54 g Maximum absorption wavelength in methanol solution 601 nm Synthesis Example 7 2.3-trimethylenebenzotellazolium iodo salt [
Exemplary Compound (112)) 2-(3-hydroxybutyl)penzotellurazole6.
A solution of 1 g (2/100 mol) of pentachloroethane 60n+J was put into a pressure tube. The system was cooled in a water bath and maintained at 0° C., the inside of the system was purged with nitrogen, and 1/2 equivalent 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 room temperature, and the mixture was further heated at 100°C.

After cooling, the platelet was collected by filtration, the crude product was dissolved in 25 mj2 of ethanol, 15 nl of ethanol in which 5 g of sodium iodide was dissolved was added, and the mixture was stirred and cooled for crystallization. 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.

Synthesis Example 8 5-(4-(IH-'2,3-dihydropyride(2
, 1-b) Penzotellazolyl]methylene-4-oxo-2-thioxo-1,3-thiazolidin-3-yl acetic acid (Exemplary Compound 115) 4-acetanilide methylene-1
, 5.6 g of 2,3,4-tetrahydropyrido (2,1-b) vezizotellazolium iodo salt and 1.9 g of 3-carboxymethylrhodanine in 60 mj of absolute ethanol!
2 g of triethylamine 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: 1.4 g Melting point: 300°C or higher Absorption maximum wavelength in methanol solution: 556 nm Synthesis Example 9 Bis-3,8-3', 10-)rimethyleneteralulpocyanine iodo salt (Exemplary Compound 121) 2.3-) 4g of methylenebenzotellazolium iodo salt and ortho#
1.5 g of acid ethyl ester was added to 30 ml 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 1.0 g of a crude product.

It was purified by repeated recrystallization from methanol.

Yield: 0.6 g Melting point: 300°C or higher Maximum absorption wavelength in methanol: 627n+m Synthesis Example 10 3-Phenyl-2-thiotelazolidine-2°4-dione (Exemplary Compound 128) 18.7 g of bistelluroacetic acid was degassed. Suspend in 50 m6 of water and stir under nitrogen atmosphere. Dextrose 11.
2g aqueous solution 40mj! and 33% caustic soda aqueous solution 3
Add 6I111 and heat on an 80°C water bath for 30 minutes.

After returning to room temperature, 100a+A of etalur solution in which 13.5g of phenyl isocyanate was dissolved and 100ml of 6N hydrochloric acid.
Add #. The mixture was heated under reflux again for 2 hours under nitrogen atmosphere and left overnight.

The precipitated crystals were collected by filtration and washed with ethanol to obtain 10 g of crude crystals.

Recrystallization from methanol gave orange-yellow prism crystals.

Yield 5.7g Melting point 208-210'll: Synthesis Example 11 5-(2-(3-ethyl-6-methyl-2(3H)penzothiazoliden)ethylidene-3-phenyl-2-
Thioterazolidine-2,4-dione (Exemplary Compound 1
35) 2-(2-acetanilidevinyl)-3-ethyl-6-
Methylbenzothiazolium iodo salt 4.58 and 3-phenyl-2-thiotelazolidine-2,4-dione 2 g
and dissolved in 30 mA of ethanol. Add 2 g of triethylamine, heat under reflux for 10 minutes, and then cool.

The precipitated crude product is collected by filtration and washed with ethanol.

Yield of recrystallizing from methanol to obtain orange-red crystals 1.2
g Maximum absorption wavelength in methanol solution 531 nm Synthesis Example 1
2 4-[5-hydroxy-3-methyl-4-(3-(4-
Oxo-3-phenyl-2-thioxotellazolidinylidene)-1-propenyl)pyrazolyl]benzenesulfonic acid potassium salt (Exemplary Compound 143) 3-phenyl-2-thiotellazolidine-2゜4-dione 1 ．． Og and 2.1 g of 4-(3-acetanilidearylidene)-3-methyl-1-(P-sulfophenyl)-5-pyrazolone in dimethylformamide 10+sj!
Add 1 g of triethylamine and stir. Dilute the water pumped for 4 hours by adding 50 mA and acidify with dilute hydrochloric acid.

The precipitate is collected by filtration and washed with methanol.

The crude product is purified by dissolving it in a methanol solution containing 1.2 equivalents of triethylamine and crystallizing it by adding 2 equivalents of potassium acetate.

Yield: 1.3 g Synthesis Example 13 2-Methyl-cheno(2,3-d)tellazole [Exemplary Compound 144] 14.1 g of 2-acetylaminothiophene and 27 g of tellurium tetrachloride were mixed with 80 mj of benzene! After heating under reflux for 2 hours, the external temperature was raised to 120°C and the solvent was distilled off.

200mj of methanol in the evaporation residue! Add and disperse, and add about 8 g of an aqueous sodium hydroxide solution to make a homogeneous solution. Attach a cooling tube and gradually add sodium borohydride under a nitrogen atmosphere until the solution becomes colorless.

Next, the container is immersed in an ice water bath and cooled while making salt M50m.
Add ti to make it strongly acidic. The black precipitate was filtered out and the filtrate was divided into 1
The crude product precipitated as a hydrochloride is dispersed and stirred in an aqueous sodium carbonate solution, and the free product is extracted with dichloromethane. The extract is washed with water and dried using anhydrous sodium sulfate.

The solvent was distilled off under reduced pressure to give a viscous yellow oil which was crystallized using isopropanol. Yield of crystals: 9.3 g Elemental analysis and nuclear magnetic resonance spectra were consistent with expectations.

Synthesis Example 14 2-(5-(2-(3-methyl-2(3H)cheno)
(2,3-d)tellazoliden)ethylidene)-4-oxo-2-thioxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (exemplified compound 159) 2-acetanilide vinyl-3-methyl-cheno ( 2
, 3-d) 2.6 g of tellazolium trifluoromethanesulfonate and 3-β-sulfoethylrhodanine 1.
Dissolve 2 g in 50 mff of absolute ethanol, add 2 g of triethylamine, and heat 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: 0.85g Maximum absorption wavelength in methanol solution: 562nm Synthesis Example 1
5 3.3'-Dimethyl-cheno(2,3-d)telluracarbocyanine trifluoromethanesulfonic acid (Exemplary Compound 169) 2-Methyl-cheno(2,3-d)tellazole 12.
5 g to dichloromethane 100s+j! Add 9.0 g of methyl trifluoromethanesulfonate to the solution, seal the solution, and leave at room temperature for one week.

The precipitated crystals were collected by filtration, followed by 120 mj of acetic anhydride! Suspend in

Add 19.6 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried. Yield: 14.8 g 2.6 g of the crude product was dissolved in 201 Ill of m-cresol, and 2.0 g of 2,3-dimethyl-cheno (2,3-d) tellrazolium trifluoromethanesulfonate and 20 g of triethylamine were added. Heat and stir at 110°C for 15 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Acetone was added and the mixture was stirred for crystallization, and the precipitate was collected by filtration, washed with ethanol, and purified by recrystallization from a mixed solvent of 2,2,3,3-tetrafluoropropanol-methanol (1:3).

Yield: 0.58 g Maximum absorption wavelength in methanol solution: 636 nm Synthesis Example 1
6 5-Chloro-2-methylbenzotellurasol (Exemplary Compound 175) 109 g of azobis-m-chlorobenzene, 1 tellurium tetrachloride
35 g and 66 g of anhydrous aluminum chloride are added to 600 mJ of 1,2-dichlorobenzene. The inside of the system was replaced with nitrogen and heated to reflux under a nitrogen stream.

After 2 hours, the mixture is allowed to cool, and the same amount of methanol is added to dilute and stir. Cool thoroughly in an ice water bath, collect the precipitate by filtration, and wash with methanol.

78 g of the crude product was added to Tanol 600a+J and stirred under a nitrogen atmosphere to give 22.5 g of sodium borohydride powder.
Add g to reduce.

After the exotherm has finished, the mixture is cooled in an ice water bath and kept at 8°C or lower, and 16.5 g of acetic anhydride is added dropwise.

The mixture was stirred for a further 30 minutes and then added with 150 μl of concentrated hydrochloric acid.
Add l.

The black precipitate was filtered off, and the filtrate was heated under reduced pressure at low temperature in 1. /3 to? l
Water after shrinkage 500 mj! ! Add and dilute.

Add a 10% aqueous sodium carbonate solution to make it slightly alkaline, and extract with chloroform. After washing with water and drying anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a pale yellow solid.
g get.

Recrystallize from isopropanol to obtain colorless crystals.

Yield: 17g Elemental analysis values are consistent with expectations.

Synthesis Example 17 2-(5-(2-(5-fluoro-3-methyl-2(3
H)-benzotellazolidene)ethylidene)4-oxo-2-thioxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (exemplary compound 2-acetanilide vinyl-5-fluoro-3-methylbenzotellazolium trifluoro) 2.8 g of lomethane sulfonate and 0.95 g of 3-carboxymethylrhodanine were added to 30 I of absolute ethanol.
111, add 2 g of triethylamine, and heat under reflux for 20 minutes.

The reaction solution is allowed to cool, and then sufficiently cooled in an ice-water bath to crystallize. The precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol. Yield: 0.6 g. Maximum absorption wavelength in methanol solution: 547 nm. Synthesis. Example 1
8 Anhydro 3-(2-(3-(5-fluoro-3-methyl-2(3H)penzotelllazolidene)-1-propenyl)-5-methoxy-3-penzoselenazolio]propanesulfonic acid within the molecule Salt (Exemplary Compound 190) 5-Fluoro-2-methylbenzotellazole 13,1
Dissolve g in 100 mjl of dichloromethane, add methyl trifluoromethanesulfonate 9 and Og, seal tightly, and leave at room temperature for 2 weeks.

The precipitated crystals were collected by filtration, and then acetic anhydride 100+wj! Suspend in

19.6 g of diphenylformamidine is processed and heated under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried. Yield 8.3g Crude product 2.8g m-cresol 2
0mj! 3-(5-methoxy-2-methyl-
1.7 g of 3-penzoselenazolio)propanesulfonic acid inner salt and 2 g of triethylamine were added for 15 minutes.
Heat and stir at 10°C.

After cooling, dilute with isopropyl ether and discard the supernatant. Acetone is added and the mixture is stirred for crystallization, and the precipitate is collected by filtration and washed with ethanol.

Chloroform-methanol (1:2) 4? Purification was performed by recrystallization from medium 9.

Yield: 0.51g Maximum absorption wavelength in methanol solution: 599nm Synthesis Example 1
9 5'-Chloro-3,5,10-)dimethyl-3'-sulfobrobyltellathiacarbocyanin inner salt [Exemplary compound 196] 2.3.5-trimethyl-benzotellazolium-trifluoromethane 4.2 g of sulfonate and 3.8 g of 3-(5-chloro-2-(2methylthio-1-propenyl)-3benzothiazolio)propanesulfonic acid inner salt were added to 30 sjl of pyridine, 2 g of triethylamine was added, and the mixture was heated at 40°C. Stir.

The precipitated dye is collected by filtration and washed with methanol.

The target product was purified by recrystallization from a mixed solution of 2.2,3.3-tetrafluoropropanol and methanol to 0.74%
I got g.

Maximum absorption wavelength in methanol solution 595 nm Synthesis example 2
0 5- (4-(3-ethyl-5-methyl-2(3H)tellazolidene)-2-methyl-2-butenylidene)-4
-oxo-2-thioxo-1,3-thiazolidine-3-
Ylacetic acid [Exemplary Compound 200] 5.9 g of 2-(3-acetanilidemethylene-2-butenyl)-3-ethyl-5-methylbenzotellazolium iodo salt and 1.9 g of 3-carboxymethylrhodanine were added to ethanol 80 TII.
Add to t.

Add 3 g of triethylamine, heat under reflux for 30 minutes, cool with water, and precipitate as acidic acetic acid.

The crude product is heated and dissolved in methanol containing triethylamine, cooled and acidified with acetic acid to crystallize.

It was collected by filtration and washed with ethanol to obtain 1.2 g of the desired product.

Maximum absorption wavelength in methanol solution: 608 nm Synthesis example 2
1 3-ethyl-5-methyl-3'sulfopropyl-9,1
1-neopentylene telllathiadicarbocyanine inner salt (Exemplary Compound 203) 3-ethyl-2-methyl-tellazolium trifluoromethanesulfonate 43.7 g
and 16.6 g of isophorone were mixed and dehydrated under nitrogen atmosphere with stirring in an external bath at 180° C. for 4 hours. Add 100II+1 each of cold water and chloroform, stir, and extract.

The black chloroform solution is washed with water, and the chloroform phase is diluted with a double amount of acetic acid ethyl ester and crystallized with stirring. 11. Filter and wash with ethyl acetate to obtain a dark brown powder.
I got 1g.

2.8 g of the crude reaction product and 1.9 g of 3-sulfopropyl-2=sulfopropylthiobenzothiazolium were suspended and stirred in 50 mZ of acetonitrile.

Subsequently, 2 g of triethylamine is added and stirred at room temperature.

After dissolution, the dye that develops color and precipitates is collected by filtration and washed with methanol.

The product was purified by recrystallization from a chloroform-methanol mixed solution to obtain 1.2 g of the desired product.

Maximum absorption wavelength in methanol solution: 666 nm Synthesis example 2
2 Anhydro-3'-(2-hydroxyethyl)-3-(
3-sulfopropyl)-naphtho[1,2-d)tellazolothiacarbocyanine hydroxide [Exemplary Compound 207
] Anhydro-2-methyl-3-(3-sulfopropyl)
Naphtho(1,2-d)tellazolium hydroxide4.
2g and 2-(2-acetanilidevinyl')-3-
(2-Hydroxyethyl)-benzothiazolium iodide 4.7g dimethylformamide 25+wj! In addition, 2 g of triethylamine was added thereto, and the mixture was stirred at about 60° C. for 1 hour.

After cooling to room temperature, the product was precipitated by addition of ether, isolated by filtration and crystallized from methanol. Yield 1.2 g Methanol λl1ax607nI1 Synthesis Example 23 Anhydro-3'-ethyl-3-(2-(3-sulfopropyloxy)ethyl)-tellathiacarbocyanine hydroxide [Exemplary Compound-211] 2-hydroxyethyltrifluoro 1.9 g of methanesulfonate and 1.2 g of propane sultone were mixed and heated on an oil bath at 120°C for 1 hour, then 2.4 g of 2-methylbenzotellurazole and chloroform 20111 were added to the viscous mixture that was allowed to cool. After heating, stirring, and refluxing for 2 hours, ether was added to the reaction solution that was allowed to cool to cause precipitation.

The supernatant was removed by decantation, and 4.5 g of 2-(2-acetanilide vinyl)-3-ethylbenzothiazolium iodide, 20 g of dimethylformamide, and 1.5 g of triethylamine were added, and the mixture was allowed to react at 60°C for 2 hours. Ta. After cooling, ether was added to the reaction mixture to precipitate the product, which was isolated by filtration and recrystallized from methanol.

Yield: 1.5g.

Methanol λ-ax 5 8 1 nm When the compound of the present invention is used as a sensitizing dye, it is in each case lXl0-' mol to 5X10-' mol, preferably lXl0-' mol to 2.5x10-' mol, per mol of silver halide. z mol, particularly preferably 4X10-'mol-1X10-' mol.

The compounds used in the present invention can be added to the emulsion as enhancing dyes using methods well known in the art. For example, these sensitizing dyes can be dispersed directly in the emulsion, or they can be dispersed in pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone,
or a mixture thereof, or diluted with water, or dissolved in water, and added to the emulsion in the form of these solutions, and the sensitizing dye is added to the emulsion. This may be done at any time during the emulsion manufacturing process, but preferably during or after chemical ripening.

When the above-mentioned compound of the present invention is used as an antifoggant, it is added to at least 11 layers, preferably a silver halide emulsion layer, of the constituent layers of a light-sensitive material.

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, and is difficult to determine unambiguously, but it is recommended that -a be in the range of 10-8 mol to 1 mol per mol of silver halide. A preferable range of addition amount is 10<-6> to 10<4> moles per 111 moles of halogenide.

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 in combination.

Silver halide grains that may be used in conjunction with the silver halide emulsion of the present invention 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. Even though the method of creating and growing seed particles is the same,
May be 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 the pH and pAg in the mixing tank. With this method,
Silver halide grains with a regular crystal shape and nearly uniform grain size can be obtained.

Silver halide grains that may be used in combination include halogenated l! Solvents can be used to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

Silver halide grains that may be used in combination include cadmium salt,
Zinc salts, lead salts, crilum salts, iridium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing)
By adding metal ions using at least one selected from the following, it is possible to contain these metal elements inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, the metal elements can be added inside the particles and/or on the particle surfaces. Alternatively, reduction sensitizing nuclei can be added to the particle surface.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains which may be used in combination are completed, or they may be left as they are contained. Research when removing the salts.

Research Disclo
sure) It can be carried out based on the method described in No. 1764.

Silver halide grains that can be used in combination in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or core/shell grains with different silver halide compositions between the grain interior and the surface layer. It may also be particles.

The silver halide grains used in the silver halide emulsion and which may be used in combination 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. good.

Silver halide grains used in silver halide emulsions, which may be used in combination, may have regular crystal shapes such as cubic, octahedral, and tetradecahedral, or may have regular crystal shapes such as spherical or plate-like. It may also have an irregular crystal shape. In these particles, any ratio of the 1001 plane to the +1111 plane can be used. Also, they may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

The silver halide emulsion of the present invention may have any grain size distribution as the distribution of silver halide grains that may be used in combination.

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.

Silver halide grains that may be used in combination in the present invention can be chemically sensitized by conventional methods. That is, sulfur sensitization method,
Selenium sensitization, reduction sensitization, noble metal sensitization using gold or other noble metal compounds, etc. 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 a dye other than the present invention known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Even if it is a dye that does not itself have a spectral sensitizing effect along with a sensitizing dye, or a compound that does not substantially absorb visible light,
A supersensitizer that enhances the sensitizing effect of the enhancing dye may be included in the emulsion.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
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 capri 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, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as 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 and other hydrophilic colloid layers of photographic elements using the silver halide emulsion of the present invention contain one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

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

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

In the emulsion layer of the photographic element of the present invention, a dye is formed by a campling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. A dye-forming coupler is used.

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, silver halide color photographic materials may be produced using different combinations from the 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. Furthermore, 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 contain development accelerators, bleaching accelerators, developing agents, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral sensitizers and desensitizers, can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or DI that releases a development inhibitor during development and improves image sharpness and image graininess.
An R 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 which undergoes a campling reaction with an oxidized form of an aromatic primary amine developer, but which 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 capri 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-ice emulsion dispersion method. It can be selected as appropriate depending on the situation. For the oil-in-ice emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent if necessary, and stir with a surfactant in a hydrophilic binder such as an aqueous gelatin solution.
After emulsifying and dispersing using a dispersion means such as a homogenizer, colloid mill, flow jet mixer, or ultrasonic device,
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 antifoggants, ultraviolet absorbers, fluorescent whitening agents, etc. have acid groups such as carboxylic acid or sulfonic acid, an alkaline aqueous solution is used. It can also be introduced into hydrophilic colloids as a hydrophilic colloid.

Anionic surfactants are used as dispersion aids when hydrophobic compounds are dissolved in low boiling point solvents or in combination with high boiling point solvents and dispersed in water using mechanical or ultrasonic waves.
Nonionic surfactants and cationic surfactants can be used.

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

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

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

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

To prevent degradation of magenta dye-forming couplers and the like by formalin during storage of the photographic element, formalin scavenging agents can be used.

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) A compound described in Section XXI B-0 of No. 17463, and the development retardant is
This is a compound described in item xr and item 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.

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

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

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

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

Antistatic agents can be added to the photographic elements of this invention for antistatic purposes. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for.

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

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

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

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 are highly reactive and would 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 protective colloid layers are prepared using Research Disclosure + - (Research Disclosure).
e) It can be applied by the method described in Section A of XV of No. 17463 and dried by the method described in Section 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, kimonon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode light, electron beams, XvA, r-rays, alpha-rays, etc. Any known light source can be used.

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

Any known method can be used for developing the photographic element of the present invention. Depending on the purpose, this development process may be either a process to form an m image (black and white development process) or a process to form a color image.If the image is created using the reversal method, the black and white negative is first developed. The process is then carried out by white exposure or by treatment with a bath containing a capri agent and color development. [Also, silver dye bleaching may be used, in which a dye is contained in the light-sensitive material, 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 photosensitive material in the processing solution, but other methods are also available, such as a spray method that supplies the processing solution in the form of a spray, or by contacting it with a carrier impregnated with the processing solution. A web method, a method of viscous development processing, etc. may be used.

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

A development process using a lithium developer as a developer may 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 treatment step using 1
A bleach-fixing process can be carried out using a bath bleach-fixing solution, or a monobath 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 treatments, 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 material and the development process is performed with an activator solution, or an activator process can be performed instead of the monobath process. This may be carried out simultaneously with bleaching and fixing treatments. Representative treatments among these treatments are shown below. (These treatments are carried out 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 staining process - Color development process - Bleach-fixing process/Pre-hardening process - Neutralization process - Color development process - Stop fixing process - Washing process - Bleach process Constant fixation process - Washing process - Post-hardening process/Color development Processing process - Washing process - Supplementary color development process - Stopping process 7 Bleaching process Constant fixation process / Monobath process / Activator process - Bleach-fixing process / Activator process - Bleach process Constant fixation process Processes In addition to these treatments, there are methods in which developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again, and various intensification treatments (amplification treatments) described in JP-A-58-154839. , processing may be performed using a developing method that increases the amount of dye produced.

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 emulsion A was prepared by the following method.

Silver halide emulsion A (silver iodobromide emulsion containing 7 mol % of silver iodide, having an average grain size of 3 μm and an average aspect ratio of 10:1) was prepared by the same method as described in JP-A-58-113928. 0 containing 59.5 g of potassium bromide,
8% gelatin solution5. Using the double jet method while stirring Ol at 80°C, 58.3 sJ of an aqueous solution containing 8.33 g of potassium bromide and 58.3*j! of an aqueous solution containing 11.9 g of silver nitrate were prepared. Then, 800+ aJ of a solution containing 17.6% phthalated gelatin was added. Then, a silver nitrate solution was added until PBr reached 1.40. Then, 38.7 g of potassium iodide, odor 2.61 g of an aqueous solution containing 340 g of potassium chloride was added at equal flow rates with 2.61 g of an aqueous solution containing 1.525 g of nitric acid by a double jet method.

During this time, PBr was maintained at 1.40. Temperature 40℃
After washing the precipitate with water, add gelatin and redisperse.
The emulsion was solidified at 20°C to prepare a 2.0 pupil emulsion.

Furthermore, 4-hydroxy-6-methyl-1,3゜3a,
100 m of a 1.0% by weight aqueous solution of 7-chitrazaindene
j! was stabilized by adding (Emulsion A) Add this emulsion to 400%
Each g was weighed into a pot and heated to 40°C to dissolve. Then, predetermined amounts of each of the compound according to the present invention and the comparative compound were added and mixed and stirred. A coating aid and a hardening agent were added to each of these emulsions, and the resulting emulsion was coated on a cellulose triacetate film base with a dry film thickness of 5 μm and a silver content of 50 μm.
/dIl! A photosensitive material sample was obtained by coating and drying.

Each sample was cut into a shape of 10 cm on a side, fixed on a horizontal glass plate with the emulsion coated side facing up, and a load was applied to a balance device equipped with a sapphire needle with a diameter of 3 fi and a hemispherical tip. The needle was placed in contact with the emulsion surface of the sample, and the glass plate to which the sample was fixed was moved at a constant speed of 2c111 per second in a constant direction. Thereafter, the sample was pre-exposed using a photosensitive needle at a Dungesten light source. 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, drying, and processing to obtain a sample with a black and white image.

Developer composition Metol 2gr anhydrous sodium sulfite 40gr hydroquinone
4g sodium carbonate monohydrate
28gr potassium bromide Ig
Add water and make to 11.

For each sample, the pressure was applied and the pressure was not applied in the low concentration area, the pressure was applied and the pressure was not applied in the high concentration area, and the pressure was applied and the pressure was not applied in the high concentration area. measure,
The results shown in Table 1 were obtained.

As can be seen from Table 1, it can be seen that pressure fog and pressure desensitization are improved by the present invention.

Comparative example-1 Comparative example-2 Comparative example-3 Example-2 Silver halide emulsion B was prepared by the following method.

Silver halide emulsion B.

A 5% ossein gelatin solution 11 was stirred at 75°C, 150 l of a 4.7 M aqueous solution of silver nitrate and ammonium iodide was added over 40 minutes using the double jet method, and then 525 mj of the same solution was added to the solution 11 at 75°C. was added over 20 minutes to form a silver iodide emulsion. At this time, pAg was maintained at 11.5. Next, 230 g of this emulsion was added to 1 liter of a 5% ossein gelatin solution stirred at 750° C. using a double jet method.
500mj of 7M silver nitrate and ammonium bromide! 1 solution
Added in 0 minutes. At this time, pAg was maintained at 6.0. The pAg of this emulsion was adjusted to 9.5, 28% aqueous ammonia 130a1 was added, and the emulsion was aged for 15 minutes.

The pH of the emulsion thus obtained was adjusted to 5.8,
4.7M solution of silver nitrate and ammonium bromide 750+mj
! was added over 15 minutes using a double jet method. During this time, 9Ag was kept at 9.5, and the addition rate was initially 33.
ll1ll /win, final 67 mj! /wi
It was sequentially increased to n. After the addition was completed, washing with desalinated water was carried out in a conventional manner.

The silver iodide content in the core of the emulsion thus obtained was 9 mol%, the volume of the core was 42%, the coefficient of grain size variation was 20%, and the average grain size was 1.40 μm.
The average aspect ratio was 5:1. (Emulsion B) The above emulsion B was chemically ripened by a conventional method, and the silver was 10.6%.
Emulsions of 0 mol/kg emulsion and gelatin 10 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 added to the coupler Dloog with 300n+1L of ethyl acetate and 100mf of dibutyl chloride.
Add and dissolve, add sodium dodecylbenzenesulfonate, and use a homogenizer to dissolve 10% aqueous gelatin solution.
The one obtained by emulsifying and dispersing it in kg was used. Predetermined amounts of each of the compound according to the present invention and the comparative compound were added to this emulsion, and the mixture was mixed and stirred.

Furthermore, 4-hydroxy-6-methyl-1,3,3a,7-
20mj of 1.0% by weight aqueous solution of tetrazaindene! A coating aid and a hardening agent were added to stabilize the emulsion, and the resulting emulsion was coated onto a cellulose triacetate film base at a coating silver amount of 5011 w/dm, and dried to obtain a sample. .

After applying pressure to each sample in the same manner using the same pressure device as in Example 1, each sample was heated to a color density of 5400.
A red filter was attached to the light source using a photosensitive needle with a light source of 100 mm to 100 mm. The dye density of each part was measured using a Sakura microdensitometer in the same manner as above.The obtained results are shown in Table 2.

Coupler D Development processing prescription 1, color development 3 minutes 15 seconds (38℃) 2,
Bleaching 6 minutes 30 seconds 3, washing with water 3 minutes 15 seconds 4, fixing 6 minutes 30 seconds 5, washing with water 3 minutes 15 seconds 6, stabilization 3 minutes 15 seconds The composition of the processing solution used in each step is as follows. It is.

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 4.5g
Add water to make 11.

Bleach solution Ammonium bromide 160.0 g Aqueous ammonia (28%) 25. Oa+J Ethylenediamine-tetraacetic acid sodium iron salt 130, Og Glacial acetic acid 14.0ml Add water to prepare 1a.

Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate 175.0mj! sodium bisulfite
Add 4.6g water to make 11.

Stabilizing liquid formalin 8 Add tall water to make 11.

As can be seen from Table 2, the present invention improves pressure fog and pressure desensitization.

Comparative Example 4 Comparative Example 5 H Comparative Example 6 ■ a03S Example-3 Each of the following constituent layers was coated on polyethylene coated paper in order from the support side to prepare a sample of a multilayer color photosensitive material.

The 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 dibutyphthalate per mol of silver halide. Contains 0.2 mol per mol of silver halide, and the amount of silver is 400 ■
/M.

Second layer: Intermediate layer This is a gelatin layer containing 2.5-di-t-octylhydroquinone and is coated at a gelatin concentration of 1.5 g/%.

Third layer - green-sensitive emulsion layer The green-sensitive silver chlorobromide emulsion layer (containing 80 mol% silver bromide) contains 500 g of gelatin per mol of silver halide and the following solution dissolved and dispersed in dibutyl phthalate. One magenta coupler per mole of silver halide, 062 mol, 2,5-di-
0.05 mol of t-octylhydroquinone per mol of magenta coupler, 1,4-di-octyloxy-2
, 0.3 mol of 5-di-1-amylbenzene per mol of magenta coupler, and the amount of silver is 500 ■
/d.

4th layer: 2,5-di-t dissolved and dispersed in intermediate layer dibutyl phthalate
- Octylhydroquinone at 30 μ/d and 2-(benzotriazol-2-yl)-4 as a UV absorber.
, 6-di-t-butylphenol at 0.7 g/r/d, and the applied gelatin is 1.5 g/r/d.
This is a layer that is coated to give the same effect.

5th layer - red-sensitive emulsion layer A red-sensitive silver bromide emulsion layer containing methanol solutions of the aggravating dyes according to the present invention and the comparative sensitizing dyes shown in Table 3, and adding a predetermined amount of 1 mol of silver halide. 5 pieces of gelatin per serving
00 gr and the following cyan coupler dissolved and dispersed in dibutyl phthalate at a concentration of 0.0 gr per mole of silver halide.
This layer contains 2 moles of silver and is coated so that the amount of silver is 500*/m.

6th layer - Intermediate layer The above-mentioned ultraviolet absorber dissolved and dispersed in dibutyl phthalate is added at 0.4 g/n? This layer is coated so that the gelatin N coating contained therein is 1.5 g/ffl.

The 71st protective layer is a seratin layer coated with a gelatin amount of 1.5 g/rd.

(Yellow coupler) (J (Magenta coupler) CI! (Cyan coupler) H The above blue-sensitive silver chlorobromide emulsion and green-sensitive silver chlorobromide emulsion are described in Japanese Patent Publication No. 7772/1972. and chemically sensitized using sodium thiosulfate pentahydrate and 4-hydroxy-6-methyl-1,3,3a as a stabilizer.

7 tetrazaindene was added, as well as a hardener and a coating aid.

Further, a red-sensitive silver bromide emulsion was prepared by the following method.

First, silver halide emulsion C was prepared by the following method.

Silver Halide Emulsion C 1.5% bone gelatin aqueous solution containing 0.14 mol of potassium bromide (8.0 ρ) was mixed with a 1.15 mol potassium bromide solution and 1.0 ρ of silver nitrate by the double jet method while stirring well. 0 molar solution at 60°C for 2 minutes at a constant flow rate.
, pBr 0.85 (3 of the gold and silver used)
．． 6% consumed)0 then a 2.0 molar solution of silver nitrate was added to p
Addition was made at a constant flow rate for approximately 5 minutes at 60° C. until Br reached 1.2 (consuming 8.8% of the gold/silver used). A 2.3 molar solution of silver potassium bromide and a 2.0 molar silver nitrate solution were heated by the double jet method while accelerating the flow rate (
The flow rate at completion was 5.6 times that at the beginning) for 255 minutes. The temperature was maintained at 60° C. and par at 1.2 (75.2% of the gold and silver used was consumed). A 2.0 molar solution of silver nitrate was then added at a constant flow rate at 60° C. over a period of 573 minutes until the pAg reached 7.8 (consuming 12.4% of the gold/silver used). The amount of silver used in preparing this emulsion was approximately 7.4 moles.

After precipitation was completed, the emulsion was cooled to 40°C and phthalated gelatin 1
Added 5.3% solution 1,471, U.S. Patent 2,614;
The emulsion was washed by the coagulation method described in No. 929.

Then, 1.31 g of a 135% bone gelatin solution was added and the pH of the emulsion was adjusted to 55.9 Ag to 82, respectively at 40°C.

The average grain diameter of the obtained tabular grain silver bromide emulsion was 1.43.
μm, thickness is 0.07 μm5 average aspect ratio is 20.
The ratio was 4:1, and the tabular grains occupied more than 95% of the total projected area. (Emulsion C) Emulsion C was chemically sensitized using sodium thiosulfate pentahydrate, and 4-hydroxy-6-methyl-1,3,3a, ? - Tetrazaindene was added, and a hardening agent and a coating aid were further added to form a red-sensitive silver bromide emulsion.

After applying pressure to each sample in the same manner using the same pressure device as in Example 1, the sample was exposed to a photosensitive needle with a light source with a color temperature of 5400°, and a red filter was attached to the light source. I took the first exposure. After exposure, the following formulation was developed, bleached and fixed, and washed with water.
A drying process was performed, and the density of the colored dye image was measured in the same manner as in Example 1 using a Sakura microdensitometer.

The results obtained are shown in Table 3.

As can be seen from Table 3, it can be seen that the present invention provides high sensitivity and also improves pressure fog and pressure desensitization.

Comparative Example-7 CHs CH3 Comparative Example-8 Comparative Example-9 1°SO2 Development treatment (processing temperature and processing time) [1] Color development 30°C 3 minutes 30 seconds [2] Bleacher 33°C 3 minutes 30 seconds [2] Bleaching person 33°C 3 minutes 30 seconds 3] Water washing treatment
25-30℃ 3 minutes [4] Drying 75-80℃ approximately 2 minutes Processing solution composition (color developing tank solution) Benzyl alcohol 15n+6 ethylene glycol 15mj! potassium sulfite,
2.0g potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0 g hydroxylamine sulfate 3.
0g polyphosphoric acid (TPPS) 2.5g
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate
5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative)
1.0g potassium hydroxide 2.
Add 0 g of water to bring the total volume to 12, and adjust the pH to 10.20.

(Bleach-fixing tank solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70%
Solution) 100'mj! Ammonium sulfite (40% solution) 27.5 m6 Potassium carbonate or glacial acetic acid to pH 7.1
Adjust to 11 and add water to bring the total volume to 11.

Example-4 The same sample as in Example-1 was prepared, except that the exemplified compound used in Example-1 was changed to the exemplified compound shown in Table-4, and the same pressure test as in Example-1 was conducted. The results obtained are shown in Table-4.

As can be seen from Table 4, it can be seen that the present invention provides high sensitivity and also improves pressure capri and pressure desensitization.

Example-5 The same sample as in Example-2 was prepared, except that the exemplified compound used in Example-2 was changed to the exemplified compound shown in Table-5, and the same pressure test as in Example-2 was conducted. The results obtained are shown in Table-5.

As can be seen from Table 5, the present invention provides high sensitivity and also improves pressure fog and pressure desensitization.

Example-6 The same sample as in Example-3 was prepared, except that the exemplified compound used in Example-3 was changed to the exemplified compound shown in Table-6, and the same pressure test as in Example-3 was conducted. The results obtained are shown in Table-6.

As can be seen from Table 6, the present invention provides high sensitivity and also improves pressure blur and pressure desensitization.

Claims (1)

[Claims] The aspect ratio is 3:1 or more, and mainly (111
) A photographic element having a silver halide emulsion layer containing tabular grains consisting of planes, the photographic element further having a five-membered heterocyclic nucleus having nitrogen atoms and tellurium atoms as layer constituent atoms with a carbon atom in between. A photographic element characterized by containing.